JP4866589B2 - Plating material, polyamic acid solution, polyimide resin solution used for the plating material, and printed wiring board using the same - Google Patents

Description

  The present invention is a plating material that can be suitably used for electroless plating, a polyamic acid solution and a polyimide resin solution used for the plating material, and particularly suitable for production of printed wiring boards. The present invention relates to a solution that can be used, a plating material, and a printed wiring board using the same.

  Electroless plating, in which a reducing agent is placed in an aqueous solution of a metal salt without using electrical energy, and the metal is deposited on the substrate by the reducing action of its decomposition, is the insulation of various plastics, glass, ceramics, wood, etc. This technique is widely applied to functionalize the surface of the conductive material. For example, apply electroless plating to ABS resin or polypropylene resin, and use functional plating such as decorative plating for parts such as grills and marks for automobiles, knobs for household appliances, and through-hole plating for printed wiring boards. Can do.

  However, electroless plating often has low adhesion to the surfaces of the various materials. In particular, when applied to the production of the above-described printed wiring board, the problem is that the adhesion between the electroless plating film and the insulating material is low. In particular, when a method of forming an electroless plating film is used as a method for directly forming a metal layer on an insulating material, the electroless plating is firmly adhered to an insulating material having a smooth surface with a small surface roughness. It was very difficult to do.

  This is because it is considered that the electroless plating is formed so as to be deposited mainly via a catalyst such as palladium. Therefore, in order to improve the adhesion to the circuit wiring formed on the resin surface having a small surface roughness, a certain underlying metal layer is formed on the polyimide film surface by a physical method such as vapor deposition or sputtering, and the good condition is obtained. It was necessary to form copper as a conductive material (see Patent Document 2).

  On the other hand, for example, when producing an electroless plating film on an insulating material when manufacturing a printed wiring board having a wiring formed on the surface, the electroless plating film is firmly formed on the smoothest surface as possible. Is highly desirable.

In order to solve the above problems, insulating resin materials used for printed wiring boards have roughened the surface by various methods, and have obtained adhesion to the electroless plating film by a so-called anchor effect (for example, Patent Documents) 1). However, in order to improve the adhesion, it is necessary to increase the roughness of the material surface. When the surface roughness is small, the adhesion between the electroless plating film and the resin material is low. There was a limit to wiring formation.
Japanese Unexamined Patent Publication No. 2000-198907 (published July 18, 2000) JP-A-8-330728 (published on December 13, 1996)

  As explained in the background art, even when the surface roughness is small, the plating material has high adhesion between the insulating resin material and the electroless plating film and can form the electroless plating well on the entire surface to be plated. Has not yet been found.

  Accordingly, the present invention has been made to solve the above-described conventional problems, and an object of the present invention is a plating material having a layer for applying electroless plating, and applying the electroless plating. When a specific polyimide resin is used as a layer for this purpose and the adhesive strength of the layer A is defined, the surface roughness of the layer A is small, but electroless plating is performed using this material. In order to improve the adhesion between electroless plating and various materials and to provide a plating material for good electroless plating, it can be suitably used particularly for the production of various printed wiring boards. Furthermore, flexible printed wiring boards, rigid printed wiring boards, multilayer flexible printed wiring boards, multilayer rigid wiring boards, build-up wiring boards, etc. that require fine wiring formation are required. The solution can be suitably used for manufacturing such a wiring board, it is to provide a plating material and the printed wiring board using the same.

  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 plating materials. That is, the present invention includes the following industrially useful inventions (1) to (6).

  (1) A plating material having at least a layer A for performing electroless plating, wherein the layer A has the following general formulas (1) to (6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _x H _2x or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
In addition to containing a polyimide resin having one or more structures among the structures represented by any of the above, the surface roughness of the layer A is 0 as the arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. A plating material having a thickness of less than 5 μm and a peel adhesion of the surface of the layer A of 1.0 N / 25 mm or less.

  (2) The plating material according to (1), wherein the electroless plating is electroless copper plating.

  (3) A layered product obtained by electroless plating on layer A according to (1).

  (4) A printed wiring board using the plating material according to (1) or (2).

  (5) The following general formulas (1) to (6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _x H _2x or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
Among the structures represented by any of the above, a polyimide resin solution containing a polyimide resin having one or more structures, which is used for forming the layer A according to (1) .

  (6) The following general formulas (1) to (6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _x H _2x or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
A solution containing a polyamic acid having one or more structures among the structures represented by any of the above, wherein the polyamic acid solution is used to form the layer A according to (1) .

  In the present invention, the surface roughness is particularly small by having a layer A for performing electroless plating, using a polyimide resin having a specific structure for the layer A, and defining the adhesive strength of the layer A. Nevertheless, the adhesive strength with the electroless plating layer is high, the adhesiveness with other various materials is excellent, and the material with excellent circuit formability can be obtained. Therefore, if the plating material of the present invention is first formed on the surface of the material to be electrolessly plated and then electroless plating is performed, the plating material of the present invention plays the role of an interlayer adhesive. There is an advantage that the plating and the material are firmly bonded. In addition, since the plating material of the present invention has excellent heat resistance by containing a polyimide resin, it can be suitably used for the production of various printed wiring boards, and in particular, surface roughening should be performed. Flexible printed wiring boards, rigid printed wiring boards, multilayer flexible printed wiring boards, multilayer rigid wiring boards, and build-up wiring boards that require fine wiring formation, taking advantage of the high adhesive strength with the electroless plating layer The effect that it can use suitably for manufacture for printed wiring boards, etc. is also produced.

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

(Plating material of the present invention, characteristics and composition of the solution)
The plating material of the present invention has a layer A for performing electroless plating, and the layer A contains a polyimide resin having a structure represented by the general formulas (1) to (6). The surface roughness of the layer A is an arithmetic average roughness Ra measured at a cutoff value of 0.002 mm, which is less than 0.5 μm, and the 90-degree peeling adhesive strength of the layer A is 1.0 N / 25 mm or less. It is characterized by that.

  By using the polyimide resin having the structure represented by the general formulas (1) to (6) for the layer A and defining the adhesive strength of the layer A, the surface roughness of the layer A is 0 in Ra. Although it is very small, less than 5 μm, the adhesive strength with the electroless plating film can be improved, and the circuit formability can be improved.

  The plating material of the present invention may be any material and form having any structure depending on the use as long as it has the layer A. For example, when the plating material of the present invention is used for a printed wiring board, it may be a material composed only of the layer A, or from the layer A and the layer B for facing the formed circuit. The material comprised may be sufficient, and the material comprised from layer A / polymer film C / layer B may be sufficient. Moreover, the material comprised from the layer A and the polymer C may be sufficient, and the material comprised from the layer A / polymer film C / layer A may be sufficient.

  In order to obtain the plating material of the present invention, a solution containing a polyimide resin is preferably used. In order to obtain the plating material of the present invention, a solution containing polyamic acid is preferably used.

  The plating material of the present invention only needs to have at least the layer A for performing electroless plating. However, the plating material of the present invention is first formed on the surface of the material to be electrolessly plated, and then the non-electrolytic plating is performed. A method of applying electrolytic plating is preferably used. As a result, the plating material 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 can be applied to various decorative plating applications and functional plating applications. Is possible. Among them, it has heat resistance and can be suitably used as a plating material for a printed wiring board by taking advantage of the ability to firmly form an electroless plating layer even when the surface roughness is small.

  The case of applying the plating material of the present invention to a printed wiring board will be described below.

(Layer A)
The layer A is a layer whose surface is subjected to electroless plating, and it is important that the layer A contains a polyimide resin having a structure represented by the general formulas (1) to (6). . If the present inventors contain a polyimide resin having a structure represented by the above general formulas (1) to (6) as a material for the surface to be subjected to electroless plating, the adhesion to the electroless plating will be described. Has been found to be good. Here, the layer A of the present invention refers to a surface having a thickness of 10 mm or more (in this specification, the layer A having a surface to which electroless plating is applied may be simply referred to as a surface A). . For example, when the plating material of the present invention having the surface A is in the form of a sheet, both surfaces of the sheet are referred to as the surface A.

  In addition, in order to uniformly perform electroless plating, it is important to design the resin and the composition that constitute the layer A so that the peel adhesive strength of the layer A is 1.0 N / 25 mm or less.

  That is, the surface roughness of the layer A of the present invention is as small as less than 0.5 μm in arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. When this condition is satisfied, when the plating material of the present invention is used for a printed wiring board, the material of the present invention is particularly prominent when used for a printed wiring board because it has good fine wiring formability. The effect is expressed. In consideration of fine wiring formability, it is preferably less than 0.3 μm, and more preferably less than 0.1 μm. When Ra is 0.5 μm or more, particularly when the plating material of the present invention is applied to a printed wiring board, surface irregularities become large and it is difficult to form fine wiring, so care must be taken.

  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.

  Further, in the present invention, the adhesive strength of the surface of the layer A is 90 ° peel adhesive strength defined in JIS Z 0237. A method for measuring the peel adhesive strength will be described in detail. As a test plate, a SUS302 steel plate specified in JIS G 4305 is used. That is, the test piece and the test plate are pressure-bonded by reciprocating the surface of the layer A and the test plate with a rubber roller at a load of 2000 g and a speed of 300 mm / min. Using the test sample, a 90 ° peel test is performed at a speed of 300 mm / min, and the 90 ° peel strength is measured.

  The 90 ° C. peel adhesive strength is 1.0 N / 25 mm or less, more preferably 0.7 N / 25 mm or less, and still more preferably 0.5 N / 25 mm or less. When the 90 ° C. peeling adhesive strength is greater than 1.0 N / 25 mm, the formation of electroless plating on the layer A becomes worse. That is, it may be difficult to form an electroless plating film uniformly on the surface to be electroless plated. In addition, when used in a printed wiring board, the fine circuit formation may be adversely affected.

  Next, the polyimide resin of the present invention will be described.

  The polyimide resin of the present invention has the following general formulas (1) to (6).

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _x H _2x or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
Of the structures represented by any of the above, any polyimide resin having at least one kind of structure may be used. As a method for producing a polyimide resin having a structure represented by the general formulas (1) to (6), for example, (1) an acid 2 having a structure represented by the general formulas (1) to (6) may be used. Using the anhydride component or the diamine component having the structure represented by the above general formulas (1) to (6), a polyamic acid which is a precursor of the polyimide resin is produced, and this is imidized to produce a polyimide resin. (2) A polyamic acid having a functional group is produced using an acid dianhydride component having a functional group or a diamine component having a functional group, the functional group capable of reacting with the functional group, and the above general formula (1) ) To (6) are reacted with a compound having a structure represented to produce a polyamic acid introduced with the structure, and imidized to produce a polyimide resin, (3) an acid having a functional group Dianhydride formation Or the polyamic acid which has a functional group is manufactured using the diamine component which has a functional group, this is imidized, the polyimide which has a functional group is manufactured, the functional group which can react with this functional group, and said general formula (1) ) To (6), a method of producing a polyimide resin having the structure introduced therein by reacting a compound having the structure represented by (6).

  Here, since the diamine having the structure represented by the general formulas (1) to (6) can be obtained relatively easily, among them, the acid dianhydride component and the general formula ( It is preferable to produce the target polyimide resin by reacting the diamine having the structure represented by 1) to (6).

  Next, a production example in the case where an acid dianhydride component and a diamine having a structure represented by the above general formulas (1) to (6) are used as the polyimide resin of the present invention 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.

  Here, when an acid dianhydride having no flexible linking group such as pyromellitic dianhydride is used, the adhesive strength tends to decrease, and 4,4 ′-(4,4′- If an acid dianhydride having a flexible linking group such as isopropylidenediphenoxy) bis (phthalic anhydride) is used, the adhesive strength tends to be improved. On the other hand, when an acid dianhydride having no flexible linking group such as pyromellitic dianhydride is used, the solubility of the resulting polyimide resin tends to decrease, and 4,4 ′-(4 , 4′-isopropylidenediphenoxy) bis (phthalic anhydride) tends to improve solubility when an acid dianhydride having a flexible linking group is used. It is important to select an acid dianhydride from the above viewpoints of tackiness and solubility.

  Subsequently, the diamine component will be described. In the present invention, as the diamine component, the following general formulas (1) to (6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _x H _2x or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
It is preferable to contain the diamine which has a structure represented by either.

  By using a diamine component containing a diamine having a structure represented by the general formulas (1) to (6), the resulting polyimide resin has a characteristic of being firmly bonded to the electroless plating layer.

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 can be mentioned. Examples of the diamine represented by the general formula (3) include Elastomer 1000P, Elastomer 650P, and Elastomer 250P (manufactured by Ihara Chemical Industry Co., Ltd.). In the case of an elastomer, R ^{2 in the} general formula (3) is C ₄ H ₈ . Examples of the diamine represented by the general formula (4) include polyether polyamines and polyoxyalkylene polyamines. Jeffamine D-2000 and Jeffamine D-4000 (manufactured by Huntsman Corporation) Etc. can be illustrated.

  Furthermore, examples of the diamine represented by the general formula (6) include 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, 1,3,3, -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) trisiloxane 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 1,1,5,5-tetramethyl-3,3-dimethoxy -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. Moreover, as a diamine which has a structure represented by the said General formula (6) which is comparatively easy to obtain, Shin-Etsu Chemical Co., Ltd. KF-8010, X-22-161A, X-22-161B, X-22- 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.

  Here, it is preferable to use a diamine having a structure represented by the general formulas (1) to (6) in combination with another diamine in order to make the adhesive strength within the scope of the present invention. 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, by combining the diamine having the structure represented by the above general formulas (1) to (6) and the other diamines described above as a diamine component, the above general formulas (1) to (6) The adhesive force is lower than when only the diamine having the structure represented is used as the diamine component.

  Moreover, adhesive force can also be controlled with the quantity of the diamine which has a structure represented by the said general formula (1)-(6), and the diamine which has a structure represented by the said general formula (1)-(6). When the amount of is decreased, the adhesive strength is lowered, and when the amount of the diamine having the structure represented by the general formulas (1) to (6) is increased, the adhesive strength tends to be increased. As described above, the adhesive strength is controlled by combining the acid anhydride component, the diamine having the structure represented by the above general formulas (1) to (6), and other diamines that can be used in combination to form a diamine component. Is possible.

  The diamine having the structure represented by the general formulas (1) to (6) is preferably 2 to 98 mol%, more preferably 5 to 95 mol% with respect to the total diamine component. When the diamine having the structure represented by the general formulas (1) to (6) is lower than 2 mol% with respect to the total diamine component, the adhesive strength tends to be low. Moreover, when the diamine which has a structure represented by the said General formula (1)-(6) is higher than 98 mol% with respect to all the diamine components, it exists in the tendency for the electroless-plating formability to worsen.

  The polyimide is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid polymer. The polyamic acid polymer 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.

The term “dissolved” as used herein refers to a state in which the solute is uniformly dissolved or dispersed in the solvent in addition to the case where the solvent completely dissolves the solute. Including cases. 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 and / or dispersed in an organic polar solvent and then polymerized using a diamine 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 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 imidation completion temperature, that is, about 250 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 commercially available polyimide resin may also be used. As an example of a polyimide resin having a structure represented by the above general formula (6) that can be used for the plating material of the present invention, X-22-8917 manufactured by Shin-Etsu Chemical Co., Ltd., X -22-8904, X-22-8951, X-22-8756, X-22-8984, X-22-8985, and the like. These are polyimide solutions.
The layer A can contain other components in addition to the above-described polyimide resin for the purpose of adjusting the adhesive strength. As other components, resins such as thermoplastic resins and thermosetting resins can be used as appropriate.

  Examples of the thermoplastic resin include a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a phenoxy resin, an acid dianhydride component, and a thermoplastic polyimide resin. These may be used alone or in appropriate combination. Can do.

  Thermosetting resins include bismaleimide resin, bisallyl nadiimide resin, phenol resin, cyanate resin, epoxy resin, acrylic resin, methacrylic resin, triazine resin, hydrosilyl cured resin, allyl cured resin, unsaturated polyester resin, etc. These can be used alone or in appropriate combination. In addition to the thermosetting resin, a side chain reactive group type thermosetting having a reactive group such as an epoxy group, an allyl group, a vinyl group, an alkoxysilyl group or a hydrosilyl group at the side chain or terminal of the polymer chain. It is also possible to use a functional polymer. In addition, when a thermosetting resin is contained, the adhesive strength of the layer A obtained tends to decrease.

  In addition, various organic fillers and inorganic fillers can be added to the layer A for the purpose of adjusting the adhesive strength. In addition, when it contains a filler, it exists in the tendency to reduce the adhesive force of the layer A obtained.

  It is important to combine the above-mentioned other components within a range that does not increase the surface roughness of the layer A to such an extent that the fine wiring formation is adversely affected, and does not decrease the adhesion between the layer A and the electroless plating layer. This point needs attention.

  Other methods for reducing adhesive strength include mechanical roughening such as polishing with abrasives and sandblasting, chemical roughening by immersion in an alkaline solution, etc., and irradiation with electron beams, ultraviolet rays, plasma, etc. Examples of the method include surface modification. Also in this case, it is important not to increase the surface roughness of the layer A so as to adversely affect the formation of fine wiring, and to combine within a range that does not reduce the adhesion between the layer A and the electroless plating layer. Be careful.

  As described above, the molar concentration of the diamine having the structure represented by the general formulas (1) to (6) with respect to all diamine components is set within a specific range, or the general formulas (1) to (6). The adhesive force of the surface of the layer A of the present invention is reduced to 1.0 N / 25 mm or less by a method such as surface roughening or surface modification by containing a polyimide resin having a structure represented by formula (II) and other components. Is possible. In this way, by adjusting the adhesive strength to a specific range, it becomes possible to form high adhesive strength and good electroless plating, and especially excellent in fine circuit formability when used for printed wiring boards. Become.

  The surface roughness of the layer A of the present invention is preferably less than 0.5 μm in terms of arithmetic average roughness Ra measured with a cutoff value of 0.002 mm. Therefore, it can be said that the layer A in the present invention has a very smooth surface when the surface roughness in a minute range is observed. Therefore, for example, even when a fine wiring having a line and space of 10 μm / 10 μm or less is formed, there is no adverse effect.

When this condition is satisfied, particularly when the plating material of the present invention is used for printed wiring board applications, it has good fine wiring formability. In order to form the layer A having such a surface, for example, the following methods (1) to (4) may be appropriately combined.
(1) The plating material of the present invention formed by forming a resin solution comprising a polyimide resin constituting the plating material of the present invention on a desired material by a known method such as spray coating or spin coating, Surface treatment is not performed on a sheet-like plating material produced by casting and drying a solution on a support.
(2) The surface roughness of the surface in contact with the layer A for electroless plating of a material such as a support or slip paper is appropriately selected.
(3) In the case of a sheet composed of at least two layers including the layer A having the surface A for performing electroless plating, the surface roughness of the layer in contact with the layer A is appropriately selected.
(4) The composition of the polyimide resin contained in the layer A and the drying conditions when forming the layer A are appropriately selected.

  Specifically, it is preferable not to perform physical surface roughening such as sandblasting or chemical surface roughening such as blending an alkali-soluble component and treating with an alkali solution.

  Further, when the plating material of the present invention is a sheet formed on a support, it is preferable that the surface roughness of the support is sufficiently small. Further, when the sheet is laminated with the inner wiring board, it is preferable that the surface roughness of the interleaving paper opposed to the sheet at the time of lamination is sufficiently reduced. Accordingly, the surface roughness of the support or slip sheet is preferably 0.5 μm or less in terms of arithmetic average roughness Ra measured at a cutoff value of 0.002 mm.

  In the case of a sheet composed of at least two layers including the layer A for performing electroless plating, the surface roughness of the layer in contact with the layer A may affect the surface of the layer A. It is preferable that the surface roughness of the layer in contact with A is sufficiently small. Therefore, the surface roughness of the layer in contact with the layer A is preferably 0.5 μm or less in terms of arithmetic average roughness measured at a cutoff value of 0.002 mm.

  Further, the surface roughness of the layer A for performing electroless plating varies depending on the type of acid dianhydride component and diamine component used in the polyimide resin contained in the layer A and the blending ratio. For example, when a diamine having a structure represented by the general formula (6) is used, Ra may increase due to phase separation depending on the type of acid dianhydride component or other diamine component to be combined. is there.

  Moreover, when mixing the polyimide resin which has a structure represented with the said General formula (6), and a thermoplastic polyimide resin, there exists a tendency which raise | generates a phase separation and Ra becomes large. Also consider the drying conditions.

  The surface roughness of the layer A for performing electroless plating of the present invention is such that the surface roughness in a minute range is small, so the composition of the polyimide resin contained in the layer A and the drying conditions of the layer A The surface roughness varies depending on the combination. Therefore, what is necessary is just to confirm that the target surface roughness is obtained by variously changing the composition of the polyimide resin and the drying conditions of the layer A.

  Also, when other components are included, depending on the blending amount and the combination of resins, phase separation may occur and Ra may increase, so various blending amounts and resins of other contained components may be changed. Then, it is sufficient to confirm that the target surface roughness is obtained.

  In addition, for the purpose of further improving the adhesion to the electroless plating layer, various additives can be added to the plating material, and the layer A can be present on the surface of the plating material by a method such as coating. Specific examples include organic thiol compounds, but are not limited thereto.

(Other layers)
The plating material of the present invention may be any material as long as it has the layer A. For example, when the plating material of the present invention is applied to a printed wiring board, particularly a rigid printed wiring board such as a build-up wiring board, the material may be composed of only the layer A, or the layer A may be formed. It may be a material composed of a layer B for facing the circuit, or a material composed of layer A / polymer film C / layer B. Further, when the plating material of the present invention is applied to a printed wiring board, particularly a flexible printed wiring board, it may be a material composed of layer A / polymer C, or layer A / polymer film C / A material composed of the layer A may be used.

  When the layer B is laminated on the surface having the formed circuit, the layer B needs to have excellent workability so that the layer B flows between the circuits and the circuit can be embedded. In general, the thermosetting resin is excellent in the processability, and the layer B preferably contains a thermosetting resin. This thermosetting resin composition includes epoxy resin, phenol resin, thermosetting polyimide resin, cyanate ester resin, hydrosilyl cured resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, allyl resin, Thermosetting resin such as saturated polyester resin; side chain reactive group type thermosetting polymer having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group at the side chain or terminal of polymer chain It can be applied as a thermosetting resin composition in combination with an appropriate thermosetting agent and a curing catalyst. It is also possible to preferably add a thermoplastic polymer to these thermosetting resin compositions. For example, a thermosetting resin composition containing an epoxy resin and a phenoxy resin, or a heat containing an epoxy resin and a thermoplastic polyimide resin. A curable resin composition, a thermosetting resin composition containing a cyanate resin and a thermoplastic polyimide resin, and the like can be preferably implemented. Among these, a thermosetting resin composition including an epoxy resin and a thermoplastic polyimide resin that are excellent in a balance of various properties required as a plating material is most preferable. In addition, various fillers can be combined for low thermal expansion.

  The polymer film C is not particularly limited, and any polymer film can be used, but a non-thermoplastic polyimide film is preferable from the viewpoint of heat resistance and low thermal expansion.

  The plating material having at least the layer A for performing electroless plating of the present invention is excellent in adhesiveness with electroless plating without special surface treatment. You can use it. However, when used for a printed wiring board, it is necessary to have a surface roughness that does not adversely affect wiring formation.

  The plating material or insulating sheet of the present invention may be subjected to an alkali treatment such as desmear before forming an electroless plating film. The surface of a conventionally known material, such as an epoxy resin material, is roughened by an alkali treatment such as desmear. On the other hand, a polyimide resin having a structure represented by the above formula (1), (2), (4), or (6) is used as the layer A for performing the electroless plating of the present invention. However, even if an alkali treatment such as desmear is performed, the surface can be kept smooth without being roughened and an electroless plating film can be formed firmly.

(Electroless plating)
Examples of the electroless plating formed on the layer A of the plating material of the present invention include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, and electroless tin plating. However, from the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable.

(Solution of the present invention)
The solution of the present invention is a solution containing a polyimide resin having a structure represented by the above general formulas (1) to (6), which is used for forming the layer A. As described above, the solution may contain other components in addition to the polyimide resin, and any solvent that dissolves these resin components can be used. Here, dissolving means that the resin component is dissolved by 1% by weight or more with respect to the solvent. The solution A can be formed on the desired material by coating and drying by a known method such as dipping, spray coating, spin coating and the like.

  The solution of the present invention is a solution containing a polyamic acid having a structure represented by the above general formulas (1) to (6), which is used for forming the layer A. As described above, the solution may contain other components in addition to the polyamic acid solution, and any solvent that dissolves these resin components can be used. Here, dissolving means that the resin component is dissolved by 1% by weight or more with respect to the solvent. The solution can be applied to the desired material by a known method such as dipping, spray coating, spin coating and imidization to form the layer A by a known method. As described above, imidation can be carried out using either a thermal method in which a polyamic acid solution is heat-treated for dehydration or a chemical method for dehydration using a dehydrating agent. Moreover, the method of imidating by heating under reduced pressure can also be used. Among these, from the viewpoint of simple treatment and good production efficiency, a method of imidization by a thermal method of heat treatment and dehydration can be preferably used.

(Form and manufacturing method of plating material of the present invention)
Next, the manufacturing method of the plating material of this invention is demonstrated.

One of the forms of the plating material of the present invention is a solution containing a polyimide resin. For example, the above solution for forming the layer A for electroless plating is manufactured, and the desired material such as an inner wiring board or a polymer film is produced by a known method such as immersion, spray coating, spin coating, etc. The layer A can be formed by applying and drying the coating. Here, in order to adjust the adhesive strength within the range of the present invention, it is preferable to dry it under drying conditions that can sufficiently remove volatile matter. (Specifically, using a TGA (TGA-50, manufactured by Shimadzu Corporation) measuring device, the volatile content quantified by measuring the weight loss% between 20 ° C. and 200 ° C. of the condition 20 ° C./min and the temperature-Tg curve. Is preferably 1% or less.)
One of the other forms of the plating material of the present invention is a polyamic acid solution. For example, the above solution for forming the layer A for electroless plating is manufactured, and the desired material such as an inner wiring board or a polymer film is produced by a known method such as immersion, spray coating, spin coating, etc. The layer A can be formed by coating and imidizing it. Here, in order to adjust the adhesive strength within the range of the present invention, it is preferable to dry it under drying conditions that can sufficiently remove volatile matter. (Specifically, using a TGA (TGA-50, manufactured by Shimadzu Corporation) measuring device, the volatile content quantified by measuring the weight loss% between 20 ° C. and 200 ° C. of the condition 20 ° C./min and the temperature-Tg curve. Is preferably 1% or less.)
Another form of the plating material of the present invention is a sheet. For example, the sheet | seat which has the layer A is manufactured by carrying out casting application | coating of the solution which forms the layer A which performs electroless plating on a support body, and making it dry after that. By laminating this sheet on a desired material such as an inner wiring board or a polymer film, the layer A can be formed. As described above, the layer A of the present invention refers to a layer having a thickness of 10 mm or more.

  As mentioned above, although it illustrated about the form and usage method of the material for plating of this invention, it is not limited to this.

<Printed wiring board>
The plating material of the present invention can be preferably used for printed wiring board applications. Here, as a method of manufacturing a printed wiring board using the sheet-like plating material of the present invention, a sheet-like plating material with a resin film base material and an inner layer substrate on which a circuit pattern is formed are sequentially laminated. Then, it is possible to obtain a metal layer for a circuit pattern by performing electroless plating on the surface of the layer A exposed by peeling the resin film substrate.

  In the above, when a flexible printed wiring board is used for the inner layer board, a multilayer flexible wiring board is manufactured, and when a printed wiring board using a glass-epoxy base material is used, a multilayer rigid wiring board or build An up-wiring board will be manufactured. In addition, vias must be formed on the multilayer printed wiring board for vertical electrical connection. In the printed wiring board of the present invention, vias are formed by a known method such as laser, mechanical drilling or punching. However, it can be made conductive by a known method such as electroless plating and is preferably carried out.

  At the time of lamination, thermocompression treatment such as heat press treatment, vacuum press treatment, laminating treatment (heat laminating treatment), vacuum laminating treatment, hot roll laminating treatment, vacuum hot roll laminating treatment 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.

  Moreover, it is also possible to heat-process after forming an electroless-plating layer in order to improve the adhesiveness of the layer A and an electroless-plating layer.

  The present invention is not limited to the configurations described above, and various modifications can be made within the scope of the claims, and the technical means disclosed in different embodiments are appropriately combined. The obtained embodiment is also included in the technical scope of the present invention.

  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 the characteristics of the plating material according to the present invention, the adhesion to the electroless plated copper, the surface roughness Ra, the adhesiveness, and the wiring formability were evaluated or calculated as follows.

[Adhesion evaluation]
A material composed of a plating material / support having layer A is prepared, and the plating material and glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd .; copper foil thickness) 50 μm, overall thickness 1.2 mm), and after heating and pressurizing for 6 minutes under the conditions of temperature 170 ° C., pressure 1 MPa, and vacuum, the polyethylene terephthalate film was peeled off at 130 ° C. The laminate was heated for 10 minutes at 150 ° C. for 10 minutes and at 180 ° C. for 30 minutes to obtain a laminate made of the plating material / FR-4 having the layer A. Thereafter, a copper layer was formed on the exposed layer A. The copper layer was formed by performing desmearing and electroless copper plating, and then forming an electroplated copper layer having a thickness of 18 μm on the electroless plated copper. 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). In addition, desmear and electroless copper plating were implemented by the process of the following Tables 1-2.
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]
In the sample preparation procedure of the adhesiveness measurement item, the surface roughness Ra of the layer A was measured using a sample in a state where desmearing was performed. In the measurement, the arithmetic average roughness of the layer A was measured under the following conditions using a light wave interference type surface roughness meter (New View 5030 system manufactured by ZYGO).

(Measurement condition)
Objective lens: 50x Mirau
Image zoom: 2
FDA Res: Normal
Analysis conditions:
Remove: Cylinder
Filter: High Pass
Filter Low Wave: 0.002mm
[Adhesiveness]
The surface having the layer A and the SUS302 steel plate were reciprocated once with a rubber roller at a load of 2000 g and a speed of about 300 mm / min to press-bond the test piece and the test plate. Using the test sample, a 90 ° peel test was performed at a speed of 300 mm / min, and the 90 ° peel adhesive strength was measured.

[Wiring formability]
A material composed of a plating material / support having the layer A is prepared, and the plating material and a glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd .; copper foil) 50μm thick, 1.2mm overall thickness), and the wiring side of the wiring formed FR-4 (wiring thickness 12μm) is made to face, temperature is 170 ° C, pressure is 1MPa, 6 minutes under vacuum After heating and pressurizing, the polyethylene terephthalate film is peeled off, and heated at 130 ° C. for 10 minutes, 150 ° C. for 10 minutes, and 180 ° C. for 30 minutes, from the plating material having layer A / FR-4 The resulting laminate was obtained. After that, a via hole with an inner diameter of 30 μm reaching the electrode is opened immediately above the FR-4 electrode of the inner layer by a UV-YAG laser, followed by electroless copper plating on the entire surface of the substrate, followed by heat treatment at 180 ° C. for 30 minutes. did. Thereafter, a resist pattern is formed on the formed copper plating layer, and after applying electrolytic copper plating with a thickness of 10 μm, the resist pattern is peeled off, and the exposed plated copper is removed with a hydrochloric acid / ferric chloride-based etchant. A printed wiring board having wirings of line and space (L / S) = 100 μm / 100 μm and L / S = 10 μm / 10 μm was produced. The wiring formability was evaluated by assuming that the case where the wiring of the printed wiring board was satisfactorily produced without disconnection or shape defect and that the case where disconnection or shape defect occurred was x.

[Synthesis Example 1: Polyimide resin]
In a glass flask having a capacity of 2000 ml, 62 g (0.075 mol) of KF8010 manufactured by Shin-Etsu Chemical Co., Ltd., 15 g (0.075 mol) of 4,4′-diaminodiphenyl ether, N, N-dimethylformamide (hereinafter referred to as DMF) Is added, dissolved while stirring, 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) is added, stirred for about 1 hour, and solid A DMF solution of polyamic acid with a partial concentration of 30% was obtained. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated in a vacuum oven at 200 ° C. for 120 minutes under reduced pressure at 665 Pa to obtain polyimide resin 1.

[Synthesis Example 2: Polyimide resin]
In a glass flask with a volume of 2000 ml, 37 g (0.05 mol) of KF8010 manufactured by Shin-Etsu Chemical Co., Ltd., 21 g (0.10 mol) of 4,4′-diaminodiphenyl ether, and DMF were added and dissolved while stirring. 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred for about 1 hour to obtain a DMF solution of polyamic acid with a solid content concentration of 30%. . The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated in a vacuum oven at 200 ° C. for 120 minutes under reduced pressure at 665 Pa to obtain polyimide resin 2.

[Synthesis Example 3: Polyimide resin]
123 g (0.15 mol) of KF8010 manufactured by Shin-Etsu Chemical Co., Ltd. and DMF were introduced into a glass flask with a volume of 2000 ml and dissolved while stirring to obtain 4,4 ′-(4,4′-isopropylidenediphenoxy. ) 78 g (0.15 mol) of bis (phthalic anhydride) was added and stirred for about 1 hour to obtain a DMF solution of polyamic acid having a solid content of 30%. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated under reduced pressure at 200 ° C. for 120 minutes at 665 Pa in a vacuum oven to obtain a thermoplastic polyimide resin 3.

[Synthesis Example 4: Polyimide resin]
In a glass flask having a capacity of 2000 ml, 41 g (0.143 mol) of 1,3-bis (3-aminophenoxy) benzene and 1.6 g (0.007 mol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl were added. DMF was added and dissolved while stirring, and 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred for about 1 hour. A DMF solution of polyamic acid with a solid content concentration of 30% was obtained. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated under reduced pressure at 200 ° C. for 180 minutes at 665 Pa in a vacuum oven to obtain polyimide resin 4.

[Synthesis Example 5: Polyimide resin]
Into a glass flask having a capacity of 2000 ml, 55 g (0.045 mol) of Elastomer 1000P (manufactured by Ihara Chemical Industry Co., Ltd.), 21 g (0.105 mol) of 4,4′-diaminodiphenyl ether, and DMF are added and stirred. Then, 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred for 1 hour, and a DMF solution of polyamic acid with a solid content concentration of 30% was added. Got. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated under reduced pressure in a vacuum oven at 200 ° C. for 180 minutes at 665 Pa to obtain polyimide resin 5.

[Synthesis Example 6: Polyimide resin]
Into a glass flask having a capacity of 2000 ml, 92 g (0.075 mol) of Elastomer 1000P (manufactured by Ihara Chemical Industry Co., Ltd.), 15 g (0.075 mol) of 4,4′-diaminodiphenyl ether, and DMF were added and stirred. Then, 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred for 1 hour, and a DMF solution of polyamic acid with a solid content concentration of 30% was added. Got. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated under reduced pressure at 200 ° C. for 180 minutes at 665 Pa in a vacuum oven to obtain polyimide resin 6.

[Formulation Example 1: Solution for forming layer A]
The polyimide resin 1 was dissolved in dioxolane to obtain a solution (a) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 2: Solution for forming layer A]
The polyimide resin 2 was dissolved in dioxolane to obtain a solution (b) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 3: Solution for forming layer A]
The polyimide resin 3 was dissolved in dioxolane to obtain a solution (c) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 4: Solution for forming layer A]
The polyimide resin 4 was dissolved in dioxolane to obtain a solution (d). The solid content concentration was 15% by weight. Moreover, the polyimide silicone solution made from Shin-Etsu Chemical Co., Ltd., X-22-8917 (solid content concentration 20 weight%, cyclohexanone solution) was used, and it was set as the solution (e) which forms the layer A. 30 g of the solution (d) and 70 g of the solution (e) were mixed to obtain a solution (f) that forms the layer A.

[Formulation Example 5: Solution for forming layer A]
Japan Epoxy Resin Co., Ltd. YX4000H 32.1g of biphenyl type epoxy resin, Wakayama Seika Kogyo Co., Ltd. bis [4- (3-aminophenoxy) phenyl] sulfone 17.9g, Shikoku Kasei Kogyo Co., Ltd. ) Epoxy curing agent, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 0.2 g, dissolved in dioxolane, and having a solid content concentration of 50% (G) was obtained. 60 g of the solution (c) and 40 g of the solution (g) were mixed to obtain a solution (h) that forms the layer A.

[Formulation Example 6: Solution for forming layer A]
The polyimide resin 5 was dissolved in dioxolane to obtain a solution (i) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 7: Solution for forming layer A]
The polyimide resin 6 was dissolved in dioxolane to obtain a solution (j) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 8: Layer B solution]
50 g of the solution (d), 15 g of the solution (g), and 50 g of silica (Admafine S0-C5, average particle size = 1.5 μm) manufactured by Tatsumori Co., Ltd. are mixed to obtain a layer B solution (k). It was.

[Example 1]
The solution for forming the layer A shown in Table 3 was cast-coated on the surface of a polyethylene terephthalate film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd.) serving as a support. Then, it was heat-dried at a temperature of 60 ° C., 100 ° C., and 150 ° C. in a hot air oven to obtain a material composed of a plating material / support having a layer A having a thickness of 25 μm. Using the obtained material, it evaluated according to the evaluation procedure of various evaluation items. The adhesive strength was measured on the surface from which the support was peeled off. The evaluation results are shown in Table 3.

[Examples 2 to 4]
According to the solution for forming the layer A shown in Table 3, a plating material having the layer A was obtained in the same procedure as in Example 1. The obtained sheet | seat was evaluated in accordance with the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 5
The solution for forming the layer A shown in Table 3 was cast-coated on the surface of a polyethylene terephthalate film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd.) serving as a support. Then, it was heat-dried at a temperature of 60 ° C. in a hot air oven to obtain a plating material having a layer A having a thickness of 5 μm.

  Subsequently, the layer B solution shown in Table 3 was cast and applied to layer A, and heated and dried at 80 ° C., 100 ° C., 120 ° C., 150 ° C., and 170 ° C. for 1 minute each in a hot air oven. A plating material having a thickness of 40 μm was obtained by combining both of the layer B and the layer B. The obtained plating material was evaluated according to evaluation procedures for various evaluation items. The measurement was performed on the surface from which the support was peeled off. The evaluation results are shown in Table 3.

Example 6
The solution for forming the layer A shown in Table 3 was cast on the surface of a 25 μm polyimide film (trade name Apical NPI, Kaneka Chemical Co., Ltd.). Then, it was heat-dried at a temperature of 60 ° C. in a hot air oven to obtain a polyimide film having a layer A having a thickness of 5 μm.

  Subsequently, the layer B solution shown in Table 3 was cast on the surface of the polyimide film opposite to the formed layer A, and each of them was heated at 80 ° C., 100 ° C., 120 ° C., 150 ° C., and 170 ° C. in a hot air oven. Heating and drying were performed for each minute to obtain a plating material composed of 5 μm layer A / 25 μm polyimide film / 35 μm layer B. The obtained plating material was evaluated according to evaluation procedures for various evaluation items. The evaluation results are shown in Table 3.

[ Reference Example 1 ]
According to the solution for forming the layer A shown in Table 3, a plating material having the layer A was obtained in the same procedure as in Example 1. The obtained sheet | seat was evaluated in accordance with the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

[ Reference Example 2 ]
According to the solution for forming layer A and the solution for layer B shown in Table 3, a plating material having layers A and B was obtained in the same procedure as in Example 5. The obtained sheet | seat was evaluated in accordance with the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

[Comparative Example 1]
Evaluation was performed according to the evaluation procedure of various evaluation items in the same procedure as in Example 1 except that the solution (c) was used. The evaluation results are shown in Table 4. As can be seen from Table 4, even if the surface roughness is small, the adhesive strength is high, but because the surface has adhesiveness, foreign matter adheres and fine wiring cannot be formed.

  Note that the present invention is not limited to the configurations described above, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments obtained by appropriate combinations are also included in the technical scope of the present invention.

The plating material according to the present invention has high adhesion not only with various materials but also with an electroless plating film. Moreover, even when the surface roughness of the present invention is small, the adhesiveness with the electroless plating film is high. Furthermore, since the adhesiveness of the surface is low, electroless plating can be satisfactorily formed on the surface of the plating material, so that it can be suitably used particularly for the production of printed wiring boards. 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 (6)

A plating material having at least a layer A for electroless plating, wherein the layer A is represented by the following general formula ( 6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, or it represents a phenoxy group, a is et a n = 3 to 100, m is an integer of 1 or more.)
With containing polyimide resin having a structure represented in the surface roughness of the layer A is a less than 0.5μm in the arithmetic mean roughness Ra measured with a cut-off value 0.002 mm, and the A plating material, wherein the surface of the layer A has a peeling adhesive strength of 1.0 N / 25 mm or less. The plating material according to claim 1, wherein the electroless plating is electroless copper plating.   A laminate comprising electroless plating on the layer A according to claim 1.   A printed wiring board using the plating material according to claim 1. The following general formula ( 6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, or it represents a phenoxy group, a is et a n = 3 to 100, m is an integer of 1 or more.)
A solution containing a polyimide resin having a structure represented in a polyimide resin solution, characterized in that used to form the layer A according to claim 1. The following general formula ( 6)

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _x H _2x or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, or it represents a phenoxy group, a is et a n = 3 to 100, m is an integer of 1 or more.)
A solution containing a polyamic acid having a structure represented in a polyamide acid solution, characterized in that used to form the layer A according to claim 1.