JP2008277717A - Resin film with metal layer, its forming method, and flexible printed board manufacturing method using the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a resin film with a metal pattern which is useful to prevent a position shift and a handling failure that are liable to result in a process of applying a cover ray and a reinforcement film in preparing a flexible printed wiring board. <P>SOLUTION: The method for forming a resin film with a metal pattern includes a process which patterns the metal layer of the resin film 10 with a metal layer that has an area where the metal layer 22 exists and an area where the metal layer does not exist to form a metal pattern 24 on the surface of a resin film base 12, a process which applies an adhesive resin on the area where the metal layer does not exist to form an adhesive layer 26, and a process which laps the adhesive layer on the area where the metal pattern is formed and applies energy to it to join the metal pattern and the adhesive layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin film with a metal layer useful for forming a metal wiring, a method for producing the resin film, and a method for producing a flexible printed circuit board using the method.

In recent years, along with demands for higher functionality of electronic devices, electronic components have been densely integrated, and further, high-density mounting has been progressing. Is becoming more and more dense.
Among them, a resin film substrate with a metal layer for forming a metal wiring is widely used as a substrate for mounting a driving semiconductor for displaying an image on a liquid crystal screen or a substrate used for an operation part requiring flexibility. Yes. In recent years, COF [Chip On Film] has attracted attention as a method for mounting a driver IC chip for liquid crystal screen display. COF is said to be capable of fine pitch mounting as well as downsizing and cost reduction of driver ICs compared to TCP (tape carrier package), which has been the mainstream of conventional mounting methods. In recent years, with the recent high definition of liquid crystal display screens and miniaturization of ICs for driving liquid crystals, COFs have been strongly required to have high definition and fine pitch electronic circuits.

  In the formation of these fine pitch wirings, “subtractive method” and “semi-additive method” are known as conventional metal pattern forming methods useful in the field of conductive patterns, particularly printed wiring boards. In the subtractive method, a metal layer formed on an insulating resin film is provided with a photosensitive layer that is exposed to actinic rays, and this photosensitive layer is exposed imagewise and developed to form a resist image. Next, the metal is etched to form a metal pattern, and finally the resist is removed. The metal-coated resin substrate used in the subtractive method is one in which a resin varnish layer is solidified on a metal foil, a thermoplastic layer is laminated on an insulating resin film, and a metal foil is laminated, or insulative. The power supply layer is formed on the surface of the resin film by some method, and electricity is applied to the power supply layer to perform electroplating. For the power feeding layer formed by this method, a plating method, a sputtering method, a vapor deposition method, a method of laminating a thin metal foil, or the like is used.

On the other hand, in the semi-additive method, a power feeding layer is provided on the surface of the insulating resin film by some method, and a photosensitive layer that is exposed by irradiation with actinic rays is provided on the power feeding layer. This is a method in which a resist image is formed, electricity is applied to the power supply layer, electroplating is performed, metal wiring is formed in the non-resist existence portion, and then the power supply layer in the nonmetal wiring portion is etched to form a metal pattern. . The power supply layer formed by this method is plating, sputtering, vapor deposition, or laminating a thin metal foil. Usually, the same film as the support is bonded with an adhesive to form a coverlay, but when making holes in the coverlay, etc., it takes time to make a separate hole in the coverlay. In addition, there is a problem in that it takes time and effort to bond the positions of the wiring and the holes with high accuracy.
Further, when the cover pattern is pasted on the wiring pattern made last time, there is a problem that the resin film with a metal layer for forming metal wiring is curled up and difficult to handle. Moreover, when trying to produce continuously by R to R, there was a problem that it was difficult to produce.
In addition, in recent years, when laminating with a cover lay or manufacturing a flexible multilayer substrate, alignment is sometimes performed with a laser, but there is also a problem that alignment is difficult due to the presence of a metal layer.

  The present invention avoids misalignment and handling defects that are likely to occur in the process of applying a coverlay or a reinforcing film during the production of a flexible printed wiring board, and a method for producing a resin film with a metal pattern that is useful for increasing production efficiency. Another object of the present invention is to provide a method for manufacturing a flexible printed wiring board.

The present inventor forms a metal pattern with excellent adhesion to the base material only on a part of the resin film base material, and uses the resin film base material in the other region as it is for a coverlay for covering the metal pattern. It has been found that the above problems can be solved, and the present invention has been completed.
That is, the configuration of the present invention is as follows.
<1> A resin film with a metal layer having a region where a metal layer in close contact with the substrate and a region without a metal layer are present on the same surface of the resin film substrate, the metal layer being in close contact with the substrate A resin film with a metal layer, wherein a circuit pattern can be formed by applying a subtract method or a semi-additive method using the metal layer forming region in a region where the metal layer exists.
<2> The partial metal according to <1>, wherein the region where the metal layer adhered to the substrate is present is a continuous region that accounts for 5 to 99.5% of the surface of the resin film substrate. Layered resin film.

<3> The metal layer in the region where the metal layer in close contact with the substrate is formed by one or more methods selected from a laminating method, a sputtering method, a vapor deposition method, and a plating method. The resin film with a metal layer as described in <1> or <2>.
<4> The metal layer in the region where the metal layer in close contact with the substrate is bonded to the resin film substrate or a layer including a polymerization initiation layer provided on the surface of the resin film substrate. A conductive substance or metal is adsorbed on a conductive substance-adsorbing resin layer having a group, or a metal ion is adsorbed and reduced by adsorbing metal ions and adsorbed on the conductive substance-adsorbing resin layer. The resin film with a metal layer according to <1> or <2>, wherein the resin film is formed by plating using a metal.
<5> A compound having a functional group having a property of adsorbing a conductive substance contained in the conductive substance-adsorptive resin layer is represented by a unit represented by the following formula (1) and a formula (2) below. <4> The resin film with a metal layer according to <4>, which is a compound derived from a copolymer containing a unit to be produced.

In the above formulas (1) and (2), R ^{1 to} R ⁵ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z are each independently A substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group is represented, and L ¹ and L ² each independently represent a substituted or unsubstituted divalent organic group.

<6> On the same surface of the resin film substrate, a metal pattern is formed by patterning a metal layer region of the resin film with a metal layer having a region where the metal layer adhered to the substrate is present and a region where the metal layer is not present. And a step of joining the metal pattern and the region where the metal layer is not present by applying energy by superimposing a region where the metal layer is not present on the region where the metal pattern is formed. Film production method.
<7> A metal pattern is formed by patterning a metal layer region of a resin film with a metal layer on the same surface of a resin film substrate, the region having a metal layer adhered to the substrate and a region having no metal layer. Forming a contact layer by applying an adhesive resin to a region where the metal layer does not exist, and applying energy by overlapping the contact layer on the region where the metal pattern is formed. A method for producing a resin film with a metal pattern, comprising: joining a metal pattern and an adhesion layer.

<8> In the region where the metal layer of the resin film with a metal layer is present on the surface of the resin film substrate, the region where the metal layer adhered to the substrate exists in a pattern and the region where the metal layer does not exist. A step of forming an adhesion layer by applying an adhesive resin, and a step of bonding the metal pattern and the adhesion layer by applying energy by overlapping the adhesion layer on a region where the metal layer exists in a pattern. And a method for producing a resin film with a metal pattern.
<9> A conductive metal having a functional group capable of adsorbing a conductive substance, in which a patterned metal layer in close contact with the substrate is bonded to a resin film substrate or a layer including a polymerization initiation layer provided on the surface of the resin film substrate. A conductive substance or metal is adsorbed on the conductive substance-adsorbing resin layer, or a metal ion is adsorbed by reducing by adsorbing metal ions, and the metal adsorbed on the conductive substance-adsorbing resin layer is used. <8> The method for producing a resin film with a metal pattern according to <8>, which is formed by plating.
<10> An adhesive layer capable of forming an interaction between a metal and an organic substance is provided between the metal pattern and the resin film substrate, and the metal pattern and the resin film group are provided by applying energy to the adhesive layer. <6>-<9> The manufacturing method of the resin film with a metal pattern of any one of <6>-<9> characterized by adhere | attaching a material.

<11> The conductive material is bonded to the conductive substance-adsorbing resin layer having a conductive substance-adsorbing functional group, wherein the metal pattern is bonded to an adhesion auxiliary layer including a polymerization initiation layer provided on the surface of the resin film substrate. Alternatively, it is a metal pattern made of a metal formed by adsorbing a metal, or adsorbing a metal ion to reduce the metal by adsorption, and plating using the adsorbed metal. The metal pattern and the resin are formed by applying energy to the adhesion auxiliary layer in the region where the conductive material adsorbing resin layer of the resin film base material is not formed and the metal auxiliary layer is not formed. <6>-<10> The manufacturing method of the resin film with a metal pattern of any one of <6>-<10> characterized by adhere | attaching a film base material.
<12> Manufacturing of a flexible printed circuit board including the process of producing the metal pattern for wiring using the manufacturing method of the resin film with a metal pattern of any one of <6>-<11>. Method.
<13> Before conducting the plating, a hole for mounting the wiring between the both sides of the film or mounting a part is made, and a metal layer is formed by plating, and at the same time a metal is formed in the hole. The method for producing a flexible printed circuit board according to <12>, wherein the conductive layer is formed by imparting.
<14> Continuously forming the wiring metal pattern so as to be electrically conductive, and then performing electroplating using the wiring metal pattern as an electrode, thickening the wiring to a desired thickness by a full additive method, The flexible printed circuit board according to <12> or <13>, wherein the circuit pattern is formed by removing a portion of the metal that is not desired to be electrically conducted in the wiring metal pattern formed after the electroplating is completed. Manufacturing method.

Hereinafter, preferable embodiments of the present invention will be listed together.
(1) A method for producing a resin film with a metal pattern, wherein the metal layer formed on one side or both sides of the resin film substrate is a continuous metal layer that can be patterned by a subtractive method or a semi-additive method.
(2) A method for producing a resin film with a metal pattern, wherein a resin film substrate in an area where no metal layer is present is applied to a cover film, a reinforcing film, a guide for handling, or the like.
(3) A method for producing a resin film with a metal pattern, wherein the metal layer is produced by a casting method, a laminating method, a sputtering method, a vapor deposition method, a plating method or the like.

(4) A step of forming a conductive substance-adsorptive resin layer in a region where a metal layer is produced by a plating method and a metal layer of a resin film base is to be formed, and metal particles in the conductive substance-adsorptive resin layer Or by adsorbing metal ions and reducing it to deposit metal, and using the metal adsorbed on the conductive material adsorbing resin layer A method for producing a resin film with a metal pattern, wherein a metal layer is formed through a step of performing the step of
(5) The conductive substance-adsorptive resin layer and the resin film substrate are in close contact with each other by causing chemical, electrical and physical bonds by applying energy, or a layer capable of adsorbing the metal. And the resin film base material are present between them, and are in close contact with each other through an adhesion auxiliary layer that is in close contact with both layers by causing chemical, electrical, and physical bonds by applying energy. The manufacturing method of the resin film with a metal pattern characterized.
(6) The method for producing a resin film with a metal pattern, wherein the application of energy is performed in a pattern to form the conductive substance adsorbing resin layer in a pattern.

(7) Before carrying out the plating step for forming the metal layer, to form a hole used for conducting between the wirings formed on both sides of the resin film substrate or for mounting the component, Thereafter, both the formation of the metal layer by plating and the conduction by forming the metal layer in the hole are carried out. A method for producing a resin film with a metal pattern,
(8) A patterned metal layer is formed by applying energy in a pattern, and then electroplating is performed using the metal layer as an electrode, and the thickness and width of the metal layer are increased to a desired thickness by a full additive method. The manufacturing method of the resin film with a metal pattern characterized by the above-mentioned.

(9) A step of providing a region where no band-like metal layer is present at the center of the resin film base, and providing a pattern-like metal layer on the surface of one part of the resin film base, and the other end of the resin film base And a step of providing a pattern-like metal layer on the back surface of the part in any order, and the two layers are overlapped so that the pattern-like metal layers formed on both ends face each other through the resin film substrate. A method for producing a resin film with a metal pattern, comprising forming a laminate of a patterned metal layer and a resin film substrate.
(10) A step of forming an adhesion layer by applying an adhesive resin on both sides of the resin film base material where a band-like metal layer is not present in the center of the resin film base material, and a surface of one part of the resin film base material A pattern formed on both wing ends, and a step of providing a patterned metal layer on the back surface of the other end of the resin film substrate and a step of providing a pattern metal layer on the back surface of the resin film substrate. Layered on the adhesion layer provided in the center so that the metal layer faces, and is adhered by applying energy to form a laminate of two patterned metal layers and a resin film substrate The manufacturing method of the resin film with a metal pattern characterized by the above-mentioned.
(11) A method for producing a flexible printed circuit board, including a step of forming metal wiring using the method for producing a resin film with a metal pattern.

According to the present invention, a metal useful for avoiding misalignment and handling defects that are likely to occur in the process of applying a coverlay or a reinforcing film during the production of a flexible printed wiring board, and in the production of a multilayer flexible substrate, and increasing the production efficiency. A method for producing a patterned resin film can be provided.
Moreover, by using the resin film with a metal pattern of the present invention, a method for producing a flexible printed wiring which can continuously and easily form a wiring and a cover film or a reinforcing plate is provided. Can do.
Furthermore, according to the preferable aspect of this invention, it becomes possible to form the flexible printed wiring board which forms the wiring which applied the full additive method by a simple method.

Hereinafter, embodiments of the present invention will be described in detail.
The method for producing a resin film with a metal pattern of the present invention uses a material obtained by forming a metal layer only on a partial region of the substrate surface on one or both surfaces of the resin film substrate. A metal pattern is formed by patterning by a known method such as a substruct method or a semi-additive method, and the metal pattern surface is overlapped with a region where the metal layer is not formed on the resin film substrate, and an adhesion layer or the like is optionally formed. In this case, the metal pattern and the protective layer are formed with good positional accuracy using one material. Here, the area | region where the metal does not exist in a resin film base material can be used as a guide for a cover film, a reinforcement film, handling, etc.

<Resin film substrate having a metal layer in a partial region of the surface>
First, the resin film base material which has a metal layer in the partial area | region of the surface used for the manufacturing method of this invention is demonstrated.
FIG. 1A is a cross-sectional view of a resin film substrate 10 having a metal layer in a partial region of the surface that can be used in the method of the present invention. The resin film substrate 10 having a metal layer in a partial region of the surface is configured by forming a continuous metal layer 22 in a partial region of the surface of the resin film substrate 12.
There are no particular restrictions on the method for forming the metal layer, and any known method may be used. However, the plating method is optimal, and the preferred method for forming the metal layer by this plating method is to adsorb the plating catalyst. It is preferable to use a conductive material-adsorptive resin layer formed by adhering to a resin film substrate by applying energy.
The material applied to the method of the present invention forms a metal layer in a predetermined region on the surface of the resin film substrate, and includes a portion where the metal layer is formed and a portion where the metal layer is not formed. In addition to a mode in which the metal layer to be formed is uniformly and continuously formed over the entire region in a predetermined region, a method of forming a patterned metal layer from the beginning can be used. In either case, the conductive substance-adsorbing resin layer is provided with a pattern of energy application to bring them into close contact with only the region where the metal layer is to be formed on the surface of the resin film substrate. The region becomes the formation region of the metal layer.

The resin film substrate according to the present invention may have a hole penetrating the front and back of the resin film substrate in the step prior to the plating step for forming the metal layer, or the conductive substance adsorbing resin. A hole may be formed after forming an adhesion auxiliary layer useful for adhering the adsorbent resin layer to the resin film substrate.
This hole is used, for example, to form a wiring for energizing a plurality of layers through an insulating layer when manufacturing a multilayer wiring board. The process of making such a hole for wiring can also be performed after the metal layer is formed in the same manner as in the usual method of using a resin film with a metal layer.
In the resin film with a metal pattern obtained by the method of the present invention, the metal pattern may be formed only on one side or on both sides, and a plurality of wiring patterns are laminated and bonded together to form a double-sided wiring board. It can also be used to form multilayer wiring boards.

  The method for forming the metal layer in the resin film substrate having the metal layer in a partial region of the surface is arbitrary. For example, the metal layer such as an adhesive layer or a thermoplastic resin layer is adhered to the region where the metal layer is to be formed. An intermediate layer that can be fixed is formed, and a metal foil is adhered to the surface by a lamination method. A non-forming region of the metal layer is covered with a resin or metal mask, and a metal layer is formed by sputtering or vapor deposition. A method in which a part of a resin film with a metal layer formed entirely on the entire surface by a casting method or a lamination method is removed by metal etching or the like to leave a metal film partially. A method of forming a metal layer by forming an active substance-adsorptive resin layer, adsorbing a plating catalyst to the active material, and performing plating.

  However, when using an adhesive or a thermoplastic resin, there is a problem that the adhesive or the thermoplastic resin protrudes from the metal foil, and it is difficult to uniformly laminate because the metal foil is partially attached. . On the other hand, the sputtering method and the deposited layer have a problem in productivity because they use vacuum equipment. The method of etching a metal is wasteful because it requires an etching operation again when cutting the wiring. For this reason, a method of applying a metal film by plating to the region where the metal layer is to be formed is most suitable.

Examples of a method for forming a metal layer on the surface of the resin film substrate by plating include a method through the following steps.
The structure of the resin film substrate 10 having a metal layer in a partial region of the surface that can be used in the method of the present invention will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view showing one embodiment of the constitution of the conductive substance adsorbing film of the present invention. Here, a mode in which the conductive substance adsorbing resin layer 20 is formed on one surface of the resin film substrate (support) 12 is shown. As shown in FIG. 2, the adhesion auxiliary layer 16 interacting with the resin film substrate 12 and the conductive substance adsorbing resin precursor layer 18 on the surface of the resin film substrate 12 and the adhesion assisting layer 16 interact with the metal. The conductive material adsorbing resin precursor layer 18 having the capability of adsorbing is sequentially provided. The adhesion assisting layer 16 may be omitted as long as the resin film substrate 12 has a function of assisting adhesion that can directly interact with the conductive substance-adsorbing resin precursor layer 18.

The method of forming the resin film substrate 10 having a metal layer in a partial region of the surface will be described. First, on one surface or both surfaces of the resin film substrate 12, the resin film substrate 12 is formed on the resin film substrate 12. A step of providing an adhesion auxiliary layer 16 that assists adhesion with the conductive substance-adsorbing resin layer 18 is performed. Here, after apply | coating the adhesion assistance layer 16 coating liquid, the process of providing energy and hardening the adhesion assistance layer 16 can be implemented.
Next, a step of providing the conductive substance adsorbing resin precursor layer 18 on the surface of the formed adhesion auxiliary layer 16 is performed. Here, by applying energy, the compound contained in the conductive substance-adsorbing resin precursor layer 18 and the compound contained in the adhesion auxiliary layer 16 have a chemical, electrical, or physical interaction. The conductive material adsorbing resin layer 20 is formed on the surface of the resin film substrate 12 by forming both of them in close contact with each other.
Thus, the conductive substance adsorbing layer 20 is formed on the surface of the resin film substrate 12. At this time, a method for forming the conductive substance adsorbing resin precursor layer 18 in close contact with the resin film substrate 12 by forming the adhesion auxiliary layer 16 in a pattern by a printing method, an inkjet method, or the like, or A method of forming a conductive substance adsorbing resin precursor layer 18 in a pattern by a printing method, an ink jet method or the like to form a conductive substance adsorbing 20 pattern in close contact with the resin film substrate 12, or an adhesion auxiliary layer 16 and the conductive substance-adsorbing resin precursor layer 18 are uniformly formed, and by applying energy in a pattern, the conductive substance-adsorbing resin layer 20 in close contact with the resin film substrate 12 is formed in a pattern. The

A step of forming a through hole (hole) to connect such a resin film laminate to the wiring on the back surface side of the resin film substrate 12, a metal is imparted to the conductive substance adsorbing resin layer 20 by adding a metal The resin film base material 10 with a metal pattern can be obtained by performing the step of forming the layer 22. In addition, after performing the process of making a hole with respect to the resin-made support body 1 as needed, you may form the contact | adherence auxiliary | assistant layer 16, the electroconductive substance adsorbing layer 20, or its precursor layer 18, and resin film You may carry out after forming the contact | adherence auxiliary | assistant layer 16, the electroconductive substance adsorption layer 20, or its precursor layer 18 in the at least 1 surface of the base material 12. FIG.
Each process, that is, the process of forming each layer or the process of making a hole may be performed sequentially or simultaneously if necessary, and may be omitted if unnecessary. However, from the viewpoint of providing stronger adhesion, the formation process of the adhesion auxiliary layer 16 is performed at the same time as or after the formation process of the resin film substrate 12, the formation process or adhesion of the resin film substrate 12. It is preferable that the step of forming the conductive substance-adsorbing resin precursor layer 18 is performed simultaneously with or after the step of forming the auxiliary layer 16.

Next, the metal layer 22 is provided to obtain a resin film with a metal layer as shown in FIG. This step is a metal layer forming step in which electroless plating, exchange plating, electroplating, or the like is performed using the metal (conductive material) applied to the conductive material-adsorbing resin layer 20, and the use of the metal layer Depending on the above, a step of connecting to the wiring on the back surface side through the hole, a step of performing a heat treatment after forming the conductor layer, and the like can be added as desired.
These steps can be performed in any order as necessary, and the respective steps can be performed sequentially or simultaneously if necessary, and can be omitted if unnecessary.
In the manufacturing method of the resin film with a metal layer of this invention, the process of forming a metal layer by the plating method etc. is made | formed by the process after the formation process of an electroconductive substance adsorption resin layer, It is characterized by the above-mentioned.
Hereinafter, the components of each layer and each process will be described in more detail.

(Resin film substrate)
The resin film used as a base material in the present invention is a resin film that is usually used for an electronic substrate, such as glass epoxy, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, paper, liquid crystal polymer, etc. In addition, phenol resin, epoxy resin, imide resin, BT resin, PPE resin, tetrafluoroethylene resin, liquid crystal resin, polyester resin, PEN, aramid resin, polyamide resin, polyethersulfone, triacetyl can be used as the resin. Any resin that can be molded into a film, such as cellulose, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polybutadiene, and polyacetylene, can be used.
When the method for producing a resin film substrate with a metal pattern of the present invention is applied to, for example, a method for producing a flexible printed circuit board, a resin film substrate such as polyimide, liquid crystal polymer, or polyethylene terephthalate used for them is usually used. It is preferable to use it.

These resin film layers 12 may be formed into a film shape so as to have a uniform and smooth surface. For the purpose of improving the adhesion with the adhesion adhering layer 16 as an upper layer, fine irregularities are formed after film formation. A polishing step may be performed to apply the resistance.
Examples of the polishing process for the support surface include mechanical polishing such as buff polishing, belt polishing, and pumice polishing. Furthermore, chemical polishing, chemical mechanical polishing, electrolytic polishing, or the like may be performed instead of the mechanical polishing. Further, plasma treatment for generating active groups on the surface of the film, corona treatment, UV treatment, ozone treatment, flame treatment or treatment for chemically decomposing and activating the surface may be used in combination. In the case of a polyimide film, treatment with a polar organic solvent such as hydrazine, N-methylpyrrolidone, sodium hydroxide solution or potassium hydroxide solution or a strong alkali is also performed.

  From the viewpoint of improving the physical properties of the conductive layer formed, a resin film having an average roughness (Rz) of 3 μm or less measured by JIS B 0601 (1994), 10-point average height method is used. It is preferable that Rz is 1 μm or less. If the surface smoothness of the substrate is within the above value range, that is, if there is substantially no unevenness, the circuit is extremely fine (for example, a circuit pattern with a line / space value of 25/25 μm or less). It is used suitably when manufacturing. The resin film having a thickness of 3 μm to 500 μm is preferably used flexibly as the film, more preferably in the range of 5 μm to 300 μm, and more preferably in the range of 7 μm to 200 μm. preferable.

  In order to directly interact with the conductive substance adsorbing resin precursor layer 18, an active species that generates an active site that can interact may be added to the resin film substrate 12. When it is desired to directly interact the resin film substrate 12 and the conductive substance adsorbing resin precursor layer 18 in close contact with each other, the conductive substance adsorbing resin precursor layer 18 when energy is imparted to the resin film in advance when the resin film is formed. An active species that generates an active site for interaction with the resin may be added, or a skeleton that generates an active species may be included in the resin skeleton.

Examples of generating active species in the resin skeleton include an example using a polyimide substrate containing a polyimide having a polymerization initiation site in the skeleton as shown below (hereinafter referred to as a specific polyimide as appropriate). It is done.
The base material comprising this specific polyimide is prepared as a polyimide precursor compound, and after this polyimide precursor compound is molded into a desired substrate shape, it is subjected to heat treatment to a polyimide precursor polyimide structure (specific polyimide). It can be produced by changing. Although the specific example of the specific polyimide produced as mentioned above is shown, it is not limited to these.

As the compound used when a material capable of generating active species is added to the resin material, either a thermal polymerization initiator or a photopolymerization initiator can be used.
Examples of the polymerization initiator that can be used here include peroxide initiators such as benzoyl peroxide and azoisobutyronitrile, and azo initiators. The photopolymerization initiator may be a low molecule or a polymer, and generally known ones are used. In addition, when the resin film can generate an active site that interacts with the metal-adsorbing resin precursor layer by applying energy, that is, when a resin having a polymerization initiation site in the skeleton described above is used, these activities are performed. It is not necessary to add seeds.

  Examples of the low molecular weight photopolymerization initiator include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Benzophenone, (benzophenones such as 4,4'-bisdimethylaminobenzophenone; benzyl ketals such as benzyldimethyl ketal and hydroxycyclohexyl phenyl ketone; Michler's ketone; benzoylbenzoate; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl Benzoins such as ethers; α-acyloxime esters, tetramethylthiuram monosulfide, trichloromethyltriazine and -chlorothioxanthone, 2-methyl Known radical generators such as thioxanthone such as oxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, etc. Usually, sulfonium salts and iodonium salts used as photoacid generators are also used as radical generators by light irradiation. In order to operate, these may be used in the present invention.

  Further, for the purpose of increasing sensitivity, a sensitizer may be used in addition to the radical photopolymerization initiator. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.

  Examples of the polymer photo radical generator include a polymer compound having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927, and a polymerization initiating group described in JP-A-2004-161995. A polymer formed by pendating a chain can also be used by mixing in a resin film. Specifically, this polymer is a polymer having a functional group (polymerization initiating group) having a polymerization initiating ability in the side chain and a crosslinkable group (hereinafter referred to as a polymerization initiating polymer). The polymer chain has a polymerization initiating group bonded thereto, and the polymer chain is immobilized by a crosslinking reaction. Specific examples include those described in paragraph numbers [0011] to [0158] of JP-A No. 2004-161995. Specific examples of particularly preferred polymerization initiating polymers include those having the structural units shown below.

  The molecular weight of the polymer is not immediately limited as long as it can be uniformly mixed with the resin film of the base material, but the weight average molecular weight is preferably 500,000 or less, more preferably 300,000 or less, and more preferably 100,000 or less. Is more preferable. When the molecular weight is 500,000 or more, phase separation may easily occur when mixing with the resin film of the base material.

  The amount of the polymerization initiator to be contained in the resin film substrate is selected according to the use and configuration of the conductive substance-adsorbing resin layer for forming the interaction, but in general, it is solid in the resin film substrate. The minute is preferably about 0.1 to 50% by mass, and more preferably about 1.0 to 30.0% by mass.

(Adhesion auxiliary layer)
In the present invention, it is preferable to provide a conductive substance-adsorbing resin layer for the purpose of efficiently performing a plating method for forming a metal layer on the surface of the resin film substrate 12, but the conductive substance-adsorbing resin layer and the resin film are provided. For the purpose of improving the adhesion to the substrate, the adhesion auxiliary layer 16 can be provided.
The adhesion auxiliary layer includes a well-known insulating resin composition that has been mainly used as a conventional multilayer laminate, build-up substrate, or flexible substrate, and a conductive substance-adsorbing resin precursor layer by the following energy application step. It includes a compound that can generate an active site that interacts to form a chemical bond and can be in close contact with the conductive substance-adsorbing resin precursor layer.
That is, as a typical structure of the adhesion auxiliary layer, one containing a polymerization initiator capable of generating an active site in the film-forming insulating resin composition can be mentioned.

The insulating resin composition used for forming the adhesion auxiliary layer may be the same as or different from the compound forming the resin film substrate 12. However, it prevents stress from being applied during heat history such as heat treatment to improve adhesion to the resin film substrate, annealing treatment after layer formation, wiring formation, etc., and solder reflow treatment. For the purpose, it is preferable to use those having the same thermophysical properties such as glass transition point, elastic modulus, and linear expansion coefficient, or exhibiting similar behavior.
Specifically, for example, it is preferable to use one or more kinds of resins constituting the adhesion auxiliary layer in the same manner as the resin forming the resin film base material in terms of adhesion. In addition, the conductive material adsorbing resin precursor layer and / or the active point that interacts with the resin film base material to form a chemical bond is generated in the next energy application step to be in close contact with the metal layer. Compounds that can be included.

  As other components, inorganic particles and organic particles may be added for the purpose of increasing the strength of the adhesion auxiliary layer and improving the electrical characteristics. In the present invention, a resin film substrate may form an interlayer insulating film, but the insulating resin composition used here has an insulating property that can be used for a known insulating film. Even if it is not a complete insulator, it may be applied to the present invention as long as it is a resin having insulation properties according to the purpose.

In the present invention, the insulating resin that can be used for forming the resin film substrate 12, the adhesion auxiliary layer 18 and the like may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, and the like.
Further, examples of the epoxy resin include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolak type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, Examples thereof include cyclopentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.
Examples of the polyolefin resin include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins.

  Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like. Other thermoplastic resins include (1) 1,2-bis (vinylphenylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or a modified resin of this with a polyphenylene ether resin (Satoru Ama et al., Journal of Applied). Polymer Science Vol. 92, 1252-1258 (2004)). (2) Liquid crystalline polymers, specifically Kuraray Bexter. (3) Fluororesin (PTFE).

  The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is performed for the purpose of compensating for each defect and producing a superior effect. For example, thermoplastic resins such as polyphenylene ether (PPE) have a low resistance to heat, and are therefore alloyed with thermosetting resins. For example, it is used for alloying PPE with epoxy and triallyl isocyanate, or alloying PPE resin into which a polymerizable functional group is introduced and other thermosetting resins. Cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but it is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. Details of these are described in Electronic Technology 2002/9, P35. A thermosetting resin containing an epoxy resin and / or a phenol resin and a thermoplastic resin containing a phenoxy resin and / or polyether sulfone (PES) are also used to improve dielectric properties.

The adhesion auxiliary layer 16 may contain a compound having a polymerizable double bond in order to promote crosslinking, specifically, an acrylate or methacrylate compound, and a polyfunctional one is particularly preferable. In addition, a thermosetting resin or a thermoplastic resin as a compound having a polymerizable double bond, for example, epoxy resin, phenol resin, polyimide resin, polyolefin resin, fluororesin, etc., using methacrylic acid or acrylic acid, A resin obtained by subjecting a part of the resin to (meth) acrylation reaction may be used.
In the adhesion auxiliary layer 16 in the present invention, a composite (composite) of a resin and other components is used to enhance the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical characteristics and the like of the resin coating. Material) can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluorine resin, polyphenylene oxide resin, and the like.

Further, the adhesion auxiliary layer 16 may be filled with a filler used for a general resin material for wiring boards, for example, an inorganic filler such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, or a cured epoxy resin. One or two or more organic fillers such as a crosslinked benzoguanamine resin and a crosslinked acrylic polymer may be blended.
Moreover, you may add 1 type, or 2 or more types of various additives, such as a coloring agent, a flame retardant, adhesiveness imparting agent, a silane coupling agent, antioxidant, and an ultraviolet absorber, as needed.
When adding these materials, it is preferable to add all in the range of 0-200 mass% with respect to resin, More preferably, it adds in the range of 0-80 mass%. In the case where the resin component constituting the adhesion auxiliary layer 16 exhibits the same or similar physical property values to heat and electricity as the adjacent resin film substrate or the like, it is not always necessary to add these additives. On the other hand, when it exceeds 200% by mass, characteristics such as strength specific to the resin are deteriorated.

In order to interact with the conductive substance-adsorptive resin precursor layer 18 described later, an active species that generates an active site that can interact may be added to the adhesion auxiliary layer 16.
As an example of the active species, any of the thermal polymerization initiator and the photopolymerization initiator that can be used when interacting with the resin film and the conductive substance-adsorbing resin precursor layer can be used.

In general, the thickness of the adhesion auxiliary layer 2 in the present invention is preferably in the range of 0.1 μm to 100 μm, and more preferably in the range of 0.1 μm to 10 μm.
When the adhesion auxiliary layer 16 is provided, if the thickness is in the above general range, sufficient adhesion strength with an adjacent layer can be obtained, and it is a thin layer compared to using a general adhesive. Adhesiveness similar to that of an adhesive layer having a predetermined thickness can be achieved, and a resin film with a metal pattern can be formed with a thin overall thickness and excellent adhesiveness.

  The adhesion auxiliary layer 16 is formed on the resin film substrate 12 on one or both surfaces as required. As the forming method, any of a coating method, a transfer method, and a printing method can be applied. In the case of forming by a transfer method, a transfer film having a two-layer structure of a conductive substance-adsorbing resin precursor layer and an adhesion auxiliary layer can be produced, and transferred and formed at a time by a laminating method.

  The step of forming the adhesion assisting layer 16 by the transfer method will be described. First, each component used for forming the adhesion assisting layer is dissolved in an appropriate solvent, prepared as a varnish-like composition, or mutually compatible with a solution. Prepare a coating solution prepared to improve coatability by preparing a coating solution prepared in a state, apply this onto a suitable temporary support, dry it, and transfer for adhesion auxiliary layer formation It can be formed by forming a film, then laminating the film on the resin film layer 12, transferring only the adhesion auxiliary layer 16 to the surface of the resin film layer 12, and peeling the temporary support. At this time, since the adhesion auxiliary layer is previously formed into a film, the thickness accuracy of the layer is increased, and the handleability and alignment accuracy are also improved. Therefore, this transfer method is suitably used for forming the adhesion auxiliary layer 16. The

A common organic solvent is used as a solvent for preparing the coating solution. As the organic solvent, either a hydrophilic solvent or a hydrophobic solvent can be used, but a thermosetting resin that forms the adhesion auxiliary layer 16 and a solvent that dissolves the thermoplastic resin are useful. Specifically, alcohol solvents such as methanol, ethanol, 1-methoxy-2-propanol, isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Ether solvents such as ethyl ether and nitrile solvents such as acetonitrile are preferred.
Furthermore, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ethylene glycol monomethyl ether, tetrahydrofuran and the like can be used. Furthermore, ordinary solvents such as ethyl acetate, butyl acetate, isopropyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol In addition to aromatic hydrocarbons such as toluene, xylene, benzene, naphthalene, hexane, cyclohexane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. can be used alone or in combination of two or more.

The blending amount of the coating liquid or the solvent for varnishing is determined from the viewpoint of the viscosity and workability of the coating liquid or varnish, coating properties, and the drying time and working efficiency. The amount is preferably 5 parts by weight or more and 3000 parts by weight or less, more preferably 10 to 2000 parts by weight, and still more preferably 10 to 900 parts by weight with respect to parts by weight.
In addition, the viscosity of the composition is preferably 5 to 5000 cps, more preferably 10 to 2000 cps, and still more preferably 10 to 1000 cps from the viewpoints of the coating property, workability, and drying time of the composition.
As a method for preparing the coating liquid composition in a varnish form, it can be prepared using a known method such as a mixer, a bead mill, a pearl mill, a kneader, or a three-roll. Various compounding ingredients may be added all at the same time, the order of addition may be set as appropriate, or some compounding ingredients may be added after pre-kneading if necessary. .

Coating onto a temporary support for transfer film formation is performed by a conventional method, for example, blade coating method, rod coating method, squeeze coating method, reverse roll coating method, transfer coal coating method, spin coating method, bar coating. Examples thereof include known coating methods such as a method, an air knife method, a gravure printing method, and a spray coating method.
The method for removing the solvent is not particularly limited, but it is preferably performed by evaporation of the solvent. As a method for evaporating the solvent, methods such as heating, decompression, and ventilation are conceivable. Among these, it is preferable to evaporate by heating from the viewpoint of production efficiency and handleability, and more preferable to evaporate by heating with ventilation.
For example, it is applied to one side of the temporary support described below, and is heated and dried at 80 ° C. to 200 ° C. for 0.5 to 10 minutes to remove the solvent, thereby eliminating the semi-cured and non-sticky state. A film is preferred.

The base film that can be used as a temporary support for transfer film includes polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyester such as polyethylene terephthalate, resin sheet such as polyamide, polyimide and polycarbonate, and surface adhesiveness such as release paper. Processed paper, copper foil, metal foil such as aluminum foil, and the like.
The thickness of the temporary support is generally 2 to 200 μm, more preferably 5 to 50 μm, and still more preferably 10 to 30 μm. If the temporary support is too thick, there is a problem in handling properties when actually transferring using this laminated film, particularly when laminating this laminated film on a predetermined substrate or wiring. There is.

The sheet surface constituting the temporary support may be subjected to a release treatment in addition to the mat treatment and the corona treatment. Furthermore, a protective layer may be formed. As the resin film for forming the protective layer, the same material as that used for the temporary support may be used, or a different material may be used. Like the temporary support, it is preferable to use surface adhesiveness such as polyethylene, polyvinyl chloride, polyolefin such as polypropylene, polyester such as polyethylene terephthalate, resin sheet such as polyamide and polycarbonate, and release paper. Examples include controlled processed paper, copper foil, and metal foil such as aluminum foil.
The thickness of the protective layer (protective film) is generally 2 to 150 μm, more preferably 5 to 70 μm, still more preferably 10 to 50 μm. Further, either the thickness of the protective film or the thickness of the support base film may be thicker than the other.
The protective film may be subjected to a release treatment in addition to a mat treatment and embossing.
In addition, by making the width of the transfer film support about 5 mm longer than the width of the insulating film or polymer precursor layer, it is possible to prevent adhesion of the resin in the laminate when laminating with other layers. In addition, there are advantages such as easy peeling of the base film constituting the temporary support in use.

The adhesion auxiliary layer is laminated under reduced pressure, and the system may be a batch system or a continuous system using a roll-shaped laminated film. In addition, when the adhesion auxiliary layer is formed on both surfaces of the resin support, it may be laminated on one side or on both sides simultaneously, but it is preferable to laminate on both sides simultaneously.
The lamination conditions as described above vary depending on the hot melt viscosity and thickness of the composition constituting the room temperature solid adhesion auxiliary layer 16 in the present invention, and the thickness of the resin film. It is preferable that the pressure is 1 to 10 kgf / cm ² and the lamination is performed under a reduced pressure of 20 mmHg or less.

Regarding the thickness of the temporary support, the thicker the temporary support (transfer film support), the better the surface smoothness of the resin composition after lamination, but it is not preferable that the thickness is too large from the viewpoint of thermal conductivity. From such a viewpoint, the thickness of the temporary support is preferably equal to or greater than the thickness of the adhesion assisting layer and 75 μm or less.
After lamination, the temporary support is peeled off after cooling to near room temperature.
When transferring by laminating, the temperature is preferably 80 ° C to 250 ° C, more preferably 100 ° C to 200 ° C, still more preferably 110 ° C to 180 ° C. Moreover, the applied pressure is preferably 0.5 to 3 MPa, more preferably 0.7 to 2 MPa. The time for applying pressure is preferably 10 seconds to 1 hour, more preferably 15 seconds to 30 minutes. Moreover, in order to improve the adhesion | attachment in a laminate, it is preferable to carry out under reduced pressure, such as a vacuum lamination. Moreover, when using the resin film with a metal layer in this invention for formation of fine wiring, it is preferable to laminate the electroconductive substance adsorbing resin film of this invention used as the raw material in a clean room.

  When the adhesion assisting layer 16 is provided on the resin film by coating or printing, the coating liquid for forming the adhesion assisting layer 16 is applied or printed on one or both surfaces of the resin film until a predetermined thickness is obtained. You may provide by repeating. Further, when the adhesion auxiliary layer 16 is provided by coating, two layers of the adhesion auxiliary layer 16 and a conductive substance adsorbing resin precursor layer described later may be applied simultaneously. The coating is carried out in the same manner as when coated on the support, for example, blade coating method, rod coating method, squeeze coating method, reverse roll coating method, transfer coal coating method, spin coating method, bar coating method. Well-known coating methods such as air knife method, gravure printing method, spray coating method, dispenser method, dip method and the like can be mentioned. Moreover, when performing by printing, it can also print by methods, such as the inkjet method other than normal gravure printing. Moreover, after apply | coating to a resin film, it may dry enough in order to block the adhesion | attachment of a resin film, a close_contact | adherence auxiliary | assistant layer, or a close_contact | adherence auxiliary | assistant layer.

In addition, after the adhesion auxiliary layer 16 is formed on the substrate, some energy may be applied to perform the curing process. Examples of energy to be given include light, heat, pressure, electron beam, etc. In this embodiment, heat or light is generally used. In the case of heat, heat of 100 ° C. to 300 ° C. is applied for 10 minutes to 120 minutes. Can do. The conditions for heat curing differ depending on the type of the material of the resin film, the type of the resin composition constituting the adhesion auxiliary layer 16 and the like, and depending on the curing temperature of these forming materials, but more preferably at 120 to 220 ° C. for 20 minutes. Selected in the range of ~ 120 minutes.
This curing treatment step may be performed immediately after the formation of the adhesion auxiliary layer, or may be performed after other steps performed after the formation of the adhesion auxiliary layer, for example, after forming the conductive substance-adsorbing resin layer. .

As examples of the compound that can generate active species contained in the adhesion auxiliary layer 16, both a thermal polymerization initiator and a photopolymerization initiator can be used. As these examples, those described in the section of the resin film can be used. Moreover, when the adhesion auxiliary layer 16 is made of a material capable of generating an active site that interacts with the conductive substance-adsorbing resin precursor layer by applying energy, it is not necessary to add these active species separately.
In addition to the above compounds, various compounds can be added to the adhesion auxiliary layer 16 depending on the purpose as long as the effects of the present invention are not impaired. Examples of such additives include various materials such as rubber that can relieve stress during heating, substances such as SBR latex, binders for improving film properties, plasticizers, surfactants, viscosity modifiers, and the like. Compounds.

  After the adhesion auxiliary layer 16 is formed, the surface may be roughened by a dry method and / or a wet method for the purpose of improving the adhesion with the conductive substance adsorbing resin layer or the precursor layer formed on the surface. Examples of the dry roughening method include mechanical polishing such as buffing and sandblasting, plasma etching, and the like. On the other hand, the wet roughening method includes chemical treatment such as a method using an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, a strong base or a resin swelling solvent. .

(Formation of conductive material adsorbing resin layer)
After the adhesion auxiliary layer is formed, a conductive substance-adsorbing resin precursor layer 18 is provided on the surface and energy is applied to form a bond by interaction with the conductive substance-adsorbing resin precursor layer 18. An active point is generated in the adhesion auxiliary layer 16 to form the conductive substance adsorbing resin layer 20 formed by bonding with the adhesion auxiliary layer 16.

(Conductive substance adsorbing resin precursor layer)
The conductive substance-adsorbing resin precursor layer in the present invention contains a compound having a functional group capable of adsorbing metal ions or metal fine particles (hereinafter, appropriately referred to as a metal-adsorbing functional group). This compound preferably has a reactive functional group capable of forming a chemical bond with an active site generated when energy is applied to the resin support 1 or the adhesion auxiliary layer 16. Specifically, the reactive compound contained in the conductive substance-adsorbing resin precursor layer 18 is a compound (polymerizable compound) capable of generating a graft polymer by applying energy such as exposure, or adjacent by applying energy. Reactive compounds such as compounds that can form a cross-linked structure with the layer to be improved and improve the adhesion between them, and polymer compounds produced by these reactive compounds include metal ions or metal fine particles. Because of the attachment, the reactivity is such that a polymerization reaction or a cross-linked structure can be formed, and a partial structure necessary for bonding to the adhesion auxiliary layer 16, such as “unsaturated double bond capable of radical polymerization”. Use a compound that has both “bond” and the “metal-adsorptive functional group” necessary for attaching metal ions or metal fine particles to be described later. Preferred.

A representative compound among the reactive compounds is a polymerizable compound capable of undergoing a polymerization reaction. The polymerizable compound is a compound having an unsaturated double bond capable of radical polymerization in the molecule.
-Radical polymerizable unsaturated double bond-
Examples of the functional group containing “radical polymerizable unsaturated double bond” include a vinyl group, a vinyloxy group, an allyl group, an acryloyl group, and a methacryloyl group. Among these, the acryloyl group and the methacryloyl group are highly reactive, and good results are obtained.
As the unsaturated compound capable of radical polymerization, any compound having a radical polymerizable group can be used. For example, an acrylate group, a methacrylate group, a monomer having a vinyl group, a macromer, a polymerizable unsaturated group, and the like. Oligomers and polymers having groups can be used.
In addition, as another embodiment of the reactive compound, an oligomer or polymer having a reactive active group in the molecule, for example, an oxetane group, an epoxy group, an isocyanate group, a functional group containing active hydrogen, an active group in an azo compound, or the like. Examples thereof include a compound or a combination of a crosslinking agent and a crosslinking compound.
It is more preferable to use a reactive compound having the above functional group and a weight average molecular weight of 1000 or more, more preferably 2000 or more, more preferably 3000 or more. It is preferable to use one. When the conductive material adsorbing resin precursor layer is formed at a weight average molecular weight of 1000 or less, the reactive compound easily diffuses or evaporates into the adhesion auxiliary layer 16, and uniform exposure occurs because it easily becomes liquid. Hard to do. On the other hand, the weight average molecular weight is preferably 300,000 or less, more preferably 200,000 or less, and still more preferably 100,000 or less. In the case of 300,000 or more, since the reactivity with respect to the active sites is poor, it is difficult to form a bond, and sufficient adhesion to the adhesion auxiliary layer 16 or the resin film cannot be obtained.

-Metal adsorbing functional group-
The reactive compound further needs to have a metal-adsorbing functional group that is a partial structure to which metal ions or metal fine particles can be attached.
A functional group capable of interacting with a metal ion or a metal fine particle is a functional group having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group. An acidic group that has or can be dissociated into a negative charge is included. These adsorb with metal ions or fine metal particles in the form of counter ions of dissociating groups. In addition, a functional group that does not generate a proton by dissociation may be used. Specifically, the interactive group is preferably a group capable of forming a multidentate coordination, a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, or the like.
More specifically, the nitrogen-containing functional group includes imidazole group, imino group, imide group, urea group, pyridine group, primary to tertiary amino group, ammonium group, pyrrolidone group, amide group, amidino group, triazine. Examples include a functional group containing a ring structure, a functional group containing an isocyanuric structure, a urethane group, a nitro group, a nitroso group, an azo group, a diazo group, an azido group, a cyano group, and a cyanate group (R—O—CN). Examples of the oxygen functional group include a hydroxyl group (including phenol), an ether group, a carbonyl group, an ester group, a functional group including an N-oxide structure, a functional group including an S-oxide structure, and a functional group including an N-hydroxy structure. Examples of the sulfur-containing functional groups include thiol groups, thioether groups, thiourea groups, thioxy groups, sulfoxide groups, sulfone groups, sulfite groups, sulfo groups. Functional group containing a Shiimin structure, functional groups containing a sulfoxide salt structure, such as a functional group containing a sulfonic acid ester structure. Other preferred functional groups include phosphorus-containing functional groups such as phosphine groups, carboxylic acid groups, sulfonic acid groups, and acid groups that can be dissociated into negative charges, such as phosphonic acid groups, Examples thereof include functional groups containing halogen atoms such as chlorine and bromine, unsaturated ethylene groups, and the like, and have high polarity and high adsorption ability to plating catalysts and the like, so that —O— (CH ₂ ) _n —O— A functional group containing a structure represented by (wherein n represents an integer of 1 to 5) or a cyano group is particularly preferred, and a cyano group is most preferred.

  From the viewpoint of physical properties, it can interact with metal ions or metal fine particles by taking nonionic polar groups such as hydroxyl groups, amide groups, sulfonamido groups, alkoxy groups, chelation and multidentate structures. Alternatively, a functional group capable of adsorbing metal fine particles and a functional group capable of inclusion, typified by crown ether, can also be applied. Furthermore, there are functional groups that can interact with the solvent held in a form typified by water of crystallization and can adsorb metals in the form of being dissolved as a salt in the solvent being held or adsorbed. included.

Specifically, (1) a method of adsorbing metal ions to a graft polymer comprising a compound having a polar group (ionic group) which is a functional group capable of interacting with a conductive material, (2) polyvinylpyrrolidone, polyvinylpyridine In addition, a solution containing a metal salt or a metal salt is added to a graft polymer composed of a nitrogen-containing or sulfur-containing polymer having a functional group capable of interacting with a conductive material such as polyvinylimidazole and a high affinity for the metal salt. There is a method of impregnation.
Furthermore, it is possible to make it easy to interact with a specific metal having a functional group capable of interacting with metal ions or metal fine particles. As a specific example, the size of the clathrate site of the clathrate compound can be matched to a certain ion, or the multidentate structure can be fixed so that a specific ion can be easily coordinated. .
Specific compounds having both “radical polymerizable unsaturated double bond” and “metal adsorbing functional group” necessary for attaching metal ions or metal fine particles to be described later have the following reactivity: Compounds can be used.

  Moreover, as a reactive compound used for formation of an electroconductive substance adsorptive resin precursor layer in this invention, the unit represented by the following formula (1) and the unit represented by the following formula (2), for example, The copolymer containing can be mentioned as a preferable thing.

In Formula (1) and Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z each independently represent a single atom. Represents a bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group. .

When R ^{1 to} R ⁵ are substituted or unsubstituted alkyl groups, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include methoxy And a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.
R ¹ is preferably a hydrogen atom, a methyl group, a hydroxy group, or a methyl group substituted with a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, a hydroxy group, or a methyl group substituted with a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom or a methyl group.

When X, Y and Z are a substituted or unsubstituted divalent organic group, the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. Is mentioned.
As the substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or these groups are substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like. Those are preferred.
The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.
Among _{them, - (CH 2) n -} (n is an integer of 1 to 3) are preferred, more preferably -CH ₂ -.
L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, and among them, those having a total carbon number of 1 to 9 are preferable. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1) or formula (1-2).

In the above formulas (1-1) and (1-2), R ^a and R ^b each independently represent a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group.

L ² is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L ² preferably has 1 to 15 total carbon atoms, and particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^2.
Specifically, methylene group, ethylene group, propylene group, butylene group, phenylene group, and those groups substituted with methoxy group, hydroxy group, chlorine atom, bromine atom, fluorine atom, etc., The group which combined these is mentioned.

  In the cyano group-containing polymerizable polymer according to the present invention, the unit represented by the formula (1) is preferably a unit represented by the following formula (3).

In the above formula (3), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond, a substituted or unsubstituted divalent organic group. Represents an ester group, an amide group, or an ether group, W represents a nitrogen atom or an oxygen atom, and L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in Formula (3), the formula (1) has the same meaning as ^{R 1} or ^{R 2} in, are the preferable examples.

Z in formula (3) has the same meaning as Z in formula (1), and the preferred examples are also the same.
Further, ^{L 1} in the formula (3) also has the same meaning as ^{L 1} in Formula (1), and preferred examples are also the same.

  As a cyano group-containing polymerizable polymer, the unit represented by the formula (3) is preferably a unit represented by the following formula (4).

In formula (4), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent a nitrogen atom or an oxygen atom. , L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in the formula (4), the formula (1) have the same meanings as ^{R 1} and ^{R 2} in, and so are the preferable examples.

L ¹ in Formula (4) has the same meaning as L ¹ in Formula (1), and the preferred examples are also the same.

In the formulas (3) and (4), W is preferably an oxygen atom.
In Formulas (3) and (4), L ¹ is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and among these, the total number of carbon atoms is 1 to 9. Are particularly preferred.

  Moreover, as a cyano group containing polymeric polymer, it is preferable that the unit represented by the said Formula (2) is a unit represented by following formula (5).

In the above formula (5), R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents a nitrogen atom or an oxygen atom, and L ² represents a substituted or unsubstituted divalent organic group. Represents a group.

R ² in Formula (5) has the same meaning as R ¹ and R ² in Formula (1), and is preferably a hydrogen atom.

L ² in formula (5) has the same meaning as L ² in formula (1), and is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. .
In particular, in Formula (5), L ² is preferably a divalent organic group having a linear, branched, or cyclic alkylene group at the site of connection with the cyano group. The organic group preferably has 1 to 10 carbon atoms.
In another preferred embodiment, L ² in Formula (5) is preferably a divalent organic group having an aromatic group at the site of connection with the cyano group. Among these, the divalent organic group is preferred. However, it is preferable that it is C6-C15.

The cyano group-containing polymerizable polymer that can be used in the present invention includes units represented by the above formulas (1) to (5), and has a polymerizable group and a nitrile group as side chains. It is a polymer having.
This nitrile group-containing polymerizable polymer can be synthesized, for example, as follows.

Examples of the polymerization reaction include radical polymerization, cationic polymerization, and anionic polymerization. From the viewpoint of reaction control, radical polymerization or cationic polymerization is preferably used.
The nitrile group-containing polymerizable polymer of the present invention includes 1) a case where the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain, and 2) a polymerization form forming the polymer main chain. And the synthesis method of the polymerizable group introduced into the side chain is different in the synthesis method.

1) When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain 1-1) An embodiment in which the polymer main chain is formed by cationic polymerization and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization, and 1-2) the polymer main chain is formed by radical polymerization. There is a mode in which the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

1-1) A mode in which polymer main chain formation is performed by cationic polymerization, and a polymerization form of a polymerizable group introduced into a side chain is radical polymerization. In the present invention, polymer main chain formation is performed by cationic polymerization, and a side chain is formed. Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into the radical polymerization is radical polymerization include the following compounds.

-Monomers used to form polymerizable group-containing units As monomers used to form polymerizable group-containing units used in this embodiment, vinyl (meth) acrylate, allyl (meth) acrylate, 4- ( (Meth) acryloylbutane vinyl ether, 2- (meth) acryloylethane vinyl ether, 3- (meth) acryloylpropane vinyl ether, (meth) acryloyloxydiethylene glycol vinyl ether, (meth) acryloyloxytriethylene glycol vinyl ether, (meth) acryloyl 1st ter Pioneer, 1- (meth) acryloyloxy-2-methyl-2-propene, 1- (meth) acryloyloxy-3-methyl-3-butene, 3-methylene-2- (meth) acryloyloxy-norbornane, 4,4′-ethylidene diphenol di (meth) acrylate, methacrolein di (meth) acryloyl acetal, p-((meth) acryloylmethyl) styrene, allyl (meth) acrylate, 2- (bromomethyl) vinyl acrylate, 2- (Hydroxymethyl) allyl acrylate and the like.

Monomers used to form nitrile group-containing units Monomers used to form nitrile group-containing units used in this embodiment include 2-cyanoethyl vinyl ether, cyanomethyl vinyl ether, 3-cyanopropyl vinyl ether, 4-cyanobutyl Vinyl ether, 1- (p-cyanophenoxy) -2-vinyloxy-ethane, 1- (o-cyanophenoxy) -2-vinyloxy-ethane, 1- (m-cyanophenoxy) -2-vinyloxy-ethane, 1- ( p-cyanophenoxy) -3-vinyloxy-propane, 1- (p-cyanophenoxy) -4-vinyloxy-butane, o-cyanobenzyl vinyl ether, m-cyanobenzyl vinyl ether, p-cyanobenzyl vinyl ether, allyl cyanide, allyl cyano Examples include acetic acid and the following compounds.

Polymerization methods include general cation polymerization methods described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 2-4 (p74) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu, Chapter 7 (p195). Can be used. In the cationic polymerization, proton acids, metal halides, organometallic compounds, organic salts, metal oxides and solid acids, and halogens can be used as initiators. As possible initiators, the use of metal halides and organometallic compounds is preferred.
Specifically, boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, tin bromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, iron chloride, Examples include dichloroethylaluminum, chlorodiethylaluminum, dichloromethylaluminum, chlorodimethylaluminum, trimethylaluminum, trimethylzinc, and methylgrineer.

1-2) A mode in which polymer main chain formation is performed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization In the present invention, polymer main chain formation is performed by radical polymerization, and the side chain Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into is cationic polymerization include the following compounds.

-Monomer used for forming polymerizable group-containing unit The same monomers as those used for forming the polymerizable group-containing unit mentioned in the embodiment 1-1) can be used.

Monomers used to form nitrile group-containing units Monomers used to form nitrile group-containing units used in this embodiment include cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 3-cyanopropyl ( (Meth) acrylate, 2-cyanopropyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 5-cyanopentyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 7-cyano Hexyl (meth) acrylate, 8-cyanohexyl (meth) acrylate, 2-cyanoethyl- (3- (bromomethyl) acrylate), 2-cyanoethyl- (3- (hydroxymethyl) acrylate), p-cyanophenyl ( (Meth) acrylate, o-cyanophenyl (meth) acrylate, m-cyanophenyl (meth) acrylate, 5- (meth) acryloyl-2-carbonitryl-norbornene, 6- (meth) acryloyl-2-carbonitryl-norbornene, 1-cyano-1- (meth) acryloyl-cyclohexane, 1,1-dimethyl-1-cyano- (meth) acrylate, 1-dimethyl-1-ethyl-1-cyano- (meth) acrylate, o-cyanobenzyl ( (Meth) acrylate, m-cyanobenzyl (meth) acrylate, p-cyanobenzyl (meth) acrylate, 1-cyanocycloheptyl acrylate, 2-cyanophenyl acrylate, 3-cyanophenyl acrylate, vinyl cyanoacetate, 1-cyano-1 -Cyclopropanecarboxylic acid Nyl, allyl cyanoacetate, allyl 1-cyano-1-cyclopropanecarboxylate, N, N-dicyanomethyl (meth) acrylamide, N-cyanophenyl (meth) acrylamide, allyl cyanomethyl ether, allyl-o-cyanoethyl ether, Examples include allyl-m-cyanobenzyl ether and allyl-p-cyanobenzyl ether.
A monomer having a structure in which a part of hydrogen of the monomer is substituted with a hydroxyl group, an alkoxy group, a halogen, a cyano group, or the like can also be used.

Polymerization methods include general radical polymerization methods described in Experimental Chemistry Course “Polymer Chemistry” Chapter 2-2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu Chapter 5 (p125). Can be used. As the initiator for radical polymerization, a high-temperature initiator that requires heating at 100 ° C. or higher, a normal initiator that starts by heating at 40 to 100 ° C., a redox initiator that starts at a very low temperature, and the like are known. In general, an initiator is preferred from the viewpoint of stability of the initiator and ease of handling of the polymerization reaction.
Usual initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, azovir-2,4-dimethylvaleronitrile.

2) When the polymerization form forming the polymer main chain is the same as the polymerization form of the polymerizable group introduced into the side chain Polymerization form forming the polymer main chain and the polymerization form of the polymerizable group introduced into the side chain Are the same, 2-1) both are cationic polymerization, and 2-2) both are radical polymerization.

2-1) Both are aspects of cationic polymerization In both aspects of cationic polymerization, as the monomer having a cyano group, the same monomers as those used for forming the nitrile group-containing unit mentioned in the aspect of 1-1) are used. Can be used.
From the viewpoint of preventing gelation during polymerization, a polymer having a cyano group is synthesized in advance, and then the polymer and a compound having a polymerizable group (hereinafter, referred to as “reactive compound” as appropriate) are reacted. And a method of introducing a polymerizable group is preferably used.

In addition, it is preferable that the polymer which has a cyano group has a reactive group as shown below for reaction with a reactive compound.
Moreover, it is preferable that the polymer having a cyano group and the reactive compound are appropriately selected so as to be a combination of the following functional groups.
Specific combinations include (polymer reactive group, functional group of reactive compound) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, Benzyl halide), (hydroxyl group, carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), etc. be able to.

Here, specifically, the following compounds can be used as the reactive compound.
That is, allyl alcohol, 4-hydroxybutane vinyl ether, 2-hydroxyethane vinyl ether, 3-hydroxypropane vinyl ether, hydroxytriethylene glycol vinyl ether, 1st terpionol, 2-methyl-2-propenol, 3-methyl-3-butenol, 3 -Methylene-2-hydroxy-norbornane, p- (chloromethyl) styrene.

2-2) Aspect in which both are radical polymerizations In a mode in which both are radical polymerizations, the synthesis method includes i) a method of copolymerizing a monomer having a cyano group and a monomer having a polymerizable group, ii) a cyano group A method of copolymerizing a monomer having a monomer and a monomer having a double bond precursor and then introducing a double bond by treatment with a base or the like; iii) reacting a polymer having a cyano group with a monomer having a polymerizable group And introducing a double bond (introducing a polymerizable group). From the viewpoint of synthesis suitability, ii) a method in which a monomer having a cyano group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like, iii) cyano In this method, a polymer having a group and a monomer having a polymerizable group are reacted to introduce a polymerizable group.

  Examples of the monomer having a polymerizable group used in the synthesis method i) include allyl (meth) acrylate and the following compounds.

  Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic group having a polymerizable group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. This is a leaving group, and the elimination reaction referred to here is one in which C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Further, in the synthesis method of ii), in order to convert the double bond precursor into a double bond, as shown below, a method for removing the leaving groups represented by B and C by elimination reaction, That is, a reaction in which C is extracted by the action of a base and B is eliminated is used.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

In the synthesis method of iii), the monomer having a polymerizable group to be reacted with a polymer having a cyano group varies depending on the type of the reactive group in the polymer having a cyano group, but has the following combinations of functional groups: Can be used.
That is, (reactive group of polymer, functional group of monomer) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide), (hydroxyl group) , Carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group) and the like.
Specifically, the following monomers can be used.

As for the polymer in this invention synthesize | combined as mentioned above, it is preferable that the ratio of a polymeric group containing unit and a cyano group containing unit is the following ranges with respect to the whole copolymerization component.
That is, it is preferable that a polymeric group containing unit is contained with 5-50 mol% with respect to the whole copolymerization component, More preferably, it is 5-40 mol%. If it is 5 mol% or less, the reactivity (curability and polymerizability) is lowered, and if it is 50 mol% or more, it is easily gelled during synthesis and is difficult to synthesize.
Moreover, it is preferable that a cyano group containing unit is contained by 1-95 mol% with respect to the whole copolymerization component, More preferably, it is 10-95 mol%.

The polymer in the present invention may contain other units in addition to the cyano group-containing unit and the polymerizable group-containing unit. As the monomer used for forming the other unit, any monomer can be used as long as it does not impair the effects of the present invention.
That is, as monomers, acrylic resin skeleton, styrene resin skeleton, phenol resin (phenol-formaldehyde resin) skeleton, melamine resin (melamine and formaldehyde polycondensate) skeleton, urea resin (urea and formaldehyde polycondensate) skeleton, polyester Resin skeleton, polyurethane skeleton, polyimide skeleton, polyolefin skeleton, polycycloolefin skeleton, polystyrene skeleton, polyacryl skeleton, ABS resin (acrylonitrile, butadiene, styrene polymer) skeleton, polyamide skeleton, polyacetal skeleton, polycarbonate skeleton, polyphenylene ether skeleton , Polyphenylene sulfide skeleton, Polysulfone skeleton, Polyether sulfone skeleton, Polyarylate skeleton, Polyetheretherketone skeleton, Polyamideimide skeleton If monomers that can form a chain structure may be used any monomer.
However, when the polymerizable group is introduced by reacting with the polymer as described above, a small amount of reactive portion remains when it is difficult to introduce 100%, so this becomes the third unit. There is a possibility.

Specifically, when the polymer main chain is formed by radical polymerization, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Unsubstituted (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, Halogen-substituted (meth) acrylic esters such as 2-chloroethyl (meth) acrylate, ammonium group-substituted (meth) acrylic esters such as 2- (meth) acryloyloxyethyltrimethylammonium chloride, butyl (meth) acrylamide, Iso (Meth) acrylamides such as propyl (meth) acrylamide, octyl (meth) acrylamide, dimethyl (meth) acrylamide, styrenes such as styrene, vinylbenzoic acid, p-vinylbenzylammonium chloride, N-vinylcarbazole, vinyl acetate, Vinyl compounds such as N-vinylacetamide and N-vinylcaprolactam, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2 -Hydroxyethyl (meth) acrylate etc. can be used.
Moreover, the macromonomer obtained using the monomer of the said description can also be used.

  When the polymer main chain is formed by cationic polymerization, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol vinyl ether, di (ethylene glycol) vinyl ether, 1,4-butanediol vinyl ether, 2-chloroethyl vinyl ether, 2 -Vinyl ethers such as ethylhexyl vinyl ether, vinyl acetate, 2-vinyloxytetrahydropyran, vinyl benzoate, vinyl butyrate, styrenes such as styrene, p-chlorostyrene, p-methoxystyrene, allyl alcohol, 4-hydroxy-1- Terminal ethylenes such as butene can be used.

  The weight average molecular weight of the polymerizable polymer in the present invention is preferably from 1,000 to 700,000, more preferably from 2,000 to 300,000. Further, it is preferable to use a polymer having a degree of polymerization of 10-mer or more, and more preferably a 20-mer or more. Moreover, 7000-mer or less is preferable, 3000-mer or less is preferable, 2000-mer or less is preferable, and 1000-mer or less is preferable.

Specific examples of the cyano group-containing polymerizable polymer that can be used in the present invention are shown below, but are not limited thereto.
In addition, as for the weight average molecular weight of these specific examples, all are the range of 3000-100000.

Here, for example, in the compound 2-2-11 in the specific example, acrylic acid and 2-cyanoethyl acrylate are dissolved in, for example, N-methylpyrrolidone, and the polymerization initiator is, for example, azoisobutyronitrile (AIBN). ) And then glycidyl methacrylate can be synthesized by addition reaction using a catalyst such as benzyltriethylammonium chloride and a polymerization inhibitor such as tertiary butylhydroquinone. .
Further, for example, in the compound 2-2-19 in the above specific example, the following monomers and p-cyanobenzyl acrylate are dissolved in a solvent such as N, N-dimethylacrylamide, and polymerization is initiated such as dimethyl azoisobutyrate. It can be synthesized by performing radical polymerization using an agent and then dehydrochlorinating using a base such as triethylamine.

  These polymerizable polymers can have a polar group in a range satisfying the water absorption of the polymerizable polymer of the present invention in addition to the polymerizable group and the interactive group. By having the polar group, the adhesion between the polymerizable polymer layer and the protective layer can be improved when the protective layer is provided after the metal film is formed by the steps described later.

When the polymerizable polymer that can be used in the present invention is added to an alkaline solution having a pH of 12 and stirred for 1 hour and the decomposition of the polymerizable group site is 50% or less, it can be washed with a highly alkaline solution. it can.
The molecular weight (Mw) of the reactive compound that can be used in the present invention is preferably 1000 or more and 300,000 or less, preferably 2000 or more and 200,000 or less, and more preferably 3000 or more and 100,000 or less.

In addition to the above reactive compounds, the conductive substance-adsorbing resin precursor layer is not limited to the above-described reactive compound. Various compounds such as an agent and a viscosity modifier can be contained. The reactive compound is 2% by mass to 50% by mass in the coating liquid composition for forming a precursor layer in a state before the conductive material adsorbing resin precursor layer is formed and energy is applied. It is preferable.
Further, when the conductive substance-adsorbing resin precursor layer 18 is formed by coating and drying, it is preferable that these reactive compounds in the precursor layer are contained in an amount of 50% by weight or more in terms of solid content, more preferably It is 60% by weight or more, more preferably 70% by weight or more. When the content of the reactive compound in the formed precursor layer is less than 50% by weight, there is a concern that the reaction to the active site is impaired and the effect of the present invention cannot be sufficiently obtained.

In addition to the reactive compound, the conductive substance-adsorbing resin precursor layer 18 may include, for example, a polymerization inhibitor and a binder for improving film properties, as long as the effects of the present invention are not impaired. Various compounds such as a plasticizer, a surfactant, and a viscosity modifier can be contained.
Polymerization inhibitors that can be added to the conductive substance-adsorbing resin precursor layer 18 as necessary include hydroquinone, ditertiary butyl hydroquinone, and 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone. Hydroquinones such as p-methoxyphenol, phenols such as phenol, benzoquinones, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy free radical), free radicals such as 4-hydroxy TEMPO, phenothiazine , Nitrosamines such as N-nitrosophenylhydroxyamine and its aluminum salt, and catechols.

In addition, a curing agent and / or a curing accelerator may be added to the conductive substance adsorbing resin precursor layer 18 as necessary in order to accelerate the curing of the adhesion auxiliary layer 16 provided adjacent thereto. Can do.
For example, as a curing agent and / or a curing accelerator when the adhesion auxiliary layer 16 contains an epoxy compound, in the polyaddition type, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, polyamide, an acid anhydride, phenol Examples of catalyst types such as phenol novolac, polymercaptan, compounds having two or more active hydrogens include aliphatic tertiary amines, aromatic tertiary amines, imidazole compounds, and Lewis acid complexes.

Curing agents that start curing with heat, light, moisture, pressure, acid, base, etc., and curing accelerators include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamidoamine, mensendiamine, isophorone. Diamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) Methane, bis (4-aminocyclohexyl) methane, m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate) ), Methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, polyazeline acid anhydride, phenol novolak, xylylene novolak, bis A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol novolak, terpene phenol novolak, Polymercaptan, polysulfide, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol-tri- -Ethylhexylate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1- Benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl S-triazine, BF ₃ monoethylamine complex, Lewis acid complex, Organic acid hydrazide, diaminomaleonitrile, melamine derivative, imidazole derivative, polyamine salt, amine imide compound, aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt, ketimine compound, etc. It is.
These curing agents and / or curing accelerators should be added up to about 0 to 50% by weight of the remaining non-volatile components from which the solvent has been removed from the viewpoints of solution applicability, adhesion to substrates and metal films, and the like. Is preferred. Further, the curing agent and / or the curing accelerator may be added directly to the adhesion assisting layer 16, and in that case, the layer formed from the polymerizable polymer and the amount added to the adhesion assisting layer (conductive substance adsorbing property). The total amount added to the resin layer) is preferably within the above range.

In addition, plasticizers, rubber components (eg CTBN), flame retardants (eg phosphorus flame retardants), diluents and thixotropic agents, pigments, antifoaming agents, leveling agents, coupling agents, etc. are added. May be. These additives can be added not only to the conductive substance adsorbing resin precursor layer 18 but also to the adhesion auxiliary layer 16 as necessary.
Properties of the polymer layer formed by applying energy to a reactive compound such as a polymerizable polymer by appropriately mixing these optional additives and the reactive compound, for example, thermal expansion coefficient, glass transition Temperature, Young's modulus, Poisson's ratio, breaking stress, yield stress, thermal decomposition temperature, etc. can be set optimally.
In particular, the conductive material-adsorptive resin layer to be formed preferably has a higher breaking stress, yield stress, and thermal decomposition temperature, so these additives are useful. The formed conductive substance-adsorptive resin layer can be measured for thermal durability by a temperature cycle test, a thermal aging test, a reflow test, and the like. For example, in the case of thermal decomposition, when exposed to a 200 ° C. environment for 1 hour It can be evaluated that it has sufficient heat durability as the weight loss of is 20% or less. In order to realize such thermal properties, the above additives are appropriately used.

The conductive substance-adsorbing resin precursor layer 18 forms a chemical bond with the adhering auxiliary layer 16 or the resin film layer 12 and an active site generated when energy is applied to form the conductive substance-adsorbing resin layer 20. The metal ions or fine metal particles may be adsorbed in advance on the metal-adsorbing functional group of the compound contained in the conductive substance-adsorbing resin precursor layer before applying energy. You may make it adsorb | suck to the metal adsorbing functional group of the compound which formed the chemical bond between the layer 16 or the resin film layer 12, and was stuck.
The thickness of the conductive substance-adsorbing resin precursor layer is preferably about 0.05 to 5 μm, more preferably 0.1 to 3 μm, and still more preferably 0.2 to 2 μm. In this range, by forming the conductive substance-adsorbing resin precursor layer, when forming the conductive substance-adsorbing resin layer after energy application in the subsequent process, sufficient adhesion strength was obtained and further formed. The strength of the coating is also maintained within a preferable range.

  As a method for forming the conductive substance adsorbing resin precursor layer 18, it can be formed by a method such as coating, transferring, printing, and the like, similar to the adhesion auxiliary layer 16. Further, when the conductive substance adsorbing resin precursor layer is provided by coating, even if the adhesion auxiliary layer 16 and the conductive substance adsorbing resin precursor layer 18 are simultaneously applied in layers, the application is sequentially performed after the adhesion auxiliary layer 16 is formed. May be formed. Similarly, when forming by transfer, a transfer film having a two-layer structure of the conductive substance adsorbing resin precursor layer 18 and the adhesion auxiliary layer 16 may be produced on a temporary support and transferred at once by a laminating method. . As a coating method, the general method described in the step of forming the adhesion auxiliary layer 16 can be used.

The solvent that can be used for the application of the conductive substance-adsorbing resin precursor layer 18 is not particularly limited as long as the compound to be used can be dissolved, and includes water or an organic solvent. An agent may be added.
Specific examples of the solvent include alcohol solvents such as water, methanol, ethanol, 1-methoxy-2-propanol, and isopropyl alcohol, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, tetrahydrofuran. Ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether, and nitrile solvents such as acetonitrile and propylonitrile are preferable. Further, amide solvents such as formamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ethylene glycol monomethyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, isopropyl acetate, methyl acetate Ester solvents such as, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, toluene, xylene, benzene, In addition to aromatic hydrocarbons such as naphthalene, hexane and cyclohexane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can also be used.
When the reactive compound used in the precursor layer is a hydrophobic compound, amide, ketone, and nitrile solvents are preferable. Specifically, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, and propionitrile preferable.
Moreover, when apply | coating a polymer composition, the solvent whose boiling point is 50-150 degreeC is preferable from handling ease.
These solvents may be used alone or in combination, but since the surface of the resin film or the adhesion auxiliary layer 16 is smooth, the resin film or the adhesion auxiliary layer 16 is used. A solvent that hardly dissolves or a combination of solvents that hardly extract active species contained in these layers is preferable.

As a guideline for selecting a solvent to be used when the conductive substance-adsorbing resin precursor layer 18 coating solution containing the polymerizable polymer or the like is applied onto the adhesion auxiliary layer 16, the solvent absorption rate of the adhesion auxiliary layer is 5 ˜25% solvent can be selected. Here, the solvent absorption rate can be determined from the change in the weight of the substrate when the substrate on which the adhesion assisting layer is formed is immersed in the solvent and pulled up after 1000 minutes.
Moreover, you may select the solvent whose swelling rate of a close_contact | adherence auxiliary | assistant layer is 10 to 45% as another standard. This swelling rate can be determined from the change in the thickness of the polymerization initiation layer when the substrate on which the adhesion assisting layer is formed is immersed in a solvent and pulled up after 1000 minutes.

  The viscosity of the coating solution is preferably adjusted to 1 to 2000 cps, more preferably 3 to 1000 cps, and more preferably 5 to 700 cps, from the viewpoint that the film thickness can be controlled more precisely. Moreover, when forming by printing, when performing by printing, besides normal gravure printing, it can also print by methods, such as an inkjet method. When printing on the electrical insulating film or the adhesion auxiliary layer 16 by a method such as a printing method or an ink jet method, it can be produced without printing in a portion where a conductor is not desired in a later step.

In the present invention, the conductive substance-adsorbing resin precursor layer 18 can be brought into close contact with the active sites generated in the resin film layer 12 or the adhesion auxiliary layer 16 by some interaction. Examples of this interaction include intermolecular interactions, ionic bonds, chemical bonds, and formation of compatible structures. Among them, those utilizing chemical bonds are preferable because of high adhesion strength.
As a method for generating an active site in the resin film or the adhesion auxiliary layer 16, energy beam irradiation such as light, electromagnetic wave, electron beam, and radiation, thermal energy, and application of pressure energy are conceivable. Specific examples include ultraviolet light irradiation, infrared light irradiation, plasma irradiation, X-ray irradiation, alpha ray irradiation, and gamma ray irradiation. Among them, irradiation with energy rays or thermal energy is preferable as a method for generating active sites, and irradiation with ultraviolet light or the like is more preferable because energy can be applied with a simple apparatus. Further, even if a special active species generating compound is not mixed in the resin film or the adhesion auxiliary layer 16, an active point is generated if high energy is applied by short wave ultraviolet light, electron beam irradiation, plasma irradiation, or the like. It is possible.

  In addition, as energy irradiation, energy such as light is applied from the conductive material adsorbing resin precursor layer side or from the opposite substrate side, or the whole is applied like thermal energy. Although it may be given by heating, when a colored resin film such as polyimide is used, it is preferably given from the upper part of the conductive material-adsorbing resin precursor layer when light energy is given. In the case where a transfer sheet in which the conductive substance adsorbing resin precursor layer and the adhesion auxiliary layer 16 are overlaid is transferred to a resin film to form these layers, even if energy is applied after the transfer, before transfer Energy may be applied. When light energy is applied before transfer, it may be applied from the protective film side or from the support side. Further, as the amount of energy to be applied, an active site is generated, and an amount capable of interacting with the conductive substance-adsorbing resin precursor layer to form a chemical bond can be appropriately given. In this way, the adhesion assisting layer 16 or the resin film can be brought into intimate contact. As such an example, the adhesion assisting layer 16 is mixed with a radical generator that generates an active site, and the conductive substance adsorbing resin precursor layer is mixed. By containing a reactive compound having both an unsaturated double bond capable of radical polymerization and a functional group capable of interacting with the conductive material, radicals are generated as active sites on the surface of the adhesion auxiliary layer 16 during energy irradiation. An example is given in which the reactive compound contained in the conductive material-adsorbing resin precursor layer forms a chemical bond as a graft.

When energy is applied by irradiation of radiation such as heat or light, a heater or infrared heating is used as heat. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and an LED. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
In addition, if you do not want to add a conductive layer, for example, do not give energy to parts such as vias, for example, attach a mask during light irradiation, and optionally adhere to the conductive substance-adsorbing resin precursor layer. It is also possible not to form a bond for close contact with the layer 16 or the resin film. Conversely, it is also possible to form a conductive substance-adsorbing resin layer on the entire surface by applying energy to the entire surface.
Here, when a polymerizable polymer having an average molecular weight of 20,000 or more and a polymerization degree of 200 or more is used as the reactive compound for forming the conductive substance-adsorptive resin layer, the polymerization is easy with low energy exposure. Therefore, decomposition of the produced polymer can be further suppressed.

In addition, after giving energy and making the electroconductive substance adsorptive resin precursor layer 18 adhere to the adhesion auxiliary layer 16 or the resin film layer 12, the unreacted electroconductive substance adsorbing resin precursor layer that does not contribute to adhesion is applied. A step (development step) of removing the contained compound and the conductive substance-adsorbing resin reactant that could not form a bond with the adhesion auxiliary layer 16 or the resin film layer 12 can be performed. This is generally performed with a solvent that dissolves the conductive substance-adsorbing resin precursor and does not dissolve the resin film and the adhesion auxiliary layer 16. Specifically, water, an alkaline developer, an organic solvent developer, or the like is used. As the developing method, a method of stirring in the solvent and a method of pressure washing such as shower are often used.
Further, after forming a conductive substance-adsorbing resin precursor layer and adhering to the adhesion auxiliary layer 16 or the resin film by the energy irradiation, excess conductive substance-adsorbing resin precursor is removed by the above method, In order to increase the adsorptivity between the conductive substance-adsorbing resin precursor layer and the metal ions or fine metal particles, plasma treatment, ultraviolet treatment, or the like may be used in combination.

In addition, when the method for producing a resin film with a metal pattern of the present invention is applied to the formation of wiring, the metal layer formed on the conductive material adsorbing film surface and the wiring on the back side of the resin film are connected as desired. In order to do so, a step of making a hole can be performed.
Drilling is generally performed by drilling, but a method of raising a via hole by laser processing or the like can also be applied in the case of fine processing. The laser used in the drilling step can be used even if the oscillation wavelength is any wavelength from the ultraviolet light region to the infrared light region. Here, the ultraviolet light region refers to a wavelength region in the range of 50 to 400 nm, and the infrared light region refers to a wavelength region in the range of 750 nm to 1 mm. Examples of the laser that can be used include an ultraviolet laser and a carbon dioxide laser.

As said ultraviolet laser, the light emission wavelength range is 180 nm-380 nm normally, Preferably it is 200 nm-380 nm, More preferably, it is 300 nm-380 nm. Examples of lasers for obtaining an ultraviolet laser include gas lasers such as Ar, N ₂ , ArF, KrF, XeCL, XeF, He—Cd, and He—Ne; solid lasers such as YAG, NdYAG, Nd glass, and alexandrite; Examples thereof include a dye laser using a dye dissolved in a solvent. In particular, a YAG laser and an NdYAG laser that can oscillate at a high output energy, have a long life, and can maintain the laser device at low cost are suitable. As the oscillation wavelength in the ultraviolet region, harmonics of these lasers are preferably used. Laser harmonics are generated by, for example, oscillating a 1.06 μm laser beam (fundamental wave) with a YAG laser or the like and passing the laser beam through two nonlinear crystals (LBO crystals) arranged in parallel at a predetermined interval in the optical path direction. The SHG light having a wavelength of 0.53 μm is converted into THG light (ultraviolet light) having a wavelength of 0.355 μm. As an apparatus for obtaining such harmonics, there is a laser processing machine disclosed in JP-A-11-342485. The laser can be irradiated continuously or intermittently, but it is preferable to intermittently irradiate with a single pulse because cracks can be prevented.

The number of times of irradiation (number of shots) in single pulse irradiation is usually 5 to 500 times, preferably 10 to 100 times. As the number of irradiations increases, the processing time becomes longer and cracks tend to occur. The pulse period is usually 3 to 8 kHz, preferably 4 to 5 kHz. The carbon dioxide gas laser is a molecular laser, has an efficiency of converting from electric power to laser light of 10% or more, and can generate a large output of several tens of kW at an oscillation wavelength of 10.6 μm. Usually, it has an energy of about 20 to 40 mJ and is performed with a short pulse of about 10 ⁻⁴ to 10 ⁻⁸ seconds. The number of shots of pulses necessary for via formation is usually about 5 to 1000 shots. The formed holes are used as through holes and blind via holes.
The ratio of the inner diameter (d1) of the bottom portion of the hole to the inner diameter (d0) of the inlet (surface) portion of the hole (hole diameter ratio: d1 / d0 × 100 [%]) is usually 40% or more, preferably 50% or more More preferably, it is 65% or more. Further, d0 is preferably in the range of 10 to 250 μm, and more preferably in the range of 20 to 80 μm. Those having a large hole diameter ratio are unlikely to cause poor conduction between insulating layers and have high reliability.

  In the present invention, the drilling step is in the state of a resin film, after the adhesion auxiliary layer 16 is formed, after the formation of the conductive substance adsorbing resin precursor layer, or after the metal fine particles or metal ions described below are adsorbed to form the metal layer. However, it can be performed even after the metal conductor layer is formed. If the resin film is to be perforated, a seed is also applied to the hole by forming the adhesion auxiliary layer 16 and the conductive substance adsorbing resin precursor layer 18 in the hole by a transfer or coating in a later step. It is possible to provide a conductor layer with good adhesion in the hole. On the other hand, when the adhesion auxiliary layer 16 is formed, the conductive substance adsorbing resin precursor layer 18 is formed, or after the seed layer formation or metal conductor layer formation which will be described later is performed, the hole can be plated as it is. However, in order to ensure better adhesion, it is necessary to perform a conditioning process or a catalyst application process that is normally performed for separately plating.

  The method of the present invention is characterized in that a region in which the metal layer is not formed is used in the resin film base material so as to overlap the metal layer formation region. However, when the region in which the metal layer is not formed is used as a coverlay, When forming holes for conduction in the area to be formed in advance, at the same time, carrying out the process of making holes in the area that overlaps the hole formed in the metal layer when the resin film substrate is used as a coverlay Can do.

Moreover, you may perform the desmear process which removes the smear which remains in a hole part in the process after this drilling process. In this case, the surface of the via hole is roughened by a dry method and / or a wet method as necessary. Examples of the dry roughening method include mechanical polishing such as buffing and sandblasting, plasma etching, and the like. On the other hand, the wet roughening method includes chemical treatment such as a method using an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, a strong base or a resin swelling solvent. . The desmear process can also be performed after electroless plating is performed on the insulating film using a seed to form a metal film serving as a power feeding layer. This process includes a swelling process, an etching process, a neutralization process, and the like. For example, a swelling process at 60 ° C. for 5 minutes using an organic solvent-based swelling liquid, an etching process at 80 ° C. for 10 minutes using a sodium permanganate-based etching liquid, and a neutralization liquid of a sulfuric acid meter at 40 ° C. for 5 minutes. A typical example is a neutralization step.
When desmearing is not performed, it is also effective to wash with a solvent that dissolves or swells the resin film.

In the production method of the present invention, when the metal layer is formed in a predetermined region, the conductive material adsorbing resin precursor is formed after forming the conductive material adsorbing resin layer or before forming the conductive material adsorbing resin. If necessary, metal ions, metal fine particles, or conductive fine particles can be adsorbed, and a metal layer can be formed using the adsorbed conductive material.
When the conductive material such as metal ions, metal fine particles, and conductive fine particles are adsorbed, the conductive material adsorbing resin precursor may be adsorbed in the state of the conductive material adsorbing resin precursor layer as described above. Energy may be applied to the layer, and the conductive material adsorbing resin layer may be formed by adhering to the adhesion auxiliary layer or the resin film substrate, and then adsorbed.
As a method of adsorbing the conductive substance, when adsorbing in the state of the conductive substance adsorbing resin precursor layer, a method of dissolving metal ions in the state of salt in the conductive substance adsorbing resin precursor coating liquid, Even if a coating liquid containing a conductive substance prepared by dispersing metal fine particles, metal salts, conductive fine particles in a conductive substance-adsorptive resin precursor coating liquid, etc. is applied to an adhesion auxiliary layer or a resin film substrate Well, after forming a conductive substance-adsorbing resin precursor layer on a resin film substrate or an adhesion auxiliary layer, these laminates can be used as a solution containing metal ions, metal fine particles, metal salts, conductive fine particles, etc. It may be adsorbed by immersing in a dispersion liquid and impregnating with these conductive substances.

  When adsorbing metal ions, metal fine particles, or conductive fine particles to the conductive substance-adsorbing resin layer of the present invention, the conductive substance-adsorbing resin precursor may be adsorbed in the state of the conductive substance-adsorbing resin precursor layer. Energy may be applied to the layer, and the conductive material adsorbing resin layer may be formed by adhering to the adhesion auxiliary layer or the resin film substrate, and then adsorbed.

When adsorbing after forming the conductive substance-adsorptive resin layer, immerse the resin film with the conductive substance-adsorptive resin layer in a metal ion solution, or a dispersion of metal fine particles, metal salt, or conductive fine particles. It can be adsorbed by impregnating with metal ions, metal fine particles, metal salts, conductive fine particles and the like. As another method, ions may be directly injected into the film and adsorbed by ion implantation or the like.
Furthermore, in order to adsorb the target metal ions, metal fine particles, and conductive fine particles to the conductive substance-adsorptive resin layer, the metal ions once adsorbed or previously existing metal ions are ion-exchanged with other metal ions. Alternatively, metal ions may be reduced and precipitated into metal fine particles. Alternatively, composite metal fine particles may be formed by depositing another metal on the surface of the metal fine particles using an electroless plating method or a displacement plating method. Furthermore, a method in which metal colloids, metal nanoparticles, conductive fine particles are allowed to interact and aggregate and precipitate may be used.
Furthermore, the above metal salt, metal fine particles, and conductive fine particles are dissolved or dispersed in an appropriate solvent, and a solution or dispersion containing the dissociated metal ions or particles is applied to the conductive substance-adsorbing resin precursor layer. Also good.

  Further, the step of adsorbing metal ions, metal fine particles or conductive fine particles to the conductive substance adsorbing resin layer of the present invention is performed by adhering to the adhesion auxiliary layer 16 or the resin film to form a conductive substance adsorbing resin layer. In the case of adsorbing from the unreacted conductive substance-adsorbing resin precursor that does not contribute to the adhesion, and the step of removing the conductive substance-adsorbing resin reactant that could not form a bond with the adhesion auxiliary layer 16 or the resin film ( It may be performed simultaneously with the development step). If it is performed simultaneously, the unreacted conductive substance-adsorbing resin precursor that does not contribute to adhesion and the conductive substance-adsorbing resin reactant that could not form a bond with the adhesion auxiliary layer 16 or the resin film are removed. Specifically, it is performed by previously dispersing or dissolving conductive fine particles, metal fine particles, metal ions, metal salts, etc. to be adsorbed in water, an alkaline developer, an organic solvent developer, or the like. it can.

  As described above, the metal ion can be adsorbed to the functional group by bringing the metal ion-containing solution or the metal fine particles or the solution in which the conductive fine particles are dispersed into contact with each other. From the viewpoint of sufficiently performing these adsorptions, the metal ion concentration or metal salt concentration of the solution to be contacted is preferably in the range of 0.01 to 50% by mass, and in the range of 0.1 to 30% by mass. More preferably it is. The contact time is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

In the present invention, the adsorbed metal ions can be reduced to adsorb metal fine particles. In this step, as a reducing agent used to form a metal (fine particle) film by reducing metal ions or metal ions present by adsorbing or impregnating the conductive substance-adsorbing resin precursor layer, The metal salt compound used is not particularly limited as long as it has physical properties that allow the metal to be precipitated, and examples thereof include hypophosphites, tetrahydroborates, and hydrazines.
These reducing agents can be appropriately selected in relation to the metal salt and metal ion to be used. For example, when a silver nitrate aqueous solution is used as the metal salt aqueous solution for supplying the metal ion or metal salt, tetrahydroboron is used. When sodium acid uses an aqueous palladium dichloride solution, hydrazine is preferred. As the method for adding the reducing agent, for example, after adding metal ions or metal salts to the surface of the electrically insulating layer where the conductive substance-adsorbing resin precursor layer is present, water, an organic solvent or a mixture thereof is used. After removing excess metal salts and metal ions by washing, a method of immersing the resin film substrate 12 with the adhesion auxiliary layer 16 provided with the surface in water such as ion-exchanged water, and adding a reducing agent thereto, Examples thereof include a method of directly applying or dropping a reducing agent aqueous solution having a predetermined concentration on the surface of the resin film substrate 12 with the adhesion auxiliary layer 16. Moreover, as an addition amount of a reducing agent, it is preferable to use an excessive amount equal to or more than the metal ion, and more preferably 10 times equivalent or more.
This reduction step is performed in a step after the metal salt and metal ions are adsorbed on the adsorptive resin precursor, and may be performed simultaneously with the electroless plating step described later.

The metal ions, metal fine particles, and conductive fine particles that can be used in this step are not particularly limited as long as they interact with the adsorptive functional group, and known metal ions, metal fine particles, and conductive fine particles are arbitrarily selected. Can be used. For example, fine metal particles such as Au, Ag, Pt, Cu, Rh, Pd, Al, Cr, In ₂ O ₃ , SnO ₂ , ZnO, CdO, TiO ₂ , CdIn ₂ O ₄ , Cd ₂ SnO ₂ , Zn ₂ SnO ₄ , oxide semiconductor fine particles such as In ₂ O ₃ —ZnO, fine particles using a material doped with impurities compatible with these, spinel compound fine particles such as MgInO and CaGaO, and conductivity such as TiN, ZrN, and HfN Preferable examples include nitride fine particles, conductive boride fine particles such as LaB, and organic materials such as conductive polymer fine particles and polymer fine particles containing metal salts.

In the case of using metal fine particles and conductive fine particles, the particle size is preferably in the range of 0.1 nm to 1000 nm, and more preferably in the range of 1 nm to 100 nm. When the particle size is smaller than 0.1 nm, the surfaces of the fine particles are continuously in contact with each other to form aggregates, and the resulting adsorptivity tends to be reduced. On the other hand, when the thickness is larger than 1000 nm, the contact area that interacts and binds to the functional group having an adsorbing ability is reduced, so that the adhesion between the hydrophilic surface and the particles is lowered, and the strength of the conductive region tends to deteriorate. .
In this step, the metal salt is not particularly limited as long as it is dissolved in an appropriate solvent to dissociate into a metal ion and a base (anion) to be applied to the conductive substance-adsorptive resin layer generation region. And M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, Pd ions, and chromium ions, and Ag and Cu are magnetic as the conductive film. Co is preferably used as the film.

  In the present invention, after the metal ions, metal fine particles, or conductive fine particles are further adsorbed on the conductive substance adsorbing resin layer, extra metal ions, metal fine particles, or conductive fine particles that could not be adsorbed as necessary are added. A step of washing and washing off may be included.

By adsorbing the metal ions, metal fine particles, or conductive fine particles, the metal deposited in the conductive substance-adsorbing resin layer is formed as a fractal microstructure, so that the fine particle layer and the conductive substance-adsorbing property are formed. Adhesion with the resin layer can be further improved.
The amount of metal present in the conductive substance-adsorptive resin layer is the amount of metal that occupies a region from the outermost surface of the conductive substance-adsorptive resin layer to a depth of 0.5 μm when the cross section of the substrate is photographed with a metal microscope. When the ratio is 5 to 50% by area and the arithmetic average roughness Ra (JIS B0633-2001) between the conductive substance-adsorbing resin layer and the metal interface is 0.05 μm to 0.5 μm, stronger adhesion is obtained. Expressed.

(Metal layer formation by plating)
When the resin film substrate formed by adsorbing a metal, which is a conductive substance formed in this way, is used for forming a flexible printed wiring board, the metal is adsorbed on the conductive substance adsorbing resin layer, It is preferable from the viewpoint of forming a metal layer (conductive layer) excellent in wire conductivity to adopt a means for plating based on a metal.
When plating on conductive material adsorbing resin film, metal, metal ions, or conductive particles are not adsorbed on the conductive material adsorbing layer when metal, metal ions, or conductive fine particles are not adsorbed on the film. What is necessary is just to adsorb what becomes the electroless-plating catalyst selected from microparticles | fine-particles etc., and to perform electroless-plating process after that.
In addition, a conductive substance-adsorbing resin film in which a metal, metal ion, or conductive fine particles, which become an electroless plating catalyst, is previously adsorbed may be directly used for the conductive substance-adsorbing layer of the resin film.
The conductive substance adsorbing resin film has previously adsorbed a predetermined amount or more of metal ions, metal fine particles or conductive fine particles, so that a layer having sufficient conductivity is formed on the surface. May be electroplated by passing electricity directly through the conductive layer.

  In the formation process of the metal layer, the electroless plating catalyst to be adsorbed on the conductive material adsorbing layer is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal to the interactive region, for example, a metal colloid whose charge is adjusted so as to interact with an interactive group on the interactive region is applied to the interactive region. A technique is used. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and the conductive colloid of the conductive material-adsorbing resin precursor layer is obtained by adjusting the charge of the metal colloid. By making it interact with metal colloid (electroless plating catalyst) can be attached to the conductive substance-adsorbing resin precursor layer.

Furthermore, the electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. There is no particular limitation as long as it is dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) ( M represents an n-valent metal atom). As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.
The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion, which is an electroless plating catalyst precursor, may be used as an electroless plating catalyst after being applied to the substrate and before being immersed in the electroless plating bath by changing it to a zero-valent metal by a reduction reaction. The plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

As an example of the present invention, a substrate is immersed in a plating catalyst solution (for example, a silver nitrate aqueous solution or a tin-palladium colloid solution) in order to attach a plating catalyst to a conductive substance-adsorbing resin precursor layer fixed on a resin film. As electroless plating catalyst, palladium, gold, platinum, silver, copper, nickel, cobalt, tin and other metal beauty powders and / or their halides, oxides, hydroxides, sulfides, peroxides, Examples include amine salts, sulfates, nitrates, organic acid salts, and organic chelate compounds. Moreover, what adsorb | sucked these to various inorganic components may be used. In this case, the inorganic components include colloidal silica, calcium carbonate, magnesium carbonate, magnesium oxide, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, mica, etc., as well as alumina and carbon. Any fine powder may be used. Further, the size of the fine powder at this time is preferably an average particle diameter of 0.1 to 50 μm.
The conductive fine particles, metal ions, metal salts, electroless plating catalyst, and electroless plating catalyst precursor are not limited to one type, and a plurality of types can be used in combination as required. In order to obtain desired conductivity, a plurality of materials can be mixed and used in advance.
Further, after immersing in the plating catalyst solution, excess plating catalyst solution is removed by washing.
If the seed layer applied to the adhesion auxiliary layer shows sufficient conductivity, electroplating may be carried out as it is to form a conductor layer, but sufficient conductivity can be obtained only by adding metal ions or an electroless plating catalyst. May not be obtained, in which case electroless plating is further performed using an electroless plating catalyst.

Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved. Electroless plating may be performed after soft etching and acid cleaning. Furthermore, it may be carried out through an activator and an accelerator process that are generally commercially available.
The electroless plating in this step is, for example, after removing the excess electroless plating catalyst (metal) by washing the substrate provided with the electroless plating catalyst obtained in the step of applying the electroless plating catalyst, etc. It is performed by immersing in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.

  In addition, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is attached to or impregnated with the conductive substance-adsorbing resin precursor layer, the substrate Is washed with water to remove excess precursor (metal salt, etc.) and then immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above. In addition, the electroless plating catalyst precursor may be reduced to be an electroless plating catalyst and then immersed in an electroless plating bath. In this case as well, excess electroless plating catalyst precursor is removed by washing or the like.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
Silver, chromium, copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath. Among them, from the viewpoint of conductivity, silver, copper, gold Particularly preferred are chromium and nickel.

In addition, there are optimum reducing agents and additives that can be adapted to the above metals, and it is a preferred embodiment to use them together. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate and sodium succinate as complexing agents. It is included. Further, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer.
In addition, components other than the optimal reducing agent and additive can be added to these plating baths depending on the purpose.

The film thickness of the conductive film (metal layer) formed in this way can be controlled by the metal salt or metal ion concentration of the plating bath, the immersion time in the plating bath, the temperature of the plating bath, or the like. From the viewpoint of conductivity, the thickness is preferably 0.1 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.
When a semi-additive method is used as a process for forming a pattern in the metal layer region, the film thickness may be 3 μm or less as long as a metal film that can conduct and is free of defects is formed.

  Also, in order to improve the adhesion with the resin that forms the electrical insulation layer, the electroless plating is performed by chromium or nickel, and the electroplating that forms the conductor layer is formed by electroless plating, such as copper plating. The first metal and the second metal formed by electroplating may be the same or different.

In addition, when producing a copper-clad plate used in the subtractive method, the electroplating process is performed after the electroless plating process to improve the thickness and film quality of the metal layer (conductive layer) as necessary. May be performed.
In the electroplating step, after the electroless plating in the electroless plating step, the metal film (conductive film) formed in this step is used as an electrode, and electroplating is further performed. As a result, a metal film having an arbitrary thickness can be easily formed on the basis of the metal film having excellent adhesion to the resin support. By adding the electroplating step, the metal film can be formed with a thickness according to the purpose, and the conductive material obtained according to this embodiment is suitable for applying to various applications.

A conventionally known method can be used as the electroplating method in this embodiment. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is preferable. More preferred. The film thickness of the metal film obtained by electroplating varies depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath, the dipping time, or the current density. In addition, from the viewpoint of conductivity, the film thickness when used for general electric wiring or the like is preferably 0.3 μm or more, and more preferably 3 μm or more. Moreover, the electroplating process in the present invention can be applied to mounting of an IC or the like by, for example, electroplating in addition to forming a patterned metal film with a thickness according to the purpose as described above. It can also be done for purposes such as The plating performed for this purpose is selected from the group consisting of nickel, palladium, gold, silver, tin, solder, rhodium, platinum, and compounds thereof on the conductive film or metal pattern surface formed of copper or the like. It can be performed using the material to be used.
In this way, a resin film substrate having a metal pattern on a part of its surface can be obtained.

When the manufacturing method of the present invention is applied to the production of a multilayer wiring board such as CCL, vias are used to connect the formed metal layer (conductive layer = wiring) and the wiring on the back side of the resin film substrate. What is necessary is just to perform the process of forming a hole part and forming a conductive material in the hole part, and ensuring the connection with the wiring which exists in a back surface side. The steps of connecting the laminated wirings are as follows: (1) A via hole is first formed in the resin film layer 12 itself, and then the adhesion auxiliary layer 16 and the conductive substance adsorbing resin are formed on the surface of the resin film layer 12 in which the hole is formed. When the precursor layer 18 is formed, by performing the electroless plating step, the inside of the hole can be plated at the same time as the surface of the conductive material adsorbing layer, and a wiring for easily connecting the multilayers is formed. Is done.
On the other hand, when the via hole is formed after the adhesion auxiliary layer 16, the conductive material adsorbing resin precursor layer 18 and the metal layer are sequentially formed on the surface of the resin film layer 12, only in the separate hole. A connection can be formed by performing electroless plating using a method similar to plating a through hole using an existing copper-clad plate.
In any of these cases, after the electroless plating, by further combining electroplating, it is possible to form a state in which the metal is filled throughout the via hole portion with the plated metal, and the connection wiring can be formed.
As another connection formation method, conductive fine particles, metal nanoparticles, metal nano paste, conductive adhesive containing metal elements such as copper, silver, gold, etc. in the hole by printing method, dispenser method, ink jet method, etc. A method of injecting an agent or the like to form connection wiring can also be used.

  Heat treatment or the like may be performed after the metal layer or a wiring for connecting the multilayers is formed. The heating temperature in the heat treatment step is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, and particularly preferably about 180 ° C. Further, depending on the resin, it may be performed near the glass transition temperature. The heating temperature is preferably 400 ° C. or lower in consideration of the processing efficiency and the dimensional stability of the electrical insulating layer. Further, the heating time is preferably 10 minutes or more, and more preferably about 30 minutes to 120 minutes. Thereby, hardening of a thermosetting resin advances and the peel strength of a metal layer can also be improved further.

  In the resin film substrate having a metal pattern used in the method of the present invention, after forming a metal layer on the entire required area of the resin film substrate surface, the metal layer is patterned by a known method to form an arbitrary wiring. Can be formed.

For example, a plating resist can be provided on the surface of the metal layer of the resin film with a metal layer, and a wiring pattern can be formed using a subtractive method or a semi-additive method.
The subtractive method is (1) applying a resist layer on a metal film made by electroplating using the above method → (2) pattern exposure and development of the resist pattern of the conductor to be left behind → (3) etching By removing unnecessary metal film, (4) refers to a method of peeling the resist layer and forming a metal pattern. The thickness of the metal film used in this embodiment is preferably 5 μm or more, and more preferably in the range of 5 to 30 μm.

  The semi-additive method is (1) applying a resist layer on a metal film formed on a conductive material-adsorbing resin precursor layer → (2) forming a resist pattern of a conductor to be removed by pattern exposure and development → (3) Forming a metal film on the non-patterned portion of the resist by plating → (4) Stripping the DFR → (5) A metal pattern forming method of removing unnecessary metal films by etching. In this method, the first metal film is used as a power feeding layer, and a conductive layer is formed on a portion without a resist by electroplating. As the plating method, the electroless plating and electroplating described above can be used. Further, the thickness of the metal film to which the resist layer is applied is preferably about 0.3 to 3 μm in order to complete the etching process in a short time. Moreover, you may perform electrolytic plating and electroless plating further with respect to the formed metal pattern.

Details of the method for forming the wiring pattern will be described below.
(1) Resist layer formation process “Registration”
As the photosensitive resist to be used, a photocurable negative resist or a photodissolvable positive resist that dissolves upon exposure can be used. As the photosensitive resist, 1. photosensitive dry film resist (DFR); 2. liquid resist; An ED (electrodeposition) resist can be used. Each of these has its own characteristics. 1. A photosensitive dry film resist (DFR) can be used in a dry manner, so that it is easy to handle. Since the liquid resist can have a thin film thickness as a resist, a pattern with good resolution can be formed. 3. Since an ED (electrodeposition) resist can have a thin film thickness as a resist, it can form a pattern with good resolution, has good follow-up to unevenness on the coated surface, and has excellent adhesion. The resist to be used may be appropriately selected in consideration of these characteristics.

"Coating method"
1. Photosensitive dry film The photosensitive dry film generally has a sandwich structure sandwiched between a polyester film and a polyethylene film, and is pressure-bonded with a hot roll while peeling the polyethylene film with a laminator.
The photosensitive dry film resist is described in detail in Japanese Patent Application No. 2005-103677 specification, paragraph Nos. [0192] to [0372] previously proposed by the applicant of the present invention for the formulation, film formation method, and lamination method. These descriptions can also be applied to the present invention.
2. Liquid resist coating methods include spray coating, roll coating, curtain coating, and dip coating. Of these, roll coating and dip coating are preferred for simultaneous application on both surfaces, since both surfaces can be coated simultaneously.
The liquid resist is described in detail in Japanese Patent Application No. 2005-188722, paragraph Nos. [0199] to [0219] previously proposed by the applicant of the present application, and these descriptions can also be applied to the present invention.
3. ED (Electrodeposition) Resist ED resist is a colloid obtained by suspending a photosensitive resist in fine particles and suspending it in water. The particles are charged. The resist is deposited on the conductor layer, and the colloids are bonded to each other on the conductor to form a film.

(2) Pattern exposure process "Exposure"
A base material provided with a resist film on the upper part of the metal film is brought into close contact with a mask film or a dry plate, and exposed to light in a photosensitive region of the resist used. In the case of using a film, the film is exposed with a vacuum printing frame. Regarding the exposure source, a point light source can be used when the pattern width is about 100 μm. When forming a pattern having a pattern width of 100 μm or less, it is preferable to use a parallel light source. In recent years, a method of forming a pattern by using a laser for digital exposure without using a mask film or a dry plate has come to be used.
"developing"
Any photo-curing negative resist can be used as long as it can dissolve the unexposed area, or a photo-dissolvable positive resist that dissolves upon exposure, so long as it dissolves the exposed area. An aqueous solution is used. In recent years, an alkaline aqueous solution has been used in order to reduce environmental burden.

(3) Forming a metal film on the non-patterned portion of the resist by plating After the pattern formation, a metal film or a conductive film (for example, a film formed by electroless plating) existing below the pattern is used as a feeding electrode, and further Plating can be performed. As a result, a metal film having an arbitrary thickness can be easily formed on the basis of the metal film having excellent adhesion to the electrical insulating layer. By adding this step, the metal film can be formed in a thickness according to the purpose, and it is suitable for applying the conductive material obtained according to this embodiment to various applications.
A conventionally known method can be used as the electroplating method in this embodiment. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is preferable. More preferred.
Further, the formation of the conductor layer by electroplating is thicker if the resist is thicker and thinner if the resist is thinner. When the conductive layer by electroplating is thicker than the thickness of the resist, the resist is difficult to peel off, and the gap between adjacent lines is not preferable.

(4) Resist peeling process “Peeling process”
After the metal (conductive) pattern is completed by electroplating, the plating resist that is no longer needed is no longer needed, and a process of peeling it off is necessary. Peeling can be performed by spraying a stripping solution. The stripping solution varies depending on the type of resist, but generally, a solvent or solution that swells the resist is wiped with a spray, and the resist is swollen and stripped.

(5) Etching process "Etching"
Etching is a process for completing the conductor pattern by chemically dissolving and removing the power supply layer that is no longer necessary to develop insulation between the conductor patterns. The etching process is mainly performed by a horizontal conveyor device by spraying an etching solution from above and below. As the etchant, the metal layer is oxidized and dissolved with an oxidizing aqueous solution. Examples of etching solutions include ferric chloride solution, cupric chloride solution, and alkali etchant. Since the resist may be peeled off by alkali, a ferric chloride solution and a cupric chloride solution are mainly used.
In the method of the present invention, since the substrate interface is not roughened, the conductive component adsorbing resin precursor in which a metal film is introduced on the base material in addition to good removability of the conductive component in the vicinity of the substrate interface Since the layer is bonded to the adhesion auxiliary layer 16 or the electrical insulating layer at the end of the polymer chain and has a very high mobility structure, the etching solution is used in the graft polymer layer in this etching step. Therefore, it is possible to form a pattern with excellent sharpness because the metal component can be easily diffused and the metal component is easily removed at the interface between the substrate and the metal layer.

  In the present invention, after the wiring pattern is formed, a step of inactivating the conductive substance adsorbing resin layer remaining in the non-wiring portion may be performed. By performing the inactivation, it is possible to easily remove the seed and prevent a failure such as ion migration. As a deactivation method, a conductive substance-adsorbing resin precursor layer and a certain ionic compound are allowed to interact with each other to form an insoluble salt, and a functional group capable of interacting with the plating catalyst is separately added. A method of chemically modifying the insulating group can be employed. Furthermore, in order to improve the adhesiveness with the electrically insulating layer and the solder resist layer that is an upper layer, it may be modified to a functional group capable of forming a chemical bond with these layers.

  Further, after the wiring pattern is formed, a step of removing the conductive substance-adsorbing resin precursor layer remaining in the non-wiring portion may be added. As a removal method, for example, a desmear process used for roughening treatment may be used. As the desmear process, a method using alkaline permanganate is known. The desmear process can also be performed after electroless plating is performed on the insulating film using a seed to form a metal film serving as a power feeding layer. This process includes a swelling process, an etching process, a neutralization process, and the like. By performing this treatment, it is possible to further improve the adhesion to the electrically insulating layer or the solder resist layer which is an upper layer. Further, since the surface is not roughened when forming the wiring, a high-definition wiring pattern can be formed.

  In the present invention, the copper surface may be processed on the formed conductor pattern. As the treatment method, a black oxidation treatment method, a copper oxide reduction method, a copper roughening method, a roughened electroless copper plating method, or the like can be applied. By carrying out these steps, it is possible to improve the adhesion to the electrically insulating layer and the solder resist layer that are on the upper layer. Moreover, in order to prevent oxidation of a metal conductor part, a rust prevention process may be performed.

A representative process of the method of the present invention will be described with reference to the drawings. FIG. 1 (A) is a schematic cross-sectional view of a resin film substrate 12 having the metal layer 22 obtained as described above in part. Here, the adhesion auxiliary layer and the conductive substance-adsorbing resin layer in the laminate shown in FIG. 2 are omitted.
FIG. 1B shows a state in which a metal pattern 24 corresponding to wiring is formed using the metal layer of the resin film substrate 12 having the metal layer 22 shown in FIG. The metal pattern 24 may be obtained by patterning the metal layer 22 in FIG. 1 (A), and a conductive substance adsorbing resin layer is formed in a pattern on the surface of the resin film substrate 12. A metal layer may be formed only on the portion to form a metal pattern.

In the method of the present invention, the portion of the resin film substrate 12 where the metal layer 22 is not formed can be used as a cover lay, used as a reinforcing plate, or used as a guide for handling. Hereinafter, the case where it uses as a coverlay is shown.
For the purpose of improving the adhesion between the resin film substrate 12 corresponding to the coverlay and the metal pattern 24, an adhesive resin is applied to the metal layer non-formation region of the resin film substrate 12 to form the adhesion layer 26. .
As the adhesive resin used for forming the adhesion layer, a general thermoplastic resin such as phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, etc. can be used. , Epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, reactive resins such as acrylic resins, isocyanate resins, and those resins to react with or react with these resins Examples include soot curing agents and reactive agents. The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. Further, for example, as an adhesive used when a resin film base material is used as a coverlay, an adhesive as described in JP-A-2006-165495 can be cited.
The coating thickness of the adhesion layer can be appropriately selected in relation to the metal wiring to be formed, but generally it is preferably in the range of 5 to 50 μm.
Note that the adhesion layer is not essential. For example, when the adhesion auxiliary layer is exposed on the surface to be bonded to the metal layer, the adhesion auxiliary layer can be overlapped to apply energy by overlapping the adhesion layer. .

After the adhesion layer 26 is formed, the region is overlapped with the metal pattern 24 formation region on the surface of the resin film substrate 12 as shown in FIG. Then, the folded portion of the resin film substrate 12 is cut and removed, so that the metal pattern 24 (on the leading edge resin layer) is formed on the surface of the resin film substrate 12 (that is, the leading edge resin layer) as shown in FIG. In other words, a laminate is formed which has a wiring) and whose surface is covered and protected by the resin film substrate 12 which functions as a coverlay.
Examples of the energy application for joining the metal pattern 24 and the adhesion layer 26 include irradiation of energy rays such as light, electromagnetic waves, electron beams, and radiation, application of heat energy, and pressure energy. Specific examples include ultraviolet light irradiation, infrared light irradiation, plasma irradiation, X-ray irradiation, alpha ray irradiation, and gamma ray irradiation. Of these, energy beam irradiation and thermal energy are preferable.

After such a laminate is formed, a multilayer substrate can be made last by repeating a step of forming a metal pattern on the surface or a step of laminating and laminating with a separately formed metal wiring pattern. . In the case of the outermost layer, it is possible to manufacture a protective film or a solder resist film forming process finish plating (for example, nickel-gold plating, solder coating, etc.) and a substrate.
Thus, according to the method of the present invention, the resin film base material on which the metal layer is not formed can be used as it is as a cover lay, used as a reinforcing plate, or used as a guide for handling.

In the steps shown in FIGS. 1A to 1D, an example in which an adhesive layer is provided on a portion over the wiring after the wiring is formed and the coverlay is provided by changing the wiring is illustrated. However, the present invention is not limited thereto. It is also possible to provide a metal pattern wiring on the portion to be the cover lay and bond them together.
After such a step, the folded portion after bonding may be left as it is, or the folded portion may be cut as shown in FIG.
When the resin film substrate 12 is used as a reinforcing plate for a laminate, it can be used as a reinforcing plate by providing an adhesive layer on a portion to be reinforced and folding it back to a lower portion of a wiring to be reinforced or a portion to be reinforced.
In the method of the present invention, since the resin film substrate 12, that is, the insulating layer and the metal pattern 24, that is, the wiring are integrated, RtoR continuous processing is also possible.
Further, when the metal layer non-formation region of the resin film substrate 12 is used as a guide for handling, since there is no metal film and the light transmittance and visibility are excellent, alignment is performed by an optical method such as a laser. It becomes possible.

Next, an embodiment in which the method of the present invention is applied and a plurality of layers of metal patterns are provided on the surface of one resin film substrate 12 will be described.
In this embodiment, as shown in FIG. 3A, a laminate having metal layers 22A and 22B in predetermined regions on both surfaces of the resin film substrate 12 is used.
FIG. 3B shows a state in which metal patterns 24A and 24B corresponding to wirings are formed using the metal layers present on both surfaces of the resin film base 12 having the metal layers 22A and 22B shown in FIG. Show. The formation of the metal patterns 24A and 24B is performed in the same manner as described with reference to FIGS.

Next, since the portion of the resin film substrate 12 where the metal layers 22A and 22B are not formed is used as a coverlay, the joint portion between the resin film substrate 12 corresponding to the coverlay and the metal patterns 24A and 24B, that is, Adhesive resin is applied to both ends of the resin film substrate 12 to form the adhesion layers 26A and 26B.
After the adhesion layers 26A and 26B are formed, as shown in FIG. 3C, the formation region of the adhesion layer 26A is formed in the formation region of the metal pattern 24A on the surface of the resin film substrate 12, and the end portion of the resin film substrate 12 is formed. It overlaps by folding up, and also overlaps the formation region of the adhesion layer 26B with the formation region of the metal pattern 24B formed on the back surface side by folding the resin film substrate 12 downward, and then gives energy. Then, the metal pattern 24A and the adhesion layer 26A, the metal pattern 24B and the adhesion layer 26B are joined, respectively, and then the folded portion of the resin film substrate 12 is cut and removed, as shown in FIG. Layered metal wiring is formed, and each surface is covered and protected with a resin film substrate 12 that functions as a coverlay.

  As described above, it is possible to easily form a printed wiring board excellent in productivity by producing a flexible printed circuit board using a resin film with a metal layer for forming a metal wiring that has been produced by the method of the present invention. .

  By utilizing the resin film with a metal layer for forming a metal wiring of the present invention and the manufacturing method thereof, it is possible to form a fine wiring pattern, and avoid misalignment and handling failure during printed circuit board production, It is also useful for increasing production efficiency.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[Example 1]
Kapton EN (manufactured by Toray DuPont Co., Ltd.), which is a polyimide film having a thickness of 25 μm, is used as the resin film base material B (hereinafter also referred to as base material B). Subsequently, the adhesion auxiliary layer coating solution 1-1 having the following polymerization initiation ability is prepared on both surfaces of the substrate B, and the solid content thickness of the adhesion auxiliary layer 1 after removing the solvent by a die coating method is 3 μm. After coating at 120 ° C. for 5 minutes, the coating auxiliary layer 16 was formed on the surface of the resin film substrate by heating at 170 ° C. for 30 minutes.
(Synthesis of polymer P1 having a polymerization initiating group)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. There, 8.1 g of [2- (acryloyloxy) ethyl] (4-benzoylbenzyl) dimethylammonium bromide [[2- (Acryloyloxy) ethyl] (4-benzoylbenzoyl) dimethyl ammonium bromide), 2-hydroxyethyl methacrylate [ Hydroxyethyl methacrylate] 9.9 g, isopropyl methacrylate [isopropyl methacrylate] 3.5 g, dimethyl-2,2′-azobis (2-methylpropionate) 0.43 g, and MFG 30 g over 2.5 hours. It was dripped. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain a polymer P1 having a polymerization initiating group.

(Formation of adhesion auxiliary layer 1-1 containing an initiator)
22 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) (hereinafter, all compounding amounts are expressed in parts by mass), cresol novolac type epoxy resin (epoxy equivalent 215, Dainippon Ink Chemical Industrial Co., Ltd. Epicron N-673) 43 parts by mass, phenol novolac resin (phenolic hydroxyl group equivalent 105, Dainippon Ink & Chemicals Phenolite) 30 parts by mass ethyl diglycol acetate 20 parts by mass, solvent After stirring and dissolving in 20 parts by mass of naphtha and cooling to room temperature, cyclohexanone varnish of phenoxy resin composed of Epicoat 828 and bisphenol S (YL6747H30 manufactured by Yuka Shell Epoxy Co., Ltd., nonvolatile content: 30% by mass, weight) (Average molecular weight 47000) 2 parts by mass, 0.8 parts of 2-phenyl-4,5-bis (hydroxymethyl) imidazole and 0.5 parts of a silicon-based antifoaming agent were added, and 10 parts of the polymerization initiating polymer P1 was added to this mixture. Further, methyl ethyl ketone was added so that the entire nonvolatile solid content was 20% by weight, and a coating solution for forming the adhesion auxiliary layer 1 was prepared.

Next, a conductive substance-adsorbing resin precursor that interacts with the conductive substance and forms a bond with the adhesion auxiliary layer 1 for forming the conductive substance-adsorbing resin precursor layer was synthesized by the following method. .
(Synthesis Example: Synthesis of Conductive Substance Adsorbing Resin Precursor P2)
60 g of polyacrylic acid (average molecular weight 25000, Wako Pure Chemical Industries) and 1.38 g (0.0125 mol) of hydroquinone (Wako Pure Chemical Industries) were placed in a 1 l three-necked flask equipped with a condenser, and N, N-dimethylacetamide (DMAc, Wako Pure Chemical Industries) 700 g was added and stirred at room temperature to obtain a uniform solution. While stirring the solution, 64.6 g (0.416 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 0.79 g (1.25 × 10 ⁻³ mol) of di-n-butyltin dilaurate (Tokyo Chemical Industry) suspended in 30 g of DMAc was added dropwise. The mixture was heated in a 65 ° C. water bath with stirring. After 5 hours, the heating was stopped and the mixture was naturally cooled to room temperature. The reaction solution had an acid value of 7.105 mmol / g and a solid content of 11.83%.
300 g of the reaction solution was placed in a beaker and cooled to 5 ° C. with an ice bath. While stirring the reaction solution, 41.2 ml of 4N aqueous sodium hydroxide solution was added dropwise over about 1 hour. The temperature of the reaction solution during the dropping was 5 to 11 ° C. After the dropping, the reaction solution was stirred at room temperature for 10 minutes, and the solid content was removed by suction filtration to obtain a brown solution. The solution was reprecipitated with 3 liters of ethyl acetate, and the precipitated solid was collected by filtration. The solid was reslurried overnight with 3 liters of acetone. After filtering off the solid, separately dissolved in a mixed solvent of 2 g of water and 1 g of acetonitrile with respect to 1 g of the polymer, this solution was completely deionized through an ion exchange resin column and vacuum-dried for 10 hours to obtain a light brown powder P2. It was. When 1 g of this polymer was dissolved in a mixed solvent of 2 g of water and 1 g of acetonitrile, the pH was 5.56 and the viscosity was 5.74 cps. (Viscosity was measured at 28 ° C. with RE80 viscometer manufactured by Toki Sangyo Co., Ltd., using rotor 30XR14). Moreover, the weight average molecular weight measured by GPC method was 30000.

Next, an adsorbent resin precursor layer forming liquid having the following composition was prepared as a conductive substance adsorbing resin precursor layer forming liquid, and the thickness after drying after removing the solvent on the adhesion auxiliary layer was 1 It was applied to both sides by a die coating method so as to be 5 microns, and then dried at 80 ° C. to 120 ° C. to form a conductive substance-adsorbing resin precursor layer.
(Liquid composition 2 for forming an adsorbent resin precursor layer)
-Conductive substance adsorbent resin precursor (P2) 3.0 g
・ Water 24.0g
・ 13.0 g of 1-methoxy-2-propanol

  After forming the adsorbent resin precursor layer on the adhesion auxiliary layer, UV light having a wavelength of 254 nm is used as an energy for generating and adhering active sites from the adsorbent resin precursor layer side. -02516S1LP01 (manufactured by USHIO INC.) And exposed at room temperature for 1 minute. After the entire surface exposure, the unnecessary conductive substance adsorbing resin precursor reactant that could not interact with the adhesion auxiliary layer 16 is sufficiently washed with ion-exchanged water and removed, and the conductive film adsorbing property on the surface of the resin film substrate is removed. A polyimide film (resin film A) with a conductive substance-adsorptive resin layer provided with a layer was produced.

After immersing in a 0.1% by weight aqueous solution of polyimide film (resin film A) silver oxide (manufactured by Wako Pure Chemical Industries, Ltd.) with conductive material adsorbing resin layer prepared as described above for 10 minutes, it was washed with distilled water. Thereafter, it was immersed in an electroless plating bath having the following composition at 60 ° C. for 10 minutes to form an electroless copper plating layer. The thickness of the electroless plating layer was 1.0 microns.
(Composition of electroless plating bath)
・ Distilled water 859g
・ Methanol 850g
・ Copper sulfate 18.1g
・ Ethylenediaminetetraacetic acid disodium salt 54.0g
・ Polyoxyethylene glycol (molecular weight 1000) 0.18g
・ 2,2'bipyridyl 1.8mg
・ 10% ethylenediamine aqueous solution 7.2g
・ 37% formaldehyde aqueous solution 9.7g
The pH of the plating bath having the above composition was adjusted to 12.5 (60 ° C.) with sodium hydroxide and sulfuric acid.

When the polyimide substrate after electroless copper plating was observed, the portion irradiated with UV light during UV exposure was electrolessly plated and a copper layer was formed. Using this copper layer as a power feeding layer, an electroplating bath having the following composition was used, and electroplating was performed for 20 minutes under the condition of 3 A / dm ² . The thickness of the obtained electrolytic copper plating film was 18 μm.

(Composition of electroplating bath)
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Copper Greeme PCM (Meltex Co., Ltd.) 3mL
・ Water 500g
Through the above process. A resin film with a metal layer for forming a metal wiring in which a portion where the metal film 22 capable of forming the metal wiring pattern 24 is present on the surface of the resin film substrate 12 and a portion of the resin where no metal exists coexist is produced.

Using this resin film with metal layer 22 for forming metal wiring, a flexible printed circuit board was produced as follows.
A dry etching resist film is laminated to a thickness of 20 μm on the portion of the substrate where the metal layer 22 is formed, and a resist film is provided on the upper part of the metal film so that the substrate is in close contact with the mask film or the dry plate. A pattern is formed so that a portion where wiring is to be formed is exposed by light in the region, and the resist of the unexposed portion is dissolved and removed using an alkaline developer until the surface of the metal pattern 24 is exposed, A pattern in which the line / space of the metal layer (conductor layer) was 10 μm / 10 μm was formed as a test.

  Next, wet etching (such as an etchant containing ferric chloride as a main component or an etchant containing cupric chloride as a main component) is performed, and the copper in the non-wiring pattern portion where the resist has been removed by development is used as a base. Etching was removed until the resin layer appeared. After that, the etching resist that became unnecessary was peeled off. Peeling was performed by spraying a stripping solution.

Next, a thermosetting epoxy adhesive having a flow start temperature of 80 ° C. was applied to the portion where the metal layer was not formed so as to have a dry coating thickness of 20 μm to form an adhesive layer 26. This portion was folded and covered on the wiring pattern 24, and bonded under the conditions of 160 ° C. pressure 20 kg / cm ² and heating and pressing time 30 minutes to form a coverlay. By sequentially applying pressure from the folded portion, the wiring board portion and the coverlay portion were completely brought into close contact with each other, and no remaining air portion was observed.
In this way, a flexible printed wiring board with a coverlay as shown in FIG. 1 (D) could be obtained.

[Example 2]
In place of the coating liquid 1-1 for forming an adhesion auxiliary layer used in Example 1, the following coating liquid 1-2 for forming an adhesion auxiliary layer was used.
(Preparation of adhesion auxiliary layer coating solution 1-2 containing polymerization initiating ability)
Under nitrogen, 4,4′-diaminophenyl ether (5.75 g: 28.7 mmol) was dissolved in N-methylpyrrolidone (30 ml) and stirred at room temperature for about 30 minutes. To this solution, 3,3 ′, 4,4 ″ -benzophenonetetracarboxylic dianhydride (9.25 g: 28.7 mmol) was added at 0 ° C. and stirred for 5 hours. The reaction solution was reprecipitated to obtain an insulating resin composition (polyimide precursor) containing polymerization initiation ability. The molecular weight (Mw) by GPC was 28,000. Further, the structure was confirmed by ¹ H-NMR and FT-IR.
The obtained insulating resin composition was dissolved in DMAc (manufactured by Wako Pure Chemical Industries, Ltd.) to give a 10% by weight solution.
(Formation of adhesion auxiliary layer 1-2)
The adhesion auxiliary layer coating solution 1-2 was applied by a die coating method so that the thickness of the adhesion auxiliary layer 1-2 from which the solvent was removed by drying was 8 μm, dried at 120 ° C. for 5 minutes, and then at 170 ° C. for 30 minutes. The adhesion auxiliary layer 1-2 was formed by heating for a minute.
Further, in the same manner as in Example 1, after providing a conductive substance-adsorptive resin precursor layer on the adhesion auxiliary layer 1-2, a portion of the surface left 1/3 as seen from the cross section of the polyimide film during UV exposure A polyimide film with a conductive material-adsorptive resin layer (resin film B) is produced by irradiating UV light with the mask so that the light hits the right third part of the back and the other part is not exposed to light. In the same manner as in Example 1, with the metal layer for forming a metal wiring having a region where a metal film capable of forming a metal wiring pattern and a region where no metal layer exists are present on both sides of the resin film substrate surface. A resin film was prepared.

Next, the metal layer forming region was patterned by the same method as in Example 1 to produce a wiring (metal pattern). The wiring formed on both ends of the resin film base is metal from the front and back in the metal layer non-formation region at the center of the resin film base and the adhesion auxiliary layer 1-2 is exposed. The pattern is folded so as to be in contact with the surface of the adhesion auxiliary layer, and the wirings on both sides face each other through the resin film substrate with the central adhesion auxiliary layer 1-2 exposed, and the condition is 4 at 300 ° C. and 25 kg / cm ^2. A flexible printed circuit board having two layers of wiring and having a protective layer (resin film base material layer) on the surface of each wiring was able to be produced by bonding by thermocompression bonding for a time.

Example 3
In Example 2, after providing the conductive substance-adsorbing resin precursor layer on the adhesion auxiliary layer 1-2, when viewed from the cross-section of the polyimide film during UV exposure, both the front and back surfaces are divided into three equal parts only. And the remaining portion is a metal that can form a metal wiring pattern as shown in FIG. 3A in the same manner as in Example 2 except that the mask is covered so that it is not exposed to light and UV light is irradiated. A resin film with a metal layer for forming a metal wiring having a region where the films 22A and 22B exist and a portion where the metal layer does not exist and the resin film substrate 12 is exposed was produced.
Next, a wiring pattern was prepared in the same manner as in Example 2 for the metal layer portion, and a laminate having metal patterns 24A and 24B on both sides of the central portion as shown in FIG. 3B was obtained. The portions of the resin film substrate 12 where the adhesion auxiliary layer 1-2 is exposed are folded back by 1/3 toward the wiring patterns 24A and 24B on both sides, and the wiring patterns 24A and 24B are overlapped so that the surface is covered. After being combined, a flexible printed circuit board having two layers of wiring and a protective layer (resin film base material layer) on the surface of each wiring by thermocompression bonding at 300 ° C. for 4 hours under the condition of 25 kg / cm ^2. Could be made.

Example 4
In Example 1, after providing the conductive substance-adsorptive resin precursor layer, a mask pattern having a line / space of 10 μm / 70 μm is formed so that the wiring pattern becomes a pattern in which electricity is released by energization. Then, UV exposure was performed through the mask pattern to form a conductive substance adsorbing resin layer having a width of 10 μm through a space of 70 μm. A conductive material is adsorbed and electroless-plated on the patterned conductive material-adsorbing resin layer in the same manner as in Example 1 to form a metal pattern, and then the formed electroless copper pattern is used as a power feeding layer. Power was applied, and electroplating was performed in the same manner as in Example 1. As a result, a wiring with a line / space of 50 μm / 30 μm was obtained by the full additive method.

Example 5
In Example 1, a flexible substrate was produced in the same manner as in Example 1 except that a polyimide film having a 200-micron hole drilled in advance on the front and back portions to be conducted was used.

Example 6
In Example 2, after forming the metal wiring, a 200 μm hole is made so as to conduct when the substrate formed on the front surface and the substrate formed on the back surface face each other on the polyimide film at the center, and the hole is filled with silver nano paste. After that, after performing the folding operation in the same manner as in Example 2, the heating and pressurizing operation was performed in the same manner as in Example 2 to produce a printed wiring board in the same manner as in Example 2.

Example 7
In Example 2, instead of using a resin film with a metal layer for forming a metal wiring in which a portion where a metal film capable of forming a metal wiring pattern is present and a portion not having a metal distribution layer are used, a metal foil is formed on one side Two polyimide films with copper foil and one polyimide film provided with the adhesion auxiliary layer 1-2 layer used in Example 2 on both sides, and a polyimide with copper foil on which one side is formed with metal foil After forming a wiring pattern in the film and making a hole in the polyimide film having the adhesion auxiliary layer 1-2 used in Example 2 on both sides in the same manner as in Example 6, and filling the hole with silver nanopaste, Three sheets were arranged so that the wiring layers face each other through the central polyimide film, and the heating and pressing operation was performed in the same manner as in Example 2 to produce a printed wiring board in the same manner as in Example 2.

Example 8
Instead of the conductive substance-adsorbing resin precursor P2 in Example 1, a conductive substance-adsorbing resin precursor P3 was synthesized as follows.
(Synthesis Example: Synthesis of Conductive Substance Adsorbing Resin Precursor P3)
A 1000 ml three-necked flask was charged with 35 g of N, N-dimethylacetamide and heated to 75 ° C. under a nitrogen stream. Thereto, 2-hydroxyethyl acrylate 6.60 g, 2-cyanoethyl acrylate 28.4 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.65 g N, N-dimethylacetamide 35 g solution was dropped over 2.5 hours. did. After completion of dropping, the mixture was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, Karenz AOI (manufactured by Showa Denko KK) 18.56 g, N, N-dimethylacetamide 19 g are added to the above reaction solution, at 55 ° C. for 4 hours. Reaction was performed. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane = 1: 1, and the solid matter was taken out to obtain 32 g of polymer A having a polymerizable group and an interactive group.
Using this conductive substance adsorbing resin precursor P3, an adsorbent resin precursor layer forming liquid having the following composition was prepared as a conductive substance adsorbing resin precursor layer forming liquid. Remove the solvent on top and apply to both sides by die coating so that the thickness after drying is 1.5 microns, and then dry at 80 ° C to 120 ° C to form a conductive material-adsorbing resin precursor layer did.

(Liquid composition 3 for forming an adsorbent resin precursor layer)
Conductive substance adsorbing resin precursor (P3) 10.5 parts by mass Acetone 73.0 parts by mass Methanol 34.0 parts by mass N, N-dimethylacetamide 5.0 parts by mass The conductive substance adsorbing resin After the precursor layer is formed on the adhesion assisting layer 1, a UV exposure machine (model number: UVF-502S, lamp: UXM-501MD) manufactured by Mitsunaga Electric Co., Ltd. is used so that only the portion where the metal layer is to be produced is exposed to UV light. Irradiating for 660 seconds with an irradiation power of 1.5 mW / cm ² (measurement of irradiation power by Ushio's UV integrated light meter UIT150-light receiving sensor UVD-S254), and then grafted in acetone in a stirred state The substrate on which the polymer was produced was immersed for 5 minutes and then washed with distilled water. Thus, a resin film C in which a conductive substance adsorbing resin layer was formed on the adhesion auxiliary layer 1 was produced.

[Applying plating catalyst]
The resin film C was immersed in 1 acetone solution of Pd for 30 minutes and then immersed in acetone for cleaning. Subsequently, the substrate A2 having the polymer layer was immersed in a 1% dimethylborane-water / methanol (water / methanol = 1/3) mixed solution for 15 minutes, and then immersed in acetone for cleaning.

Next, in the same manner as in Example 1, the electroless plating process and the electroplating process are performed, and the metal film portion where the metal wiring pattern can be formed and the metal resin portion where the metal wiring pattern cannot be formed coexist. A resin film with a metal layer for forming a metal wiring as a feature was produced.
Thereafter, by producing a wiring pattern in the same manner as in Example 1, it was possible to obtain a flexible printed circuit board with a coverlay in the same manner as in Example 1.

  From the above results, it is possible to easily form a printed wiring board excellent in productivity by producing a flexible printed board using the resin film with a metal layer for forming a metal wiring, which was made by the method of the present invention. .

(A)-(D) It is a manufacturing method of the resin film with a metal pattern of this invention, Comprising: It is a schematic sectional drawing which shows the structure for every process in the aspect in which a metal pattern is formed in the single side | surface of a resin film base material. It is a schematic sectional drawing which shows the one aspect | mode of the resin film base material which has the electroconductive substance adsorptive resin layer which can be used for the manufacturing method of this invention. (A)-(D) It is a manufacturing method of the resin film with a metal pattern of this invention, Comprising: It is a schematic sectional drawing which shows sequentially the structure for every process in the aspect which forms a metal pattern on both surfaces of a resin film base material.

Explanation of symbols

10. Resin film substrate having a metal layer in a partial region of the surface (described in a resin film with a metal layer)
12 Resin Film Base 16 Adhesion Auxiliary Layer 18 Conductive Substance Adsorbent Resin Precursor Layer 20 Conductive Substance Adsorbent Resin Layer 22, 22A, 22B Metal Layers 24, 24A, 24B Metal Pattern (Wiring)
26 Adhesive layer

Claims (14)

  A resin film with a metal layer having a region where a metal layer adhered to the substrate exists and a region where a metal layer does not exist on the same surface of the resin film substrate, wherein the metal layer adhered to the substrate exists A resin film with a metal layer, wherein a circuit pattern can be formed in a region by applying a subtract method or a semi-additive method using the metal layer forming region.   2. The resin film with a metal layer according to claim 1, wherein the region where the metal layer in close contact with the substrate is present is a continuous region which accounts for 5 to 99.5% of the surface of the resin film substrate.   2. The metal layer in the region where the metal layer adhered to the substrate exists is formed by one or more methods selected from a laminating method, a sputtering method, a vapor deposition method, and a plating method. Or the resin film with a metal layer of Claim 2.   The metal layer in the region where the metal layer in close contact with the substrate is bonded to the resin film substrate or a layer including a polymerization initiation layer provided on the surface of the resin film substrate, and has a functional group capable of adsorbing a conductive substance. Use the metal adsorbed on the conductive substance-adsorbing resin layer by adsorbing the conductive substance or metal to the conductive substance-adsorbing resin layer, or adsorbing metal by adsorbing and reducing metal ions. The resin film with a metal layer according to claim 1, wherein the resin film is formed by plating. A unit having a functional group having a property of adsorbing a conductive substance contained in the conductive substance-adsorbing resin layer is represented by a unit represented by the following formula (1) and a unit represented by the following formula (2): The resin film with a metal layer according to claim 4, which is a compound derived from a copolymer containing.

In Formula (1) and Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z each independently represent a single atom. Represents a bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group. .   Forming a metal pattern by patterning a metal layer region of a resin film with a metal layer having a region where a metal layer adhered to the substrate is present and a region where no metal layer is present on the same surface of the resin film substrate; And a step of joining the region where the metal layer does not exist to the region where the metal pattern is formed to apply energy, thereby joining the metal pattern and the region where the metal layer does not exist, to produce a resin film with a metal pattern Method. On the same surface of the resin film substrate, a metal pattern is formed by patterning a metal layer region of a resin film with a metal layer having a region where a metal layer adhered to the substrate is present and a region where no metal layer is present. Process,
A step of forming an adhesion layer by applying an adhesive resin to a region where the metal layer does not exist;
A step of joining the metal pattern and the adhesion layer by applying energy by overlapping the adhesion layer on the region where the metal pattern is formed;
A method for producing a resin film with a metal pattern comprising: Adhesiveness to the region where the metal layer of the resin film with a metal layer having a region where the metal layer adhered to the substrate exists in a pattern and a region where the metal layer does not exist on the surface of the resin film substrate A step of applying the resin to form an adhesion layer;
A step of joining the metal pattern and the adhesion layer by applying energy by overlapping the adhesion layer in a region where the metal layer exists in a pattern; and
A method for producing a resin film with a metal pattern comprising:   Conductive substance adsorption having a functional group capable of adsorbing a conductive substance by bonding a patterned metal layer in close contact with the base material to a resin film base material or a layer including a polymerization initiation layer provided on the surface of the resin film base material A conductive material or metal is adsorbed on the conductive resin layer, or a metal ion is adsorbed and reduced to adsorb the metal, and plating is performed using the metal adsorbed on the conductive material adsorbent resin layer. The method for producing a resin film with a metal pattern according to claim 8, wherein the method is formed.   An adhesive layer capable of forming an interaction between a metal and an organic substance is provided between the metal pattern and the resin film base material, and the metal pattern and the resin film base material are provided by applying energy to the adhesive layer. The method for producing a resin film with a metal pattern according to any one of claims 6 to 9, wherein adhesion is performed.   The metal pattern is bonded to an adhesion auxiliary layer including a polymerization initiation layer provided on the surface of the resin film substrate, and a conductive substance or metal is applied to the conductive substance-adsorbing resin layer having a conductive substance-adsorbing functional group. It is a metal pattern made of a metal formed by adsorbing or reducing a metal ion by adsorbing and reducing the metal ion, and plating using the adsorbed metal. The conductive film adsorbing resin layer of the resin film substrate is not formed, and the metal pattern and the resin film substrate are formed by applying energy to the adhesion auxiliary layer in the region where the metal layer where the adhesion auxiliary layer is formed does not exist. The method for producing a resin film with a metal pattern according to any one of claims 6 to 10, wherein:   The manufacturing method of the flexible printed circuit board characterized by including the process of producing the metal pattern for wiring using the manufacturing method of the resin film with a metal pattern of any one of Claims 6-11.   Before conducting the plating, make holes between the wirings on both sides of the film or mount parts, and apply metal to the holes by attaching a metal layer by plating. The method of manufacturing a flexible printed circuit board according to claim 12, wherein continuity is formed.   The wiring metal pattern is continuously formed so as to be electrically conductive, and then electroplating is performed using the wiring metal pattern as an electrode. The wiring is thickened to a desired thickness by a full additive method, and the electroplating is completed. 14. The method of manufacturing a flexible printed circuit board according to claim 12, wherein a circuit pattern is formed by removing a portion of a metal pattern that is not desired to be electrically conducted in a wiring metal pattern that is formed later. .

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