JP2009012366A - Laminate and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate, suitable to microwiring, which can be suitably used for the manufacture of various kinds of printed wiring boards, allowing a metallic layer to be formed fixedly even on the surface, of the laminate, whose surface roughness is inconspicuous, and revealing excellent microwiring moldability, and especially, can be suitably used for printed wiring requiring a microwiring pattern. <P>SOLUTION: The laminate features the following characteristics: at least, one surface of a composite (a) of a fiber and a resin, has a resin layer (b) for forming a metal-plated layer, and the resin layer (b) contains (A) a resin composition component and (B) a filler component as essential components. In addition, the surface roughness of the resin layer (b) is not more than 0.4 um in terms of arithmetic mean roughness Ra as measured at a cut-off value of 0.002 mm. Besides, the specific surface area of the filler (B) is in 20-600 m<SP>2</SP>/g, and the elastic modulus of the resin layer (b) at 20°C, is 2.3-15 GPa. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminate and a printed wiring board excellent in fine wiring formability.

  Conventionally, as copper-clad laminates used as printed wiring board materials, so-called glass epoxy substrates in which glass woven fabric is impregnated with epoxy resin, or so-called BT substrates in which glass woven fabric is impregnated with bismaleimide / triazine resin and copper One obtained by thermocompression bonding with a foil is known. The copper foil used as the copper coating layer formed on the surface of the insulator in this type of copper clad laminate is a so-called electrolytic copper foil. Generally, the thickness is 35 μm and 18 μm. With the development of fine wiring of printed wiring boards, development of copper-clad laminates using very thin electrolytic copper foils such as 9 μm thick foils has recently been used.

  When wiring is formed using such a copper-clad laminate, it is obtained by a so-called subtractive method in which wiring is formed by dissolving and removing copper foil other than the wiring portion by etching. However, since the surface roughness of the electrolytic copper foil is large and the unevenness thereof has digged into the resin of the substrate, the copper in the recesses cannot be removed unless it is sufficiently etched, so that the wiring is formed thinner than the design. On the other hand, if etching is not performed sufficiently, there is a problem that copper remains in the recess. As described above, unless the unevenness on the surface of the insulating layer is made as small as possible, the circuit shape, circuit width, circuit thickness, and the like cannot be satisfactorily formed as designed. Therefore, in order to form fine wiring, it is important that the surface of the resin forming the wiring is smooth.

In response to such a problem, a laminate using at least one surface of a plating material using a polyimide resin having a specific structure has been created (for example, see Patent Documents 1 and 2). This prepreg material has an advantage that it is excellent in fine wiring formability because a copper layer can be firmly formed on a smooth surface. However, it has been found that not all chemicals can be used in the plating process. A laminate using a smooth surface plating material may be affected by the bath load of the plating solution, the build bath condition of the plating solution, and the like. For example, when an electroless plating film is formed on the plating material using a solution that has been aged for a certain period of time by using a plating chemical solution, the electroless plating film may swell. On the other hand, in the adhesion improving method using the anchor effect, the particle size of the filler to be used is large, and there is a limit to the formation of fine wiring, and since the inorganic filler is mixed with the resin, the elastic modulus is increased. Therefore, as a resin composition, it becomes difficult to relieve the stress of the electroless plating film, and the electroless plating film tends to swell. The anchor effect cannot be expected so much by the technique of roughening the fine wiring to such an extent that the fine wiring formability is not excluded, and since the elastic modulus of the resin composition is high, it is difficult to relieve the stress of the electroless plating film. It was very difficult to firmly adhere the electrolytic plating film without swelling.
JP 2006-183132 A JP 2006-138014 A

  Accordingly, the present invention has been made to solve the above-described conventional problems, and improves the adhesion between the electroless plating and various materials, and prevents swelling after the electroless plating and the heat resistance test. The object is to provide a laminate having at least one electroless plating material that is not generated.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by the following laminate. That is, the present invention includes the following inventions.

(1) A laminate having a resin layer (b) for forming a metal plating layer on at least one surface of a composite of fiber and resin (a), wherein the resin layer (b) is (A) The resin composition component and the (B) filler component are contained as essential components, and the surface roughness of the resin layer (b) is 0.4 um or less in arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. B) A laminate in which the specific surface area of the filler is 20 m ² / g or more and 600 m ² / g or less, and the elastic modulus at 20 ° C. of the resin layer (b) is 2.3 GPa or more and 15 GPa or less. .

  (2) The laminate according to (1), wherein the filler component (B) is contained in an amount of 20% to 90% by weight in the total solid content of the resin layer (b).

  (3) The laminate according to any one of (1) to (2), wherein the filler component (B) contains an inorganic filler.

  (4) (B) The filler component contains at least one selected from the group consisting of finely divided silica and fumed silica, as described in any one of (1) to (3) Laminated body.

  (5) The laminate according to any one of (1) to (4), wherein the (B) filler component contains fumed silica.

  (6) (A) The resin composition component is a resin composition component containing a resin having one or more structures among the structures represented by any one of the following general formulas (1) to (6). The laminate according to any one of (1) to (5), wherein

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3 to 10, n = 3 to 100, and m is an integer of 1 to 200).

  (7) In any one of (1) to (6), the resin composition component (A) is a resin composition component containing a resin having a structure of the following general formula (6) The laminated body of description.

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3 to 10, n = 3 to 100, and m is an integer of 1 to 200).

  (8) (A) The resin composition component is a polyimide resin having one or more structures among the structures represented by any of the following general formulas (1) to (6), or the following general formula (1) (1) to (7), which is a resin composition component containing at least one of polyamideimide resins having one or more structures among the structures represented by any one of (6) to (6) The laminated body as described in any one of these.

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. And each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, where x = 3 to 10, and m is an integer of 1 to 200.

  (9) Any one of (1) to (8), wherein the resin composition component (A) is a resin composition component containing a polyimide resin having the structure of the following general formula (6). The laminated body as described in.

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3 to 10, n = 3 to 100, and m is an integer of 1 to 200).

  (10) The laminate according to any one of (1) to (9), wherein the resin composition component (A) is a resin composition component containing a thermosetting component.

  (11) The laminate according to (10), wherein the thermosetting component is an epoxy resin.

  (12) The laminated body according to any one of (1) to (11), wherein the composite (a) of the fiber and the resin is a B stage.

  (13) The laminated body according to any one of claims 1 to 11, wherein the composite (a) of the fiber and the resin is a C stage.

  (14) A laminate in which an electroless plating film is formed on the surface of the laminate according to any one of (1) to (13).

  (15) The laminate according to (14), wherein the electroless plating film is an electroless copper plating film.

  (16) A printed wiring board using the laminate according to any one of (1) to (15).

  The laminate of the present invention has a resin layer (b) for forming a metal plating layer on at least one surface of a composite of fiber and resin (a), and the resin layer (b) is (A) resin. An aged plating chemical solution that contains a composition component and (B) filler component as essential components and controls the elastic modulus within a specific range, but does not hinder the formation of fine wiring, despite the very fine surface roughness. It is possible to firmly bond the electroless plating film without swelling even if a plating chemical solution in any state such as. Moreover, the laminated body of this invention is excellent also in adhesiveness with other various materials. Moreover, since the laminated body of this invention contains the (B) filler component in the resin layer for forming a metal plating layer, it is excellent in heat resistance, and also shows low thermal expansibility.

    One embodiment of the present invention will be described in detail below, but the present invention is not limited to the following description.

(Configuration of Laminate and Printed Wiring Board of the Present Invention)
The laminate of the present invention has a resin layer (b) for forming a metal plating layer on at least one surface of a composite of fiber and resin (a), and the resin layer (b) is (A) resin. The composition component and the (B) filler component are contained as essential components, and the surface roughness of the resin layer (b) is 0.4 um or less in arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. ) The specific surface area of the filler is 20 m ² / g or more and 600 m ² / g or less, and the elastic modulus of the resin layer (b) at 20 ° C. is 2.3 GPa or more and 15 GPa or less. The structure may be (a) / (b), (b) / (a) / (b), (a) / resin layer (c) / (b), or (a ) / Resin layer (c) / polymer film / (b), or any structure as long as it includes (a) and (b). As a printed wiring board using the laminated body of the present invention, for example, a single-sided or double-sided printed wiring board can be obtained by performing wiring formation on the laminated body of the present invention. Also, a build-up wiring board can be obtained using the single-sided or double-sided printed wiring board as a core substrate. Furthermore, it is also possible to obtain a buildup wiring board by using the laminate of the present invention as a buildup material. Since the laminate of the present invention is excellent in fine wiring formability, it can be preferably applied to other various high-density printed wiring boards. The composite (a) of fiber and resin, which is one of the components of the laminate of the present invention, may be a B stage or a C stage. The resin layer (b) for forming a metal plating layer, which is a constituent of the above laminate, preferably contains a polyimide resin having a siloxane structure from the viewpoint of adhesion to the metal plating layer. The laminate may have any structure, and a metal plating layer may be formed on the resin layer (b).

(Composite of fiber and resin (a))
The fiber and resin composite (a) of the present invention can be any combination of fibers and resins. For example, the resin may be a resin composed of only a thermoplastic resin, or a thermosetting component. It may be a resin composed of only a resin, or may be a resin composed of a thermoplastic resin and a thermosetting component. Among these, in order to obtain a composite (a) of B-stage or C-stage fibers and resin, the resin used for the composite (a) of the present invention preferably contains a thermosetting component.

  Here, the B stage is also referred to as a semi-cured state, and is an intermediate stage of the reaction of the thermosetting component used in the composite of fiber and resin (a), and (a) is softened by heating. However, even if it contacts with a certain kind of liquid, it does not melt or dissolve completely. Therefore, when the composite of fiber and resin (a) is a B stage, the laminate of the present invention is softened by heat processing and can embed an inner layer circuit, and therefore preferably used as a build-up material. Can do. The C stage is a stage in which the thermosetting component used in the composite of fiber and resin (a) is substantially cured and insoluble and infusible. Therefore, when the composite (a) of fiber and resin is a C stage, a printed wiring board can be obtained by forming a metal layer as it is and patterning it.

  The fiber is not particularly limited, but it is preferably at least one selected from paper, glass woven fabric, glass non-woven fabric, aramid woven fabric, aramid non-woven fabric, and polytetrafluoroethylene in consideration of the use of a printed wiring board. . As the paper, paper made from pulp such as paper pulp, dissolving pulp, synthetic pulp and the like prepared from raw materials such as wood, bark, cotton, hemp and synthetic resin can be used. As the glass woven fabric and the glass nonwoven fabric, a glass woven fabric or glass nonwoven fabric made of E glass or D glass and other glass can be used. As the aramid woven fabric and the aramid nonwoven fabric, a nonwoven fabric made of aromatic polyamide or aromatic polyamideimide can be used. Here, the aromatic polyamide is a conventionally known meta-type aromatic polyamide, para-type aromatic polyamide, or a copolymerized aromatic polyamide thereof. As polytetrafluoroethylene, polytetrafluoroethylene having a fine continuous porous structure that has been stretched can be preferably used.

  Next, the resin of the composite of fiber and resin (a) used in the present invention will be described. There is no restriction | limiting in particular as resin, Resin consisting only of a thermoplastic resin may be sufficient as resin which consists only of a thermosetting component, and resin consisting of a thermoplastic resin and a thermosetting component It may be. Examples of the thermoplastic resin include polysulfone resin, polyether sulfone resin, thermoplastic polyimide resin, polyphenylene ether resin, polyolefin resin, polycarbonate resin, and polyester resin. Thermosetting components include epoxy resins, thermosetting polyimide resins, cyanate ester resins, hydrosilyl cured resins, bismaleimide resins, bisallyl nadiimide resins, acrylic resins, methacrylic resins, allyl resins, unsaturated polyester resins. , Etc. Moreover, you may use together said thermoplastic resin and a thermosetting component.

  The composite (a) of the fiber and resin of the present invention has an advantage that low thermal expansion is obtained because of the presence of the fiber. From the viewpoint of obtaining further low thermal expansion, various organic and inorganic fillers are used. It may be added.

  The fiber / resin composite (a) of the present invention is obtained by dissolving the above-described resin in an appropriate solvent to obtain a resin solution, impregnating the above-described fiber, and further drying by heating. Here, the heat drying may be stopped at the B stage, or the heat drying may be further advanced to the C stage.

  The thickness of the composite (a) of the fiber and resin of the present invention is not particularly limited, but when the laminate of the present invention is applied to a high-density printed wiring board, it is preferably thinner, specifically 2 mm or less. Preferably, it is 1 mm or less. In addition, when using the laminate of the present invention as a build-up material, it is preferably as thin as possible from the viewpoint of thinning the resulting build-up wiring board, and has a resin component sufficient to embed the inner layer circuit sufficiently. Is preferred. At present, the thinnest glass woven fabric is said to be 40 μm. By using such a glass fiber, the composite (a) of the fiber and the resin of the present invention can be thinned. In addition, if a fiber such as a thinner glass woven fabric is obtained as a result of technological advancement, it is possible to further reduce the thickness of the composite (a) of the fiber and resin of the present invention by using such a fiber. Become.

(Resin layer (b) for forming a metal plating layer)
The resin layer (b) for forming a metal plating layer in the present invention can form a metal plating layer firmly on its smooth surface, and also adheres firmly to the composite of fiber and resin (a). A resin layer that can be used. That is, it can be said that it is a resin layer having the function of an adhesive formed between the composite of fiber and resin (a) and the metal plating layer.

  In the present invention, the surface roughness of the resin layer (b) for forming the metal plating layer (this surface may be referred to as “surface a” in the following description) has a cutoff value of 0.002 mm. The arithmetic roughness Ra measured in (1) is 0.4 μm or less, and the elastic modulus at 20 ° C. of the resin layer (b) is 2.3 GPa or more and 15 GPa or less.

(Surface roughness)
The surface a according to the present invention will be described. The surface a refers to a surface having a thickness of 10 mm or more. The surface a according to the present invention has an arithmetic average roughness Ra measured at a cutoff value of 0.002 mm and is 0.4 μm or less. When this condition is satisfied, it has good fine wiring formability. Arithmetic mean roughness Ra is defined in JIS B 0601 (revised on February 1, 1994). In particular, the numerical value of the arithmetic average roughness Ra of the present invention is a numerical value obtained by observing the surface with an optical interference type surface structure analyzer. The cutoff value of the present invention is described in the above JIS B 0601, and indicates a wavelength set when a roughness curve is obtained from a cross-sectional curve (measured data). That is, the value Ra measured with a cut-off value of 0.002 mm is an arithmetic average roughness calculated from a roughness curve obtained by removing irregularities having a wavelength longer than 0.002 mm from measured data. The surface roughness of the surface a of the present invention is an arithmetic average measured at a cutoff value of 0.002 mm in consideration of the balance of conflicting properties of coexistence of adhesion with the electroless plating film and fine wiring formability. The roughness Ra is preferably in the range of 0.005 μm to 0.4 μm, and particularly preferably in the range of 0.01 μm to 0.3 μm.

(Elastic modulus)
The elastic modulus according to the present invention will be described.
The elastic modulus of the resin layer (b) according to the present invention is confirmed as follows. That is, a 25 μm thick single layer sheet of the resin layer (b) having the surface a is prepared, and the elastic modulus is measured using the sheet. Specifically, the resin solution for forming the electroless plating material of the present invention is prepared, and the thickness after drying on the shine surface of a rolled copper foil (BHY-22BT, manufactured by Japan Energy) is 25 μm. The sheet is casted and dried, and the volatile matter is sufficiently removed to obtain a sheet. The rolled copper foil is removed by etching with a hydrochloric acid / ferric chloride-based etchant and dried at 60 ° C./30 minutes to obtain a 25 μm-thick single layer sheet having a surface a. The elastic modulus at 20 ° C. can be obtained by measuring the elastic modulus of the sheet under the following conditions.
Measuring device: DMS6100 (manufactured by SII Nanotechnology)
Temperature range: 10 ° C to 300 ° C
Rate of temperature increase: 3 ° C./min Measurement direction of sheet: measured in the direction of 45 degrees from the orientation angle The elastic modulus of the resin layer (b) of the present invention is the specific surface area of (B) filler component, the mixing amount, the type, Further, it can be controlled by the mixing amount, type, etc. of the (A) resin composition, and in particular, it is easy to control by the specific surface area of the (B) filler component and the mixing amount, which is preferable. . In addition, it exists in the tendency for an elasticity modulus to become high, so that the specific surface area of (B) filler component is large and there are many mixing amounts.

  Here, when the elastic modulus of the resin layer (b) of the present invention is higher than 15 GPa, the adhesiveness with the electroless plating film is lowered, and the electroless plating film is liable to swell. This is because the resin layer (b) is hard and lacks in tenacity and cannot relieve the stress of the electroless plating film.

  In addition, the elastic modulus of the electroless plating material is lower than 2.3 GPa because (B) the specific surface area of the filler component is small and the amount of mixing is small. Since it cannot be formed, the electroless plating film tends to swell.

  The resin layer (b) on at least one surface of the laminate of the present invention may be in any form as long as it has at least the surface a for performing electroless plating, but the material to be subjected to electroless plating A method in which the electroless plating material of the present invention is first formed on the surface and then electroless plating is preferably used. As a result, the material for electroless plating of the present invention plays the role of an interlayer adhesive, making use of the advantage that the electroless plating and the material are firmly bonded, and is applicable to various decorative plating applications and functional plating applications. Is possible. Among these, the electroless plating solution can be suitably used as an electroless plating material for a printed wiring board by taking advantage of the ability to form an electroless plating film firmly without selecting an electroless plating solution.

((A) Resin composition component)
The (A) resin composition component concerning this invention is demonstrated. Although there is no limitation in particular as (A) resin composition component concerning this invention, From a viewpoint of adhesiveness with an electroless-plating film, among the structures represented by either of General formula (1)-(6) A resin composition containing a resin having one or more structures is preferable.

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3 to 10, n = 3 to 100, and m is an integer of 1 to 200).

  Moreover, considering not only adhesion with the electroless plating film but also a balance of characteristics such as heat resistance, one or more structures among the structures represented by any one of the general formulas (1) to (6) are included. More preferably, it is a resin composition containing at least either a polyimide resin or a polyamideimide resin. Below, a polyimide resin and a polyamideimide resin are demonstrated.

(Polyimide resin)
First, a polyimide resin having one or more structures among the structures represented by any one of the general formulas (1) to (6) will be described. Of the structures represented by any one of the above general formulas (1) to (6), the polyimide resin having one or more structures is represented by any one of the above general formulas (1) to (6). Any polyimide resin may be used as long as it has one or more structures. For example, in the structure represented by any one of the general formulas (1) to (6), the acid dianhydride component having one or more structures or the general formulas (1) to (6) Among the structures represented, a diamine component having one or more structures is used to produce a polyamic acid that is a precursor of a polyimide resin, and a method of imidizing this to produce a polyimide resin, an acid having a functional group A polyamic acid having a functional group is produced by using a dianhydride component or a diamine component having a functional group, and the functional group capable of reacting with the functional group and any one of the general formulas (1) to (6). A polyamic acid in which one or more structures are introduced among the structures represented by any one of (1) to (6) is produced by reacting a compound having one or more structures And imidize this to polyimide A method for producing a fat, an acid dianhydride component having a functional group or a diamine component having a functional group is used to produce a polyamic acid having a functional group, and this is imidized to produce a polyimide having a functional group. A compound having one or more structures among the functional group capable of reacting with the functional group and the structure represented by any one of the general formulas (1) to (6) is reacted, and (1) to (6 ), A method for producing a polyimide resin in which one or more structures are introduced, and the like. Here, among the structures represented by any one of the general formulas (1) to (6), a diamine having one or more structures can be obtained relatively easily. A target polyimide resin is produced by reacting an acid dianhydride component with a diamine component having one or more structures among the structures represented by any of the general formulas (1) to (6). It is preferable.

  Next, as the polyimide resin of the present invention, an acid dianhydride component and a diamine component having one or more structures among the structures represented by any of the general formulas (1) to (6) are used. An example of manufacturing in the case of such a case will be described.

  The acid dianhydride component is not particularly limited, and pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetra Carboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 3, 3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propanic acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, p-phenylenediphthalic anhydride Such Aromatic tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidenediphthalic anhydride, 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalate Acid anhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4′-hydroquinonebis (phthalic anhydride), 2,2-bis (4-hydroxyphenyl) ) Propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride) And the like. These may be used alone or in combination of two or more.

  Subsequently, the diamine component will be described. In the present invention, the diamine component preferably includes a diamine component having one or more structures among the structures represented by the following general formulas (1) to (6).

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3 to 10, n = 3 to 100, and m is an integer of 1 to 200).

  Examples of the diamine having the structure represented by the general formula (1) include hexamethylene diamine and octamethylene diamine. Examples of the diamine having the structure represented by the general formula (2) include 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, and 1,5-bis (4 -Aminophenoxy) pentane and the like. Examples of the diamine having the structure represented by the general formula (3) include Elastomer 1000P, Elastomer 650P, and Elastomer 250P (manufactured by Ihara Chemical Industry Co., Ltd.). Further, examples of the diamine having the structure represented by the general formula (4) include polyether polyamines and polyoxyalkylene polyamines, such as Jeffamine D-2000 and Jeffamine D-4000 (Huntsman Corporation). Etc.). Furthermore, as the diamine having the structure represented by the general formula (6), 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3 , 3, -tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,3,3-Tetraphenyl-1,3-bis (2-aminophenyl) disiloxane, 1,1,3,3, -tetraphenyl-1,3-bis (3-aminopropyl) disiloxane 1,1,5,5, -tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5, -tetraphenyl-3,3-dimethoxy -1,5-bis (3-aminobutyl) trisiloxy Sun 1,1,5,5, -tetraphenyl-3,3-dimethoxy-1,5-bis (3-aminopentyl) trisiloxane, 1,1,3,3, -tetramethyl-1,3- Bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3, -tetramethyl-1, 3-bis (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,5,5, -tetramethyl- 3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane Siloxane, 1,1,5,5-tetramethyl-3,3-dimeth Xyl-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3 3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane , Etc. Further, as relatively easily available diamines having a structure represented by the general formula (6), KF-8010, X-22-161A, X-22-161B, X-22-manufactured by Shin-Etsu Chemical Co., Ltd. 1660B-3, KF-8008, KF-8012, X-22-9362, and the like. The diamine having the structure represented by the general formulas (1) to (6) may be used alone or in combination of two or more.

  For the purpose of improving the heat resistance of the surface a, among the structures represented by the general formulas (1) to (6), it is also preferable to use a diamine having one or more structures in combination with another diamine. Used. As the other diamine component, any diamine can be used, and m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-amino). Phenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, Bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3, 3'-diaminodiphenylmethane, 3,4'-di Minodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (Aminophenoxy) phenyl] sulfoxide, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 3,4′-diamino Diphenylthioether, 3,3'-diaminodiphenylthioether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfur 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 4, 4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) ) Phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenyl) Enoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) benzene, 4, 4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3- Minophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-Aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] ben Phenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4 -Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′- Examples thereof include dihydroxy-4,4′-diaminobiphenyl.

  Here, from the viewpoint of easy availability of raw materials and adhesion with the electroless plating film, among the diamines having one or more structures among the structures represented by the general formulas (1) to (6), the following It is preferable that the diamine which has a structure represented by General formula (6) is contained.

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. And each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, where x = 3 to 10, and m is an integer of 1 to 200.

  Among the structures represented by the general formulas (1) to (6), the diamine having one or more structures is preferably 2 to 100 mol%, more preferably 5 to 100 mol%, based on the total diamine component. It is. When the diamine having one or more structures among the structures represented by the general formulas (1) to (6) is less than 2 mol% with respect to the total diamine component, the surface a and the electroless plating film Adhesive strength may be lowered.

  The polyimide is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid. The polyamic acid is obtained by reacting an acid dianhydride component and a diamine component in substantially equimolar amounts.

  A typical procedure for the reaction is a method in which one or more diamine components are dissolved or dispersed in an organic polar solvent, and then one or more acid dianhydride components are added to obtain a polyamic acid solution. The order of addition of each monomer is not particularly limited, and the acid dianhydride component may be added to the organic polar solvent in advance, and the diamine component may be added to form a polyamic acid polymer solution, or the diamine component may be added to the organic polar solvent. A suitable amount of the acid dianhydride component may be added first, and then an excess amount of the dianhydride component may be added, and a diamine component corresponding to the excess amount may be added to form a polyamic acid polymer solution. There are various other addition methods known to those skilled in the art. Specifically, the following method is mentioned.

As used herein, “dissolution” refers to the case where the solute is uniformly dispersed in the solvent and substantially dissolved in addition to the case where the solvent completely dissolves the solute. Including. The reaction time and reaction temperature are not particularly limited.
1) A method in which a diamine component is dissolved in an organic polar solvent, and this is reacted with a substantially equimolar acid dianhydride component for polymerization.
2) An acid dianhydride component and a small molar amount of the diamine component are reacted with each other in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using a diamine component so that an acid dianhydride component and a diamine component may become substantially equimolar in all the processes.
3) The acid dianhydride component is reacted with an excess molar amount of the diamine component in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after the diamine component is additionally added, polymerization is performed using the acid dianhydride component so that the acid dianhydride component and the diamine component are substantially equimolar in all steps.
4) A method in which an acid dianhydride component is dissolved in an organic polar solvent and then polymerized using a diamine compound component so as to be substantially equimolar.
5) A method of polymerizing by reacting a substantially equimolar mixture of an acid dianhydride component and a diamine component in an organic polar solvent.

  Examples of the organic polar solvent used for the polyamic acid polymerization reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N- Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, Examples thereof include phenol solvents such as halogenated phenols and catechols, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  The polyamic acid solution obtained by the above method is dehydrated and cyclized by a thermal or chemical method to obtain a polyimide, and a thermal method in which the polyamic acid solution is subjected to heat treatment for dehydration, a chemical method for dehydration using a dehydrating agent. Any of these can be used. Moreover, the method of imidating by heating under reduced pressure can also be used. Each method will be described below.

  As a method of thermally dehydrating and cyclizing, a method of evaporating the solvent at the same time that the polyamic acid solution is subjected to an imidation reaction by heat treatment can be exemplified. By this method, a solid polyimide resin can be obtained. The heating conditions are not particularly limited, but it is preferably performed at a temperature of 200 ° C. or lower for a time range of 1 second to 200 minutes.

  Further, as a method of chemically dehydrating and cyclizing, a method of causing a dehydration reaction by adding a dehydrating agent and a catalyst having a stoichiometric amount or more to the polyamic acid solution and evaporating the organic solvent can be exemplified. Thereby, a solid polyimide resin can be obtained. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic rings such as pyridine, α-picoline, β-picoline, γ-picoline, and isoquinoline. And tertiary amines of the formula. The conditions for chemically dehydrating and cyclizing are preferably 100 ° C. or less, and the organic solvent is preferably evaporated at a temperature of 200 ° C. or less for a period of about 5 minutes to 120 minutes.

  Further, as another method for obtaining a polyimide resin, there is a method in which the solvent is not evaporated in the thermal or chemical dehydration ring closure method. Specifically, a polyimide solution obtained by performing a thermal imidization treatment or a chemical imidization treatment with a dehydrating agent is put into a poor solvent, a polyimide resin is precipitated, and unreacted monomers are removed and purified and dried. And obtaining a solid polyimide resin. As the poor solvent, a solvent that is well mixed with the solvent but is difficult to dissolve polyimide is selected. Illustrative examples include, but are not limited to, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, methyl ethyl ketone, and the like.

  Next, although it is the method of imidating by heating under reduced pressure, according to this imidization method, water generated by imidization can be actively removed out of the system, so that hydrolysis of polyamic acid is suppressed. And a high molecular weight polyimide is obtained. In addition, according to this method, one-sided or both-side ring-opened products existing as impurities in the raw acid dianhydride are closed again, so that a further improvement in molecular weight can be expected.

  The heating condition of the method of heating imidization under reduced pressure is preferably 80 to 400 ° C., more preferably 100 ° C. or more, more preferably 120 ° C. or more, in which imidization is efficiently performed and water is efficiently removed. is there. The maximum temperature is preferably equal to or lower than the thermal decomposition temperature of the target polyimide, and a normal imidization completion temperature, that is, about 150 to 350 ° C. is usually applied.

The conditions for pressure reduction are preferably smaller, but specifically, 9 × 10 ⁴ to 1 × 10 ² Pa, preferably 8 × 10 ⁴ to 1 × 10 ² Pa, more preferably 7 × 10 ⁴ to 1. × 10 ² Pa.

  Although the polyimide resin has been described above, a polyimide resin having one or more structures among the structures represented by any one of the above-described general formulas (1) to (6) may be used. As an example of the polyimide resin containing the said general formula (6) which can be used for the electroless-plating material of this invention and is comparatively easily available, X-22-8917, X-22- by Shin-Etsu Chemical Co., Ltd. 8904, X-22-8951, X-22-8756, X-22-8984, X-22-8985, and the like. These are polyimide solutions.

(Polyamideimide resin)
Next, the polyamideimide resin having one or more structures among the structures represented by any one of the general formulas (1) to (6) will be described.

  In the case of the polyamideimide resin, it can be synthesized by using tricarboxylic acid or a reactive derivative component thereof instead of the acid dianhydride in the case of the polyimide resin described above. Therefore, tricarboxylic acid or its reactive derivative component will be described below.

There is no limitation in particular as a tricarboxylic acid, Trimellitic acid, 3,3,4'-benzophenone tricarboxylic acid, 2,3,4'-diphenyltricarboxylic acid, 2,3,6-pyridinetricarboxylic acid, 3,4,4 '-Benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2-methoxy-3,4,4'-diphenyl ether tricarboxylic acid, 2'-chlorobenzanilide-3,4,4'-tricarboxylic acid, etc. Can be mentioned. The reactive derivative of tricarboxylic acid means an anhydride, halide, ester, amide, ammonium salt, or the like of the tricarboxylic acid. Examples of these include trimellitic anhydride, trimellitic acid monochloride, 1,4-dicarboxy-3-N, N-dimethylcarbamoylbenzene, 1,4-dicarbomethoxy-3-carboxybenzene, 1, 4-dicarboxy-3-carbophenoxybenzene, 2,6-dicarboxy-3-carbomethoxypyridine, 1,6-dicarboxy-5-carbamoylnaphthalene, ammonium comprising the above tricarboxylic acids and ammonia, dimethylamine, triethylamine, etc. Salt, and the like. Of these, trimellitic acid anhydride and trimellitic acid monochloride are preferable because they have good adhesion to the electroless plating film of the resulting polyamideimide resin, are easily available, and are inexpensive.
The said tricarboxylic acid or its reactive derivative may be used only by 1 type, and can also be used in combination of 2 or more type.
What is necessary is just to use the diamine component described with the above-mentioned polyimide resin for a diamine component.

  In the present invention, the polyamideimide is produced by an isocyanate method (for example, Japanese Patent Publication No. 44-19274), an acid chloride method (for example, Japanese Patent Publication No. 42-15637), or a direct polycondensation method (for example, Japanese Patent Publication No. 49-49). 4077) and melt polycondensation methods (for example, Japanese Examined Patent Publication No. 40-8910) can be obtained by polycondensation, but cost, raw material procurement is relatively easy, and high molecular weight is easily obtained. In view of obtaining a polymer and solubility of the obtained polymer in an organic solvent, the acid chloride method and the direct polycondensation method are preferably applied.

Hereinafter, the acid chloride method will be described.
Reacting substantially equivalent diamine component and tricarboxylic anhydride monochloride in a non-reactive polar organic solvent at -50 ° C to 100 ° C, preferably -20 ° C to 50 ° C for several minutes to several days. Thus, a polyamideimide precursor is obtained as an intermediate. At this time, an inorganic acid acceptor may be added during the reaction. Examples of the inorganic acid acceptor include tertiary amines such as triethylamine, tripropylamine, tributylamine, triamylamine, and pyridine, and 1,2-epoxides such as propylene oxide, styrene oxide, and cyclohexene oxide. Non-reactive organic solvents include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, cresol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like. , N-dimethylacetamide, N-methyl-2-pyrrolidone and diethylene glycol dimethyl ether are preferred, and diethylene glycol dimethyl ether, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are preferred. Next, in order to obtain polyamideimide from this polyamideimide precursor, a dehydration cyclization method may be used. The dehydration cyclization method includes (1) a method in which a polymer is once isolated and then cyclized by heat, (2) a method in which the polymer is cyclized by heat, and (3) a chemical dehydrating agent in the solution state. There is a method of cyclization.

  About (1), it is preferable to heat at a heating temperature of 100-400 degreeC. More specifically, the obtained reaction solution is compatible with the reaction solvent and poured into a large excess of a solvent that is a poor solvent for the resin, and the resin is isolated and then heated to 100 to 400 ° C. Alternatively, the obtained reaction solution is cast to a desired thickness, the solvent is evaporated to dryness, the resin is isolated in a file shape, and then heated to 100 to 400 ° C.

  The method (2) is carried out by heating the solution to 80 to 400 ° C, preferably 100 to 250 ° C. At this time, it is preferable to use a solvent azeotropically with water such as benzene, toluene and xylene.

  In the method (3), the reaction is carried out at 0 to 120 ° C, preferably 10 to 80 ° C in the presence of a chemical dehydrating agent. Examples of the chemical dehydrating agent include acid anhydrides such as acetic acid, propionic acid, butyric acid, and benzoic acid. At this time, it is preferable to use pyridine or the like as a substance that promotes the cyclization reaction. The chemical dehydrating agent is preferably used in an amount of 90 to 600 mol% based on the total amount of diamine. The substance that promotes the cyclization reaction is preferably used in an amount of 40 to 300 mol% based on the total amount of diamine.

Next, the direct polycondensation method will be described next.
Of substantially equivalent structures represented by any one of the general formulas (1) to (6), a diamine component containing a diamine having one or more structures, and a tricarboxylic acid or a reactive derivative thereof (however, an acid) (Except for halide derivatives) in a non-reactive polar organic solvent at 160 to 350 ° C., preferably 200 to 270 ° C.

  Examples of the dehydration catalyst include triphenyl phosphite, tricyclohexyl phosphite, phosphoric acid, triphenyl phosphite, phosphorus compounds such as phosphorus pentoxide, boric acid, boric anhydride, and the like. Non-reactive organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-caprolactam, cresol, xylenol, chlorophenol and the like. N-methyl-2-pyrrolidone is particularly preferable.

  The reaction solution obtained as described above is compatible with the above organic solvent such as lower alcohol such as methanol and water, and poured into a large excess of a solvent that is a poor solvent for the resin, The polyamideimide resin according to the present invention can be recovered by obtaining, filtering, and drying.

((B) filler component)
In the present invention, the filler component (B) is 0.4 μm or less in arithmetic average roughness Ra measured at a cut-off value of 0.002 mm on the surface a during pre-treatment before electroless plating, particularly desmear treatment. It is used as the main purpose of roughening.

  The filler component that can be used in the present invention is not particularly limited, and barium sulfate, barium titanate, finely divided silica, fumed silica, synthetic silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, hydroxide Examples thereof include inorganic fillers such as aluminum and mica powder, and organic fillers such as epoxy resins, phenol resins, benzoguanamine resins, polyimide resins, acrylic resins, and silicone resins.

As described above, in order to roughen the surface a to 0.4 μm or less with the arithmetic average roughness Ra measured at a cutoff value of 0.002 mm, the specific surface area of the filler component used is 20 g / m ² or more and 600 g / m. ² or less is preferable, and 25 g / m ² or more and 550 g / m ² or less is particularly preferable. When the specific surface area is less than 20 g / m ² , the surface roughness becomes too high and the fine wiring formability is impaired. On the other hand, if it is 600 g / m ² or more, the filler tends to agglomerate, the surface roughness becomes too large, and the fine wiring formability is impaired.

  In addition, the filler used in the present invention preferably has an average particle size of 0.3 μm or less in consideration of the fine wiring formability.

  In order to achieve the purpose of more uniformly roughening the roughened surface formed by the pretreatment of electroless plating, inorganic fillers are preferably used, among which finely divided silica, fumed silica, synthetic silica, More preferably, inorganic fillers such as finely divided silica and fumed silica are more preferably used, and fumed silica is particularly preferably used.

Specific examples of finely divided silica include UFP (manufactured by Denki Kagaku Kogyo, specific surface area of 30 to 80 m ² / g).

Examples of fumed silica include various grades of Aerosil (manufactured by Degussa) (specific surface area of 50 to 380 m ² / g), and the like.
Fumed silica is one of the preferred embodiments of the present invention from the viewpoint that the elastic modulus is controlled within a specific range and that it is suitable for fine wiring and has good adhesion to electroless plating. is there. Moreover, since fumed silica has excellent dispersibility, it has an advantage that a uniform roughened surface can be easily obtained.

  Similarly, in order to achieve the purpose of more uniformly roughening the roughened surface formed by the pretreatment of electroless plating, the filler component is contained in an amount of 5 to 90% by weight in the total solid content. The content is preferably 7 to 85% by weight. When the filler component is less than 5% by weight in the total solid content, the roughened surface formed by the pretreatment of electroless plating becomes non-uniform, and sufficient anchoring effect cannot be obtained, and the electroless plating film tends to swell. In addition, when the amount is more than 90% by weight, the filler is likely to aggregate and a uniform fine roughened surface cannot be obtained.

  The (B) filler component may be surface-treated for the purpose of (A) increasing the affinity with the resin composition, or for suppressing or controlling the aggregation of the filler component. Such a surface treatment method is not particularly limited, but may be carried out under known conditions using a known surface treating agent.

  Specific examples of the compound that can be used as the surface treatment agent include various coupling agents such as silane coupling agents and titanate coupling agents, fatty acids such as stearic acid, various surfactants, and various resins. Acid, various phosphate esters, and the like can be used.

As mentioned above, (A) resin composition component and (B) filler component used for the electroless plating material of the present invention have been described, but the electroless plating material of the present invention is (A) resin composition component. As a polyimide resin having a structure of the general formula (6), and (B) fumed silica having a specific surface area of 20 m ² / g or more and 600 m ² / g or less as a filler component in the total solid content, 5 wt% to 90 wt% contained suppresses the swelling of the electroless plating film, is excellent in adhesion to the electroless plating film, is excellent in heat resistance, and further has a fine wiring formability. It is preferable because it is excellent.

<Electroless plating>
The electroless plating according to the present invention will be described.
Examples of the electroless plating according to the present invention include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and direct plating. However, electroless copper plating and electroless nickel plating are preferable from the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, and electroless copper plating is particularly preferable.

As the electroless plating material of the present invention, a commercially available electroless copper plating chemical can be applied. In addition, when the electroless copper plating chemical solution after aging is used somewhat, the electroless copper plating film generally tends to swell, but if the electroless copper plating material of the present invention is used, the formation of fine wiring is possible. By using a filler that generates a surface roughness that does not hinder and having an elastic modulus within a specific range, the electroless plating film does not swell and exhibits good adhesion.
The degree of chemical solution aging can be determined by examining the specific gravity of the electroless copper plating chemical solution.

  Although there is no restriction | limiting in particular in the thickness of the electroless-plating film | membrane to form, From a viewpoint of productivity, 0.1-5 micrometers is preferable and 0.2-3 micrometers is more preferable.

(Laminate)
The laminate of the present invention is characterized by having a resin layer (b) for forming a metal plating layer on at least one side of a composite of fiber and resin (a). The structure may be (a) / (b), (b) / (a) / (b), (a) / resin layer (c) / (b), or (a ) / Resin layer (c) / polymer film / (b), or any structure as long as it includes (a) and (b).

  As a printed wiring board using the laminated body of the present invention, for example, a single-sided or double-sided printed wiring board can be obtained by performing wiring formation on the laminated body of the present invention. Also, a build-up wiring board can be obtained using the single-sided or double-sided printed wiring board as a core substrate. Furthermore, it is also possible to obtain a buildup wiring board by using the laminate of the present invention as a buildup material. Since the laminate of the present invention is excellent in fine wiring formability, it can be preferably applied to other various high-density printed wiring boards.

  The fiber and resin composite (a) of the present invention can be any combination of fibers and resins. For example, the resin may be a resin composed of only a thermoplastic resin, or a thermosetting component. It may be a resin composed of only a resin, or may be a resin composed of a thermoplastic resin and a thermosetting component. Among these, in order to obtain a composite (a) of B-stage or C-stage fibers and resin, the resin used for the composite (a) of the present invention preferably contains a thermosetting component. Here, the B stage is also referred to as a semi-cured state, and is an intermediate stage of the reaction of the thermosetting component used in the composite of fiber and resin (a), and (a) is softened by heating. However, even if it contacts with a certain kind of liquid, it does not melt or dissolve completely. Therefore, when the composite of fiber and resin (a) is a B stage, the laminate of the present invention is softened by heat processing and can embed an inner layer circuit, and therefore preferably used as a build-up material. Can do.

  The C stage is a stage in which the thermosetting component used in the composite of fiber and resin (a) is substantially cured and insoluble and infusible. Therefore, when the composite (a) of fiber and resin is a C stage, a printed wiring board can be obtained by forming a metal layer as it is and patterning it.

  The resin layer (b) for forming a metal plating layer, which is a constituent of the above laminate, preferably contains a polyimide resin having a siloxane structure from the viewpoint of adhesion to the metal plating layer.

  The laminated body may have any configuration, and a state in which a metal plating layer is formed on the resin layer (b).

  The laminate of the present invention can firmly form a metal plating layer on the smooth resin layer (b). Therefore, fine wiring can be formed as designed. Here, in order to have good fine wiring formability, the surface roughness of the resin layer (b) is preferably less than 0.5 μm in terms of arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. Arithmetic mean roughness Ra is defined in JIS B 0601 (revised on February 1, 1994). In particular, the numerical value of the arithmetic average roughness Ra of the present invention is a numerical value obtained by observing the surface with an optical interference type surface structure analyzer. The cutoff value of the present invention is described in the above JIS B 0601, and indicates a wavelength set when a roughness curve is obtained from a cross-sectional curve (measured data). That is, the value Ra measured with a cut-off value of 0.002 mm is an arithmetic average roughness calculated from a roughness curve obtained by removing irregularities having a wavelength longer than 0.002 mm from measured data.

  Although there is no restriction | limiting in particular in the thickness of the laminated body of this invention, When the application to a high density printed wiring board is considered, the thinner one is preferable. Specifically, it is preferably 2 mm or less, and more preferably 1 mm or less.

(Laminate manufacturing method)
Any method conceivable by those skilled in the art may be used as a method for producing the laminate of the present invention. Here, the manufacturing method is illustrated about the case where the composite (a) of the fiber and resin which is one of the structures of the laminated body of this invention is a B stage.

  A B-stage fiber / resin composite (a) obtained by impregnating a fiber with a resin solution in which a resin forming the fiber / resin composite (a) is dissolved in an appropriate solvent, and further drying by heating. A resin solution in which the resin forming the resin layer (b) is dissolved in an appropriate solvent is applied by a known method such as dipping, spray coating, spin coating, curtain coating, bar coating, and drying. Can do. At this time, it is essential to carry out the drying under conditions that maintain the B stage.

  Also, the resin layer (b) / B-stage fiber / resin composite (a) formed into a film is overlaid, hot press, vacuum press, laminate (heat laminate), vacuum laminate, hot roll laminate, It can be obtained by laminating and integrating by thermocompression bonding such as vacuum hot roll lamination. In this case as well, it is essential to carry out the lamination and integration under the condition that the B stage is maintained.

  Next, the manufacturing method is illustrated about the case where the composite (a) of the fiber and resin which is one of the structures of the laminated body of this invention is a C stage. A B-stage fiber / resin composite (a) obtained by impregnating a fiber with a resin solution in which a resin forming the fiber / resin composite (a) is dissolved in an appropriate solvent, and further drying by heating. A resin solution in which the resin forming the resin layer (b) is dissolved in an appropriate solvent is applied by a known method such as dipping, spray coating, spin coating, curtain coating, bar coating, and drying. Can do. At this time, it is essential to carry out the drying under conditions such that the curing proceeds to the C stage. In the above, a composite (a) of C-stage fibers and resin can be used in advance.

  Also, the resin layer (b) / B-stage fiber / resin composite (a) formed into a film is overlaid, hot press, vacuum press, laminate (heat laminate), vacuum laminate, hot roll laminate, It can be obtained by laminating and integrating by thermocompression bonding such as vacuum hot roll lamination. Also in this case, it is essential to carry out the lamination and integration under the condition that the curing proceeds to the C stage. In the above, a composite (a) of C-stage fibers and resin can be used in advance.

  In addition, the copper foil on both sides of a commercially available copper-clad laminate is removed by a method such as etching, and a resin layer (b) is formed thereon, so that the resin layer (b) / B stage fibers It is also possible to obtain a laminate comprising a composite (a) of a resin and a resin.

  The lamination integration will be described. At the time of lamination and integration, some interleaving paper is required for the film-like resin layer (b). For example, if the film is a film produced by casting and drying a resin solution on a support, For example, the support can be used as a slip sheet by laminating and integrating together with the support and then peeling the support. As the support, various resin films such as PET, and metal foils such as aluminum foil and copper foil can be used. As another method, it is also possible to peel the film from the support, superimpose it on the composite of fiber and resin (a), and laminate and integrate them using a fluororesin film or the like as interleaving paper. In any case, it is important that the interleaving paper can be peeled off from the resin layer (b), and is sufficiently smooth so as not to have irregularities that impair the formation of fine wiring. After stacking and integrating by thermocompression bonding according to the above method, heat treatment is performed using a hot air oven or the like for the purpose of improving the adhesive force at the interface between the resin layer (b) / fiber and resin composite (a). You can go.

  A laminate including the structure of metal plating layer / resin layer (b) / fiber / resin composite (a) is formed by forming a metal plating layer on the obtained laminate by electroless plating or the like. You can get a body. In order to adjust the thickness of the metal plating layer, after electroless plating, electrolytic plating may be further performed. In addition, applying an alkaline aqueous solution such as desmear treatment before electroless plating activates the surface of the resin layer (b) and leads to an improvement in the adhesion between the metal plating layer and the resin layer (b). Can be preferably implemented.

(Printed wiring board)
As a printed wiring board using the laminated body of the present invention, for example, a single-sided or double-sided printed wiring board can be obtained by performing wiring formation on the laminated body of the present invention. Also, a build-up wiring board can be obtained using the printed wiring board as a core substrate. Moreover, it is also possible to obtain a build-up wiring board using the laminate of the present invention as a build-up material. Since the laminate of the present invention is excellent in fine wiring formability, it can be preferably applied to other various high-density printed wiring boards.

  The manufacture example of the single-sided or double-sided printed wiring board using the laminated body which consists of the composite (a) of the fiber and resin of the resin layer (b) / C stage of this invention is shown.

(1) Form vias as necessary.
Known drill machines, dry plasma devices, carbon dioxide lasers, UV lasers, excimer lasers, etc. can be used, but UV-YAG lasers and excimer lasers are preferable for forming vias having a small diameter, particularly 50 μm or less, particularly preferably 30 μm. It is as follows. Further, a via having a good shape can be formed, which is preferable. Needless to say, panel plating by electroless plating may be performed after a through-hole is formed by a drill machine. Further, after drilling, desmearing can be performed by a known technique such as a wet process using permanganate or dry desmear such as plasma.

(2) Perform electroless plating.
Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and the like. From the viewpoint of electrical properties such as migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable.

(3) A plating resist is formed.
As the photosensitive plating resist, known materials widely available on the market can be used. In the method for producing a printed wiring board of the present invention, it is preferable to use a photosensitive plating resist having a resolution of 50 μm pitch or less in order to cope with fine wiring. Of course, a circuit having a pitch of 50 μm or less and a circuit having a pitch higher than that may be mixed in the wiring pitch of the printed wiring board of the present invention.

(4) Perform pattern plating by electrolytic copper plating.
By applying many known methods, electrolytic copper pattern plating is applied to the portion where the resist is not formed. Specific examples include electrolytic copper plating, electrolytic solder plating, electrolytic tin plating, electrolytic nickel plating, and electrolytic gold plating. From the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, electrolytic copper plating and electrolytic nickel plating are preferable, and electrolytic copper plating is particularly preferable.

(5) Strip resist.
For resist stripping, a material suitable for stripping the used plating resist can be used, and there is no particular limitation. For example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

(6) A wiring is formed by quick etching the electroless plating layer.
A known quick etchant can be used for the quick etching. For example, a sulfuric acid / hydrogen peroxide-based etchant, an ammonium persulfate-based etchant, a sodium persulfate-based etchant, a diluted ferric chloride-based etchant, a diluted cupric chloride-based etchant, or the like can be preferably used.

  The above method is a so-called semi-additive method applied to fine wiring formation, but the method can be preferably applied to the laminate of the present invention. On the other hand, since the laminated body of the present invention can form plated copper firmly on a smooth surface, a copper residue after etching does not occur in the concavo-convex portion of the resin, so a resist was formed. After that, a subtractive method in which unnecessary copper is removed by etching to form a wiring can be applied. While the subtractive method has the advantage of fewer steps, it includes problems such as poor wiring shape due to side etching. Therefore, the subtractive method and the semi-additive method may be selected in consideration of the wiring pitch to be formed, productivity, cost, and the like.

  It is also possible to produce a build-up wiring board using the printed wiring board produced as described above as a core substrate. In this case, since fine wiring can be formed on the core substrate itself, a higher-density build-up wiring board can be produced.

  Next, the manufacture example of the buildup wiring board which used the laminated body which consists of the composite (a) of the fiber and resin of a resin layer (b) / B stage as a buildup material is shown.

(1) Laminate with core substrate.
In order, the core substrate on which the interleaving paper, the laminate, and the wiring are formed is laminated with the fiber and resin composite (a) and the core substrate facing each other. In this step, it is important to sufficiently embed between the wiring patterns formed on the core substrate. The thermosetting component of the composite of fiber and resin (a) used in the laminate of the present invention is B. It is essential to be a stage. As the laminating method, various thermocompression bonding methods such as hot pressing, vacuum pressing, laminating (thermal laminating), vacuum laminating, hot roll laminating, and vacuum hot roll laminating can be performed. Among these, processing under vacuum, that is, vacuum press processing, vacuum laminating processing, and vacuum hot roll laminating processing can be preferably performed without voids between the circuits, and can be preferably performed. After the lamination, for the purpose of proceeding the curing to the C stage, it is also possible to perform heat drying using a hot air oven or the like.

(2) Form vias.
Known drill machines, dry plasma devices, carbon dioxide lasers, UV lasers, excimer lasers, etc. can be used, but UV-YAG lasers and excimer lasers are preferable for forming vias having a small diameter, particularly 50 μm or less, particularly preferably 30 μm. It is as follows. Further, a via having a good shape can be formed, which is preferable. Needless to say, panel plating by electroless plating may be performed after a through-hole is formed by a drill machine. Further, after drilling, desmearing can be performed by a known technique such as a wet process using permanganate or dry desmear such as plasma.

(3) Perform electroless plating.
Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and the like. From the viewpoint of electrical properties such as migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable.

(4) A plating resist is formed.
As the photosensitive plating resist, known materials widely available on the market can be used. In the method for producing a printed wiring board of the present invention, it is preferable to use a photosensitive plating resist having a resolution of 50 μm pitch or less in order to cope with fine wiring. Of course, a circuit having a pitch of 50 μm or less and a circuit having a pitch higher than that may be mixed in the wiring pitch of the printed wiring board of the present invention.

(5) Perform pattern plating by electrolytic plating.
Many known methods can be applied to the electrolytic plating. Specific examples include electrolytic copper plating, electrolytic solder plating, electrolytic tin plating, electrolytic nickel plating, and electrolytic gold plating. From the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, electrolytic copper plating and electrolytic nickel plating are preferable, and electrolytic copper plating is particularly preferable.

(6) Strip resist.
For resist stripping, a material suitable for stripping the used plating resist can be used, and there is no particular limitation. For example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

(7) A wiring is formed by quick etching the electroless plating layer.
A known quick etchant can be used for the quick etching. For example, a sulfuric acid / hydrogen peroxide-based etchant, an ammonium persulfate-based etchant, a sodium persulfate-based etchant, a diluted ferric chloride-based etchant, a diluted cupric chloride-based etchant, or the like can be preferably used.

  Thereafter, the laminate of the present invention is further laminated and integrated with the outermost layer of the obtained build-up wiring board, and a build-up having a desired number of layers is formed by forming the wiring by the steps (2) to (7) described above. A wiring board can be obtained.

  In addition, the resin layer (b) is obtained by laminating and integrating the interleaving paper, the film-like resin layer (b), the B-stage fiber-resin composite (a), and the core substrate on which the wiring is formed. / Before forming a laminate comprising a composite of fiber and resin (a) and simultaneously forming a resin layer (b) / composite of fiber and resin (a) / core substrate formed with wiring A method of obtaining a build-up wiring board is also preferably applicable.

  The present invention will be described more specifically based on examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. In addition, as a characteristic of the laminated body concerning this invention, adhesiveness with electroless-plated copper, surface roughness Ra, and wiring formation property were evaluated or calculated as follows.

[Adhesion evaluation]
On the resin layer (b) of the obtained laminate, desmear and electroless copper plating were performed under the conditions shown in Tables 1 and 2 below. Furthermore, electrolytic copper plating was performed so that the total copper thickness was 18 μm. Thereafter, after drying at 180 ° C. for 30 minutes, the adhesive strength after normal and pressure cooker tests (PCT) was measured according to JPCA-BU01-1998 (published by Japan Printed Circuit Industry Association).
Normal-state adhesive strength: Adhesive strength measured after standing for 24 hours in an atmosphere of 25 ° C. and 50%.
Adhesive strength after PCT: Adhesive strength measured after standing for 96 hours in an atmosphere of 121 ° C. and 100%.

[Surface roughness Ra measurement]
The electroless plated copper layer of the laminate with electroless copper plating obtained in the above-mentioned adhesive evaluation items was removed by etching, and the surface roughness Ra of the exposed surface was measured. The measurement measured the arithmetic mean roughness of the surface a on condition of the following using the light wave interference type surface roughness meter (NewView5030 system by ZYGO).
(Measurement condition)
Objective lens: 50x Mirau Image zoom: 2
FDA Res: Normal
Analysis conditions:
Remove: Cylinder
Filter: High Pass
Filter Low Wave: 0.002 mm.

[Elastic modulus]
The outermost layer A was formed into a sheet shape, and the elastic modulus at 20 ° C. was measured. In addition, it was confirmed that the measurement sheet was sufficiently dried and the volatile content was 1% or less. The measurement of volatile content was quantified by measuring the weight loss between 20 ° C. and 200 ° C. of the condition 20 ° C./min and temperature-Tg curve using a TGA (TGA-50, manufactured by Shimadzu Corporation) measuring device.
The specific method for producing the sheet is to first prepare a resin solution constituting the outermost layer A, and cast and apply the solution onto the shine surface of a rolled copper foil (BHY-22B-T, manufactured by Japan Energy). Heat drying at 60 ° C./5 minutes, 150 ° C./5 minutes, 180 ° C./60 minutes was performed in a hot air oven. Thereafter, the rolled copper foil was removed by etching with a hydrochloric acid / ferric chloride etchant and dried at 60 ° C./30 minutes to obtain a 25 μm thick sheet comprising the outermost layer A. The elastic modulus at 20 ° C. was obtained by measuring the elastic modulus of the sheet under the following conditions.
Measuring device: DMS6100 (manufactured by SII Nanotechnology)
Temperature range: 10 ° C to 300 ° C
Temperature increase rate: 3 ° C./min Measurement direction of sheet: Measured in a direction 45 degrees from the orientation angle.

[Reflow resistance]
A laminate comprising outermost layer A / outermost layer B / glass epoxy substrate / outermost layer B / outermost layer A is obtained, a copper layer is formed on the exposed outermost layer A, and a drying process is performed at 180 ° C. for 30 minutes. Was prepared in the same manner as in the adhesive evaluation, and the laminate was cut into 15 mm and 30 mm sizes and allowed to stand for 200 hours under conditions of a temperature of 30 ° C. and a humidity of 70% to obtain test pieces. The test piece was placed in an IR reflow furnace (trade name: FT-04, manufactured by CIS) under conditions set so that the maximum temperature reached 260 ° C., and a solder heat resistance test was performed. In addition, this test was repeated 3 times, the thing without a swelling was set as (circle) and the thing with a swelling was set as x.

[Fine wiring formability]
A laminate comprising outermost layer A / outermost layer B / glass epoxy substrate / outermost layer B / outermost layer A is obtained, a copper layer is formed on the exposed outermost layer A, and a drying process is performed at 180 ° C. for 30 minutes. A laminate was prepared in the same manner as the adhesive evaluation. The exposed outermost layer A is desmeared and electroless-plated, dried at 100 ° C / 30 minutes, and then processed in each step of dry film resist formation, electrolytic copper pattern plating, resist stripping, and quick etching. = A fine wiring of 10 μm / 10 μm was formed. The case where the fine wiring was not peeled off and was successfully formed as designed was rated as “◯”, and the case where the fine wiring was peeled off or was not able to be satisfactorily formed as designed was marked as “X”.

(Polyimide resin synthesis example 1)
In a glass flask with a volume of 2000 ml, 37 g (0.045 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd., 21 g (0.105 mol) of 4,4′-diaminodiphenyl ether, N, N-dimethylformamide (hereinafter, DMF) was added and dissolved while stirring, and 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added. The mixture was stirred for a time to obtain a DMF solution of polyamic acid having a solid content concentration of 30%. The polyamic acid solution was placed in a vat coated with a fluororesin and heated under reduced pressure at 665 Pa at 200 ° C. for 120 minutes in a vacuum oven to obtain polyimide resin 1.

  The chemical structure of KF-8010 is shown below.

(Where m = 3-12).

(Polyimide resin synthesis example 2)
In a glass flask with a capacity of 2000 ml, 62 g (0.075 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd., 15 g (0.075 mol) of 4,4′-diaminodiphenyl ether, and DMF are added and dissolved while stirring. 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred at 20 ° C. for about 1 hour. A DMF solution was obtained. The polyamic acid solution was placed in a vat coated with a fluororesin and heated under reduced pressure at 665 Pa at 200 ° C. for 120 minutes in a vacuum oven to obtain polyimide resin 2.

(Polyamideimide resin synthesis example 1)
In a glass flask having a volume of 2000 ml, 147.8 g (0.36 mol) of 2,2-bis (4-aminophenoxyphenyl) propane, 33.2 g (0.04 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd., propylene 34.8 g (0.6 mol) of oxide and 617 g of N, N-dimethylacetamide were weighed and dissolved by stirring. The solution was cooled to 0 ° C., and 84.2 g (0.4 mol) of trimellitic acid monochloride was added at this temperature. After stirring at room temperature for 3 hours, 200 g of acetic anhydride and 50 g of pyridine were added, and the mixture was stirred at 60 ° C. for 24 hours. The obtained solution was put into methanol to obtain a solid content. After drying the obtained solid content, the process which melt | dissolved in N, N- dimethylacetamide again, put this into methanol, and dried the obtained solid content was repeated 3 times, and the polyamideimide resin 3 was obtained.

(Formulation Example 1 of solution forming surface a)
In a ball mill, 10 g of polyimide resin 1, 10 g of filler (Aerosil R972, manufactured by Degussa; specific surface area 110 m ² / g) and 180 g of a mixed solvent of dioxolane and toluene (mixing ratio = 50 wt% / 50 wt%) The solution (A) which forms the surface a by mixing was obtained.

(Formulation example 2 of solution for forming surface a)
A solution (B) for forming the surface a was obtained in the same manner as in Preparation Example 1 except that the filler (Aerosil 380, manufactured by Degussa; specific surface area 380 m ² / g) was used.

(Formulation example 3 of solution for forming surface a)
Filler (UFP, Denki Kagaku Kogyo Co., Ltd .; specific surface area 80 m ² / g) except for using to obtain a solution (C) to form a surface a in the same manner as in Formulation Example 1.

(Formulation example 4 of solution for forming surface a)
A solution (D) for forming the surface a was obtained in the same manner as in Preparation Example 1 except that the filler (UFP, manufactured by Denki Kagaku Kogyo Co., Ltd .; specific surface area of 30 m ² / g) was used.

(Formulation example 5 of solution for forming surface a)
A solution (E) for forming the surface a was obtained in the same manner as in Preparation Example 1 except that 1.1 g of filler (Aerosil R972, manufactured by Degussa; specific surface area 110 m ² / g) was used.

(Formulation example 6 of solution for forming surface a)
A solution (F) for forming the surface a was obtained in the same manner as in Preparation Example 1 except that 23.3 g of filler (Aerosil R972, manufactured by Degussa; specific surface area 110 m ² / g) was used.

(Formulation example 7 of solution for forming surface a)
A solution (G) for forming the surface a was obtained in the same manner as in Preparation Example 1 except that 10 g of polyimide resin 2 was used.

(Formulation Example 8 of solution forming surface a)
A solution (H) for forming the surface a was obtained in the same manner as in Preparation Example 1, except that 10 g of polyamideimide resin 3 was used.

(Formulation Example 9 of solution for forming surface a)
10 g of polyimide resin 1, 10 g of filler (Aerosil R972, manufactured by Degussa; specific surface area 110 m ² / g), 0.54 g of epoxy resin (JER152, manufactured by Japan Epoxy Resins Co., Ltd.), melamine / cresol resin (PS-6492) , Manufactured by Gunei Chemical Co., Ltd.) 0.32 g, a mixed solvent of dioxolane and toluene (mixing ratio = 50% by weight / 50% by weight) is mixed with 180 g by a ball mill to form a surface a (I) Got.

(Formulation example 1 of adhesive layer solution)
Into a glass flask having a capacity of 2000 ml, 87.7 g (0.30 mol) of 1,3-bis (3-aminophenoxy) benzene and DMF were added and dissolved while stirring, and 4,4 ′-(4,4 78 g (0.15 mol) of '-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred at 20 ° C. for about 1 hour to obtain a DMF solution of polyamic acid having a solid content concentration of 30%. The polyamic acid solution was placed in a vat coated with a fluororesin and heated under reduced pressure at 180 ° C. for 120 minutes at 665 Pa in a vacuum oven to obtain polyimide oligomer 4.
12 g of dioxolane and 23 g of imide oligomer 4 were weighed and dissolved by heating at 60 ° C. After adding 5.2 g of toluene, the mixture was cooled while stirring, 15 g of epoxy resin (JER152, manufactured by Japan Epoxy Resin Co., Ltd.) was added, and the mixture was stirred and mixed to obtain a solution X.
18 g of dioxolane and 2 g of polyimide resin (ULTEM-1000-1000, manufactured by GE Plastics) were weighed and dissolved by heating at 60 ° C. with stirring. After cooling, 6 g of a filler (SFP-130MC phenylaminosilane-treated product, manufactured by Denki Kagaku Kogyo Co., Ltd.) was added, and 7.7 g of toluene was further added, followed by mill dispersion to obtain a Y solution.
5.52 g of solution X and 8.77 g of solution Y were weighed and mixed by stirring, and then filtered using a 40 μm-diameter filter to obtain a resin solution (J).

(Production Example 1 of non-thermoplastic polyimide film)
A 25 μm non-thermoplastic polyimide film was prepared and used as the polymer film. In a separable flask, 1 equivalent each of paraphenylenediamine (hereinafter referred to as PDA) and 4,4′-diaminodiphenyl ether (hereinafter referred to as ODA) was dissolved in DMF, and then p-phenylenebis (trimellitic acid monoester anhydride) (hereinafter referred to as TMHQ). ) 1 equivalent was added and stirred for 30 minutes. Thereafter, 0.9 equivalent of pyromellitic dianhydride (hereinafter PMDA) was added and stirred for 30 minutes. Next, a DMF solution of PMDA (concentration 7%) was added while paying attention to an increase in viscosity, and the viscosity at 23 ° C. was adjusted to 2000 to 3000 poises to obtain a DMF solution of a polyamic acid polymer. The amount of DMF used was such that the monomer charge concentration of the diamine component and tetracarboxylic dianhydride component was 18% by weight. Moreover, superposition | polymerization was performed at 40 degreeC. To 100 g of the above polyamic acid solution, 10 g of acetic anhydride and 10 g of isoquinoline are added and stirred uniformly, then defoamed, cast on a glass plate, dried at about 110 ° C. for about 5 minutes, and then polyamic acid. The coating film was peeled off from the glass plate to obtain a gel film having self-supporting properties. The gel film is fixed to a frame, then heated at about 200 ° C. for about 1 minute, about 300 ° C. for about 1 minute, about 400 ° C. for about 1 minute, about 500 ° C. for about 1 minute, dehydrated and ring-closed and dried, A non-thermoplastic polyimide film (K) having a thickness of about 25 μm was obtained. The thermal expansion coefficient of this film was 12 ppm. The obtained non-thermoplastic polyimide film had a surface roughness Ra of 0.01 μm.

[Example 1]
The resin solution (J) used for the composite of fiber and resin (a) is applied and impregnated on a 100 μm thick glass woven fabric, dried at a temperature of 160 ° C., and further dried at 170 ° C. for 90 minutes to obtain a resin component. A composite (a) of 45% by weight of C-stage fiber and resin was obtained. The solution (A) for forming the resin layer (b) on one side of the composite (a) is applied by spin coating, and further dried at 60 ° C. and 150 ° C. to obtain a resin layer (b) / C having a thickness of 5 μm. A laminate comprising stage (a) was obtained. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

[Example 2]
The resin solution (J) used for the composite of fiber and resin (a) is applied and impregnated on a 100 μm thick glass woven fabric, dried at a temperature of 160 ° C., and further dried at 170 ° C. for 90 minutes to obtain a resin component. A composite (a) of 45% by weight of C-stage fiber and resin was obtained. On the other hand, the solution (A) for forming the resin layer (b) was cast-coated on the surface of a support (trade name Lumirror T60 manufactured by Toray). Then, it heat-dried at the temperature of 60 degreeC with hot-air oven, and obtained the resin layer (b) film with a thickness of 2 micrometers. The film with the support was superposed on both sides of the fiber / resin composite (a) with the support, and vacuum press-laminated under conditions of 170 ° C., 1 MPa, 6 minutes. The resin layers (b) and (a) were laminated so as to be in contact with each other. Thereafter, the support was peeled off and dried at 170 ° C. for 90 minutes to obtain a laminate comprising resin layer (b) / C stage (a) / resin layer (b). Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 3
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (B) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 4
A laminate was obtained in the same manner as in Example 2 except that a 25 μm thick resin layer (b) film with a support obtained using the solution (C) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 5
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (D) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 6
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (E) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 4.

Example 7
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (F) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 4.

Example 8
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (G) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 4.

Example 9
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (H) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 4.

Example 10
A laminate was obtained in the same manner as in Example 2 except that the 25 μm thick resin layer (b) film with a support obtained using the solution (I) for forming the resin layer (b) was used. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 4.

Example 11
The resin solution (J) used for the composite of fiber and resin (a) is applied and impregnated on a 100 μm thick glass woven fabric, dried at a temperature of 160 ° C., and further dried at 170 ° C. for 90 minutes to obtain a resin component. A composite (a) of 45% by weight of C-stage fiber and resin was obtained. The solution (A) for forming the resin layer (b) on one side of the composite (a) is applied by spin coating, and further dried at 60 ° C. and 150 ° C. to obtain a resin layer (b) / C having a thickness of 5 μm. A laminate comprising stage (a) was obtained. Using this laminated body, it processed by the desmear and electroless-plating process shown in Table 2, and evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

[Comparative Example 1]
The resin solution (J) used for the composite of fiber and resin (a) is applied and impregnated on a 100 μm thick glass woven fabric, dried at a temperature of 160 ° C., and further dried at 170 ° C. for 90 minutes to obtain a resin component. A composite (a) of 45% by weight of C-stage fiber and resin was obtained. On the other hand, a solution obtained by dissolving the polyimide resin 1 in a dioxolane solution was cast on the surface of a support (trade name Lumirror T60 manufactured by Toray). Then, the film which heat-dried at the temperature of 60 degreeC with a hot-air oven, and formed the resin layer (b) with a thickness of 2 micrometers was obtained. The film with the support was superposed on both sides of the fiber / resin composite (a) with the support, and vacuum press-laminated under conditions of 170 ° C., 1 MPa, 6 minutes. The resin layers (b) and (a) were laminated so as to be in contact with each other. Thereafter, the support was peeled off and dried at 170 ° C. for 90 minutes to obtain a laminate comprising resin layer (b) / C stage (a) / resin layer (b). Using the obtained laminated body, it processed by the desmear and electroless plating process shown in Table 2, and evaluated according to the evaluation procedure of various evaluation items. As can be seen from Table 5, since the stress of the plating solution used was large, swelling occurred after electroless plating, and the adhesive strength and reflow resistance could not be evaluated. Moreover, although fine wiring property was confirmed in the location where the swelling did not generate | occur | produce, since the dry film resist peeled off, the fine wiring was not able to be formed favorably.

[Comparative Example 2]
The resin solution (J) used for the composite of fiber and resin (a) is applied and impregnated on a 100 μm thick glass woven fabric, dried at a temperature of 160 ° C., and further dried at 170 ° C. for 90 minutes to obtain a resin component. A composite (a) of 45% by weight of C-stage fiber and resin was obtained. On the other hand, a solution in which 10 g of filler (Sunsphere H-31, manufactured by Asahi Glass: specific surface area 800 m2 / g, average particle size 3 μm) is dissolved in 10 g of polyimide resin 2 in dioxolane and toluene (weight ratio 1: 1). The film was cast on the surface of a support (trade name Lumirror T60 manufactured by Toray). Then, the film which heat-dried at the temperature of 60 degreeC with a hot-air oven, and formed the resin layer (b) of thickness 2 micrometers was obtained. The film with the support was superposed on both sides of the fiber / resin composite (a) with the support, and vacuum press-laminated under conditions of 170 ° C., 1 MPa, 6 minutes. The resin layers (b) and (a) were laminated so as to be in contact with each other. Thereafter, the support was peeled off and dried at 170 ° C. for 90 minutes to obtain a laminate comprising resin layer (b) / C stage (a) / resin layer (b). Using the obtained laminated body, it processed by the desmear and electroless-plating process shown in Table 1, and evaluated according to the evaluation procedure of various evaluation items. As can be seen from Table 5, the adhesiveness and reflow resistance were good, but the surface roughness was very high. Although the fine wiring was not peeled off, the wiring shape was distorted due to the large surface roughness of the resin, and the wiring as designed could not be achieved.

  The present invention is not limited to the configurations described above, and various modifications can be made within the scope of the claims, and technical means disclosed in different embodiments and examples can be used. Embodiments obtained by appropriate combinations are also included in the technical scope of the present invention.

  Although the laminate according to the present invention has a low surface roughness, the electroless plating film does not swell even in any state of the electroless plating chemical solution, and the adhesiveness with the electroless plating film is high. In particular, it can be suitably used for the production of printed wiring boards that require fine wiring formation. Therefore, the present invention can be suitably used not only in the material processing industry such as resin compositions and adhesives and various chemical industries, but also in the industrial field of various electronic components.

Claims (16)

A laminate having a resin layer (b) for forming a metal plating layer on at least one surface of a composite of fiber and resin (a),
The resin layer (b) contains (A) a resin composition component and (B) a filler component as essential components, and the surface roughness of the resin layer (b) is measured with a cutoff value of 0.002 mm. Ra is 0.4 um or less, (B) the specific surface area of the filler is 20 m ² / g or more and 600 m ² / g or less, and the elastic modulus at 20 ° C. of the resin layer (b) is 2.3 GPa or more and 15 GPa. A laminate having the following characteristics.   The laminate according to claim 1, wherein the (B) filler component is contained in an amount of 20% to 90% by weight in the total solid content of the resin layer (b).   (B) A filler component contains an inorganic filler, The laminated body of any one of Claims 1-2 characterized by the above-mentioned.   (B) The laminate according to any one of claims 1 to 3, wherein the filler component contains at least one selected from the group consisting of finely divided silica and fumed silica.   The laminate according to any one of claims 1 to 4, wherein the filler component (B) contains fumed silica. (A) The resin composition component is a resin composition component containing a resin having one or more structures among the structures represented by any of the following general formulas (1) to (6). The laminate according to any one of claims 1 to 5.

(In the formula, R ¹ and R ³ each independently represents a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3 to 10, n = 3 to 100, and m is an integer of 1 to 200.) The laminate according to any one of claims 1 to 6, wherein the resin composition component (A) is a resin composition component containing a resin having a structure of the following general formula (6).

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. And each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, x = 3 to 10, and m is an integer of 1 to 200.) (A) The resin composition component is a polyimide resin having one or more structures among the structures represented by any of the following general formulas (1) to (6), or the following general formulas (1) to (6) 8) A resin composition component containing at least one of the polyamide-imide resins having one or more structures among the structures represented by any of the above). The laminated body as described in.

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. Each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, and R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group. X = 3-10,
Further, n = 3 to 100, and m is an integer of 1 to 200. ) (A) Resin composition component is a resin composition component containing the polyimide resin which has a structure of following General formula (6), The laminated body of any one of Claims 1-8 characterized by the above-mentioned. .

(In the formula, R ¹ and R ³ each independently represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ may be the same or different. And each independently represents an alkyl group, a phenyl group, an alkoxy group, or a phenoxy group, x = 3 to 10, and m is an integer of 1 to 200.)   The laminate according to any one of claims 1 to 9, wherein the resin composition component (A) is a resin composition component containing a thermosetting component. (A) The thermosetting component is an epoxy resin, The laminate according to claim 10.   The laminate (1) according to any one of claims 1 to 11, wherein the composite (a) of the fiber and the resin is a B stage.   The laminate (1) according to any one of claims 1 to 11, wherein the composite (a) of the fiber and the resin is a C stage.   The laminated body in which the electroless-plating film is formed in the laminated body surface of any one of Claims 1-13.   The laminate according to claim 14, wherein the electroless plating film is an electroless copper plating film.   The printed wiring board formed using the laminated body of any one of Claims 1-15.