JP5106025B2 - Method for producing surface metal film material, surface metal film material, method for producing metal pattern material, metal pattern material, and composition for forming polymer layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a metallic-pattern material having excellent insulating reliability on the non-formation region of a metallic-pattern. <P>SOLUTION: A process for producing a metallic-pattern material comprises: a step of (a1) forming on a substrate a polymer layer made of a polymer which has a functional group interacting with a plating catalyst or a precursor therefor and is directly chemically bonded to the substrate, a step of (a2) imparting the plating catalyst or precursor therefor to the polymer layer, a step of (a3) plating the plating catalyst or precursor therefor, and a step of (a4) pattern-wise etching the deposit film formed. The polymer layer satisfies all of the following requirements 1 to 4: requirement 1: to have a saturation water absorption as measured at 25&deg;C and 50% of 0.01 to 10 mass%; requirement 2: to have a saturation water absorption as measured at 25&deg;C and 95% of 0.05 to 20 mass%; requirement 3: to have a water absorption after 1 hour immersion in 100&deg;C boiling water of 0.1 to 30 mass%; and requirement 4: to have a contact angle, as measured after dropping of 5 &mu;L of distilled water thereonto and standing for 15 seconds of 50 to 150 degrees at 25&deg;C and 50%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a surface metal film material, a surface metal film material, a method for producing a metal pattern material, a metal pattern material, and a polymer layer forming composition.

2. Description of the Related Art Conventionally, a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
As a method for producing such a metal pattern material, a “subtractive method” is mainly used. In this subtractive method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image. In this method, the metal film is etched to form a metal pattern, and finally the resist is removed.

  In the metal pattern obtained by this method, the adhesion between the substrate and the metal film is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, there is a problem that the high frequency characteristics when used as a metal wiring are deteriorated due to the unevenness of the obtained metal pattern at the substrate interface. In addition, in order to obtain a metal pattern with excellent adhesion between the metal film and the substrate, it is necessary to treat the substrate surface with a strong acid such as chromic acid in order to make the substrate surface uneven. There is a problem that a complicated process is necessary.

In order to solve this problem, plasma treatment is performed on the surface of the substrate, a polymerization initiating group is introduced on the surface of the substrate, a monomer is polymerized from the polymerization initiating group, and a surface graft polymer having a polar group is generated on the substrate surface. By performing this surface treatment, a method for improving the adhesion between the substrate and the metal film without roughening the surface of the substrate has been proposed (see, for example, Non-Patent Document 1). However, according to this method, since the graft polymer has a polar group, moisture absorption and desorption are likely to occur due to temperature and humidity changes, and as a result, the formed metal film and substrate are deformed. Had.
In addition, when a metal pattern obtained by using this method is used as a wiring of a metal wiring board, a graft polymer having a polar group remains at the interface portion of the board, and moisture, ions, etc. are easily retained. There were concerns about temperature and humidity dependence, resistance to ion migration between wires, and changes in shape. In particular, when applied to fine wiring such as printed wiring boards, high insulation between wirings (metal patterns) is required, and there is a demand for further improvement in insulation reliability between wirings. It is.
Advanced Materials 2000 No. 20 1481-1494

The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object thereof is to achieve the following object.
That is, a first object of the present invention is to provide a surface metal film material that is excellent in adhesion of a metal film and has little fluctuation in adhesion due to changes in humidity, and a method for producing the same.
A second object of the present invention is to provide a metal pattern material excellent in insulation reliability in a region where a metal pattern is not formed, and a method for manufacturing the metal pattern material.
Furthermore, the third object of the present invention is to provide a composition for forming a polymer layer that can form a polymer layer having low water absorption, high hydrophobicity, and excellent adsorption to the plating catalyst or its precursor. There is.

As a result of intensive studies in view of the above problems, the present inventor has found that the above object can be achieved by the following means.
That is, the first surface metal film material production method of the present invention is: (a1) Directly chemicalizing a polymer having a polymerizable group and a functional group that interacts with a plating catalyst or its precursor on a substrate. by generating a port Rimmer by binding, forming a polymer layer made of the polymer, and applying a plating catalyst or a precursor thereof (a2) the polymer layer, (a3) the plating catalyst or a A step of plating the precursor, and the polymer layer satisfies all of the following conditions 1 to 4.
Condition 1: Saturated water absorption is 0.01 to 10% by mass in a 25 ° C.-50% relative humidity environment.
Condition 2: Saturated water absorption in a relative humidity environment at 25 ° C. to 95% is 0.05 to 20% by mass.
Condition 3: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 30% by mass
Condition 4: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 50 to 150 degrees.

In the present invention, it is preferable that the polymer layer satisfies all of the following conditions 1 ′ to 4 ′.
Condition 1 ′: Saturated water absorption in a relative humidity environment at 25 ° C.-50% is 0.01 to 5% by mass
Condition 2 ′: Saturated water absorption at 0.05 ° C. to 95% relative humidity is 0.05 to 10% by mass
Condition 3 ′: Saturated water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 20% by mass
Condition 4 ′: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 55 to 150 degrees.

Further, the step (a1) in the present invention is preferably carried out by directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor on the substrate.
The step (a1) comprises a step (a1-1) of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; -2) It is also a preferable aspect to include a step of directly chemically bonding a polymer having a functional group that forms an interaction with the plating catalyst or its precursor and a polymerizable group to the polymerization initiation layer.

  In the present invention, a functional group that interacts with the plating catalyst or its precursor, and a polymer having a polymerizable group are represented by the unit represented by the following formula (1) and the following formula (2). It is preferable that it is a copolymer containing a unit.

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 Represents a single bond or a substituted or unsubstituted divalent organic group, ester group, amide group, or ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group; Represents.

Moreover, in this invention, it is a preferable aspect that the weight average molecular weights of the polymer which has the functional group which forms interaction with the said plating catalyst or its precursor, and a polymeric group are 20000 or more.
Furthermore, in the present invention, it is a preferable aspect that the polymer is a polymer having a functional group that interacts with a plating catalyst or a precursor thereof and directly chemically bonded to the substrate.

The method for manufacturing a second surface metal film material of the present invention, (a1 ') on a substrate by generating a port Rimmer by directly chemically bonding a polymer having a cyano group and a polymerizable group, consisting of the polymer A step of forming a polymer layer, (a2) a step of imparting a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of plating the plating catalyst or a precursor thereof. Features.
The step (a1 ′) is preferably performed by directly chemically bonding a polymer having a cyano group and a polymerizable group on the substrate.
Furthermore, the step (a1 ′) includes a step (a1-1 ′) of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed; (A1-2 ') It is also a preferable aspect to include a step of directly chemically bonding a polymer having a cyano group and a polymerizable group to the polymerization initiation layer.
In addition, it is a preferred embodiment that the polymer having a cyano group and a polymerizable group has a weight average molecular weight of 20000 or more.
In addition, it is a preferred embodiment that the polymer is a polymer having a cyano group and directly chemically bonded to the substrate.

In the present invention, in the step (a3), electroless plating is preferably performed, and it is more preferable that electroplating is further performed after the electroless plating.
Moreover, it is preferable that the plating catalyst used at the (a2) process in this invention is palladium.

The method for manufacturing a third surface metal film material of the present invention, have a functional group forming a duplex with respect to the interaction with the plating catalyst or a precursor thereof (a1 ") resin film, and, the resin film by generating a direct chemical bond with the port Rimmer When, forming a polymer layer made of the polymer, and applying a plating catalyst or a precursor thereof (a2) the polymer layer, (a3) the plating catalyst or Plating the precursor, and the polymer layer satisfies all of the following conditions 1 to 4.
Condition 1: Saturated water absorption is 0.01 to 10% by mass in a 25 ° C.-50% relative humidity environment.
Condition 2: Saturated water absorption in a relative humidity environment at 25 ° C. to 95% is 0.05 to 20% by mass.
Condition 3: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 30% by mass
Condition 4: 5 μL of distilled water is dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds is 50 to 150 degrees. That is, the method for producing the third surface metal film material of the present invention According to (a1 ″), a resin film is used as a substrate by the step (a1 ″), a polymer layer is formed on both sides thereof, and further, a metal film is formed on both sides by performing steps (a2) and (a3). A surface metal film material can be obtained.
In addition, it is preferable that the said (a1 ") process, the said (a2) process, and the said (a3) process are simultaneously performed with respect to both surfaces of the said resin film for every process.
Further, in the third method for producing a surface metal film material of the present invention, the polymer is a polymer having a functional group that interacts with a plating catalyst or a precursor thereof, and that is directly chemically bonded to the substrate. It is a preferable aspect.

  The surface metal film material of the present invention is obtained by the method for producing the surface metal film material of the present invention.

The first composition for forming a polymer layer of the present invention contains a polymer having a cyano group and a polymerizable group and a solvent capable of dissolving the polymer, and the method for producing the surface metal film material of the present invention. It is used for.
The second polymer layer-forming composition of the present invention, a polymer having a _{-O- (CH 2) n -O- (} n is an integer of from 1 to 5) represented by the structure and a polymerizable group, the And a solvent capable of dissolving the polymer, which is used in the method for producing a surface metal film material of the present invention.

The method for producing a metal pattern material of the present invention is characterized by comprising (a4) a step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material of the present invention into a pattern.
That is, the metal pattern material is produced by performing the steps (a1), (a2), and (a3) in the method for producing the surface metal film material, and then etching the formed plating film in a pattern [ (A4) Step] is performed.

  The metal pattern material of the present invention is obtained by the method for producing a metal pattern material of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the surface metal film material which is excellent in the adhesiveness of a metal film, and there are few fluctuation | variations of the adhesive force by a humidity change, and its preparation method can be provided.
Moreover, according to this invention, the metal pattern material excellent in the insulation reliability of the non-formation area | region of a metal pattern, and its manufacturing method can be provided.
Furthermore, according to the present invention, it is possible to provide a composition for forming a polymer layer that can form a polymer layer having low water absorption, high hydrophobicity, and excellent adhesion to the plating catalyst or its precursor. .

Hereinafter, the present invention will be described in detail.
<Method for producing surface metal film material, method for producing metal pattern material>
In the first method for producing a substrate with a metal film of the present invention, (a1) a functional group capable of interacting with a plating catalyst or a precursor thereof and a polymer having a polymerizable group are directly chemically bonded on the substrate. by generating a port Rimmer by the steps of forming a polymer layer made of the polymer, and applying a plating catalyst or a precursor thereof (a2) the polymer layer, (a3) the plating catalyst or a precursor thereof And the step of performing plating on the polymer layer, wherein the polymer layer satisfies all of the following conditions 1 to 4.
Condition 1: Saturated water absorption is 0.01 to 10% by mass in a 25 ° C.-50% relative humidity environment.
Condition 2: Saturated water absorption in a relative humidity environment at 25 ° C. to 95% is 0.05 to 20% by mass.
Condition 3: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 30% by mass
Condition 4: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 50 to 150 degrees.

Also, a manufacturing method of the second metal film-coated material of the present invention, (a1 ') on a substrate by generating a port Rimmer by directly chemically bonding a polymer having a cyano group and a polymerizable group, the polymer A step of forming a polymer layer comprising: (a2) a step of applying a plating catalyst or a precursor thereof to the polymer layer; and (a3) a step of plating the plating catalyst or a precursor thereof. It is characterized by that.

The method for producing a metal pattern material of the present invention is characterized by comprising (a4) a step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material of the present invention into a pattern.
In other words, the metal pattern material is produced by performing the steps (a1), (a1 ′), (a2), and (a3) in the method for producing the surface metal film material, and then forming the formed plating film in a pattern. Etching step [(a4) step].

In the first surface metal film material production method and metal pattern material production method of the present invention, the polymer layer satisfying the above four conditions has low water absorption even under high temperature and high humidity, and is hydrophobic. Is expensive. In addition, the polymer layer formed by the method for producing the second surface metal film material of the present invention also has low water absorption and high hydrophobicity even under high temperature and high humidity.
Moreover, after giving a plating catalyst etc. to the polymer layer which consists of a polymer couple | bonded with the board | substrate, metal film excellent in adhesiveness with a polymer layer can be obtained by plating using this.
From these points, the obtained surface metal film material has a metal film excellent in adhesion to the substrate, and further, the polymer layer does not change according to the humidity change. There will be little fluctuations in. Such a surface metal film material is applied to a method for producing a metal pattern material, which will be described later, and can be used as an electromagnetic wave prevention film, a shield material, and the like in addition to being used as an electric wiring material.
Also, in the case of a method for producing a metal pattern material, in the step (a4), the plating film formed on the entire surface of the substrate is etched into a pattern to obtain a metal pattern, so that this metal pattern is not formed in the region where the metal pattern is not formed. Even if the polymer layer is exposed, the exposed portion does not absorb water, and the insulation is not lowered due to this. As a result, the metal pattern material formed in the method for producing the metal pattern material of the present invention has excellent insulation reliability in the non-formation region of the metal pattern.

Hereinafter, each condition of 1-4 in the manufacturing method of the 1st surface metal film material of this invention is demonstrated.
The saturated water absorption rate and water absorption rate under conditions 1 to 3 can be measured by the following method.
First, after leaving the substrate in a vacuum dryer to remove moisture contained in the substrate, in the case of conditions 1 and 2, the substrate is left in a constant temperature and humidity chamber set to a desired temperature and humidity. In this case, the saturated water absorption and the water absorption are measured by immersing in a water bath containing boiling water at 100 ° C. for 1 hour and measuring the mass change. Here, the saturated water absorption in the conditions 1 and 2 indicates the water absorption when the mass does not change after 24 hours. Separately, for a laminate in which a polymer layer is formed on the substrate whose mass change is known in advance, by measuring the saturated water absorption rate and the water absorption rate of the laminate in the same manner, The water absorption rate of the polymer layer can be measured by the difference from the water absorption rate. In addition, using a petri dish or the like without providing a polymer layer on the substrate, a single polymer film constituting the polymer layer was prepared, and the water absorption rate of the obtained single polymer film was directly measured by the above method. May be.

The contact angle in condition 4 can be measured by the following method.
First, the laminated body which formed the polymer layer on the board | substrate is prepared, and it stores in the constant temperature / humidity tank set to 25 degreeC-50% relative humidity. Using the surface contact angle contact angle measuring device (OCA20 manufactured by Dataphysics) in a measurement chamber adjusted to 25 ° C.-50% relative humidity, 5 ul of distilled water was stored on the substrate (polymer layer). Is automatically dropped from a syringe, an image in the cross-sectional direction of the substrate is taken into a personal computer by a CCD camera, and the contact angle of water droplets on the substrate (polymer layer) is numerically calculated by image analysis.

Moreover, in this invention, it is a preferable aspect that the polymer layer obtained at the (a1) process satisfy | fills all the conditions of following 1'-4 '.
Condition 1 ′: Saturated water absorption in a relative humidity environment at 25 ° C.-50% is 0.01 to 5% by mass
Condition 2 ′: Saturated water absorption at 0.05 ° C. to 95% relative humidity is 0.05 to 10% by mass
Condition 3 ′: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 20% by mass
Condition 4 ′: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 55 to 150 degrees.

  Here, in order to obtain a polymer layer satisfying all of the above conditions 1 to 4 (preferably 1 ′ to 4 ′), the polymer constituting the polymer layer has a low water absorption property or a hydrophobic property ( A method using a material having low hydrophilicity), a method for adding a substance for reducing water absorption or a substance for improving hydrophobicity to the polymer layer, and further, after forming the polymer layer, the polymer layer For example, the polymer molecules that form a polymer can be immersed in a solution containing a reactive substance that hydrophobizes, and the polymer reacts with the reactive substance to make it hydrophobic, but it is easy to control water absorption and hydrophobicity. From the viewpoint of property, it is preferable to use a method using a polymer having a low water absorption or a hydrophobic polymer (a polymer having low hydrophilicity) as the polymer constituting the polymer layer.

  First, steps (a1) to (a3) in the method for producing the first surface metal film material of the present invention, and (a1 ′) to (a3) in the method for producing the second surface metal film material of the present invention. ) Will be described.

[Step (a1)]
In the step (a1) in the first surface metal film material production method of the present invention, a functional group that interacts with a plating catalyst or its precursor and a polymer having a polymerizable group are directly chemistry on the substrate. by generating a port Rimmer by coupling, to form a polymer layer made of the polymer. By this step, the substrate has a functional group that interacts with the plating catalyst or its precursor (hereinafter, may be simply referred to as “interactive group”), and directly with the substrate. A polymer layer comprising a chemically bonded polymer can be formed.
This polymer layer is required to satisfy all the above conditions 1 to 4.

The step (a1) is preferably performed by directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor on the substrate.
The step (a1) comprises a step (a1-1) of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; -2) It is also a preferable embodiment that the polymerization initiation layer is a step of forming a polymer layer made of a polymer having an interactive group and directly chemically bonded to the polymerization initiation layer.
In the step (a1-2), after the polymer having a polymerizable group and an interactive group is brought into contact with the polymerization initiation layer, energy is applied to the entire substrate surface (polymerization initiation layer). It is preferably a step of directly chemically bonding the polymer to the entire surface).

(Surface graft)
Formation of the polymer layer on the substrate uses a general method called surface graft polymerization. Graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on a polymer compound chain, thereby further polymerizing another monomer that initiates polymerization. In particular, when a polymer compound that gives active species forms a solid surface, this is called surface graft polymerization.

Any known method described in the literature can be used as the surface graft polymerization method applied to the present invention. For example, New Polymer Experimental Science 10, edited by Polymer Society, 1994, published by Kyoritsu Shuppan Co., Ltd., p135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams.
As a specific method of the photograft polymerization method, the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.

When forming the polymer layer in the present invention, in addition to the surface graft method described above, a reactive functional group such as a trialkoxysilyl group, an isocyanate group, an amino group, a hydroxyl group, or a carboxyl group is attached to the end of the polymer compound chain. It is also possible to apply a method in which these are bonded by a coupling reaction between this and a functional group present on the substrate surface.
Among these methods, from the viewpoint of generating more graft polymers, it is preferable to form a polymer layer using a photograft polymerization method, particularly a photograft polymerization method using UV light.

〔substrate〕
The “substrate” in the present invention has a function that allows the surface to form a state in which a polymer having a functional group that interacts with a plating catalyst or a precursor thereof is directly chemically bonded. The surface layer may have such surface characteristics, and a separate intermediate layer (for example, a polymerization initiation layer described later) may be provided on the substrate, and the intermediate layer may have such characteristics. Also good.

(Base material, substrate)
The substrate used in the present invention is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example, , Aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide Epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), paper or plastic film on which a metal as described above is laminated or deposited. As a base material used for this invention, an epoxy resin or a polyimide resin is preferable.
In addition, when these substrate surfaces have a function capable of forming a state in which a polymer having a functional group that interacts with a plating catalyst or its precursor has a direct chemical bond, the substrate itself May be used as a substrate.

  As the substrate in the present invention, a substrate containing polyimide having a polymerization initiation site described in paragraphs [0028] to [0088] of JP-A-2005-281350 in the skeleton can also be used.

  Moreover, the metal pattern material obtained by the method for producing a metal pattern material of the present invention can be applied to semiconductor packages, various electric wiring boards, and the like. When used in such applications, the following substrate containing an insulating resin, specifically, a substrate made of an insulating resin or a substrate having a layer made of an insulating resin on a base material is used. It is preferable.

When obtaining a substrate made of an insulating resin or a layer made of an insulating resin, a known insulating resin composition is used. In addition to the main resin, various additives can be used in combination with the insulating resin composition depending on the purpose. For example, a means such as adding a polyfunctional acrylate monomer for the purpose of increasing the strength of the insulating layer, or adding inorganic or organic particles for the purpose of increasing the strength of the insulating layer and improving electrical characteristics, etc. It can also be taken.
In addition, the “insulating resin” in the present invention means a resin having an insulating property that can be used for a known insulating film or insulating layer, and is not a perfect insulator. In addition, any resin having insulating properties according to the purpose can be applied to the present invention.

Specific examples of the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a bismaleimide. Examples thereof include resins, polyolefin resins, isocyanate resins and the like.
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 novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclo Examples include pentadiene 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 1,2-bis (vinylphenylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or a modified resin of this and a polyphenylene ether resin (Satoru Amaha et al., Journal of Applied Polymer Science). Vol. 92, 1252-1258 (2004)), liquid crystalline polymers (specifically, Kuraray Bexter, etc.), fluororesin (PTFE), and the like.

  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 thereof are described in "Electronic Technology" 2002/9, P35. Moreover, what contains an epoxy resin and / or a phenol resin as a thermosetting resin, and contains a phenoxy resin and / or polyether sulfone (PES) as a thermoplastic resin is also used in order to improve a dielectric characteristic.

  The insulating resin composition may contain a compound having a polymerizable double bond in order to promote crosslinking, specifically, an acrylate or methacrylate compound, and particularly a polyfunctional one. preferable. In addition, as a compound having a polymerizable double bond, methacrylic acid or acrylic acid is used for a thermosetting resin or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, or the like. Alternatively, a resin obtained by subjecting a part of the resin to (meth) acrylation reaction may be used.

  The insulating resin composition according to the present invention includes a composite of a resin and other components (in order to enhance the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical characteristics, etc.) of the resin film. Composite materials) 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, this insulating resin composition may be filled with a filler used for general wiring board resin materials as necessary, for example, inorganic fillers such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, and cured epoxy. You may mix | blend 1 type, or 2 or more types of organic fillers, such as resin, crosslinked benzoguanamine resin, and a crosslinked acrylic polymer. Among these, silica is preferably used as the filler.
Furthermore, the insulating resin composition may contain one or two various additives such as a colorant, a flame retardant, an adhesion imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. More than seeds may be added.

  When these materials are added to the insulating resin composition, it is preferable to add them in the range of 1 to 200% by mass, and more preferably in the range of 10 to 80% by mass with respect to the resin. Is done. When this addition amount is less than 1% by mass, there is no effect of enhancing the above properties, and when it exceeds 200% by mass, properties such as strength specific to the resin are lowered.

Specifically, the substrate used in such applications is a substrate made of an insulating resin having a dielectric constant (relative dielectric constant) at 1 GHz of 3.5 or less, or made of the insulating resin. A substrate having a layer on a substrate is preferred. Moreover, it is preferable that it is a board | substrate which consists of insulating resin whose dielectric loss tangent in 1 GHz is 0.01 or less, or a board | substrate which has the layer which consists of this insulating resin on a base material.
The dielectric constant and dielectric loss tangent of the insulating resin can be measured by a conventional method. For example, the cavity resonator perturbation method (for example, εr, tanδ measuring instrument for ultra-thin sheet, manufactured by Keycom Corporation) based on the method described in “18th Annual Conference of Electronics Packaging Society”, p189, 2004. ).
Thus, in the present invention, it is also useful to select an insulating resin material from the viewpoint of dielectric constant and dielectric loss tangent. Examples of insulating resins having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.01 or less include liquid crystal polymers, polyimide resins, fluororesins, polyphenylene ether resins, cyanate ester resins, and bis (bisphenylene) ethane resins. Furthermore, those modified resins are also included.

  The substrate used in the present invention preferably has a surface irregularity of 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and most preferably 20 nm in consideration of applications to semiconductor packages, various electric wiring boards and the like. It is as follows. The smaller the surface irregularity of this substrate (the surface irregularity of the layer when an intermediate layer or polymerization initiation layer is provided), the smaller the electrical loss during high-frequency power transmission when the obtained metal pattern material is applied to wiring etc. Is preferable.

In this invention, if a board | substrate is a plate-shaped object, for example, a resin film (plastic film), a polymer layer can be formed on both surfaces of a resin film by performing the (a1) process on both surfaces (this book Step (a1 ″) in the third method for producing a surface metal film material of the invention).
When the polymer layers are formed on both surfaces of the resin film (substrate) as described above, the surface metal in which the metal film is formed on both surfaces by further performing the steps (a2) and (a3) described later. A membrane material can be obtained.

In the present invention, when a surface graft polymerization method in which an active species is given to the substrate surface and a graft polymer is generated from the active species is used, a polymerization initiator is contained on the substrate or polymerization is performed when the graft polymer is generated. It is preferable to use a substrate on which a polymerization initiating layer having an initiating functional group is formed. By using this substrate, active sites can be efficiently generated and more graft polymers can be generated.
Hereinafter, the polymerization initiation layer in the present invention will be described. In addition, if a base material is a plate-shaped object, you may form a polymerization start layer on both surfaces.

(Polymerization initiation layer)
Examples of the polymerization initiation layer in the present invention include a layer containing a polymer compound and a polymerization initiator, a layer containing a polymerizable compound and a polymerization initiator, and a layer having a functional group capable of initiating polymerization.
The polymerization initiating layer in the present invention can be formed by dissolving necessary components in a soluble solvent, providing on the surface of the substrate by a method such as coating, and hardening by heating or light irradiation.

  The compound used for the polymerization initiation layer in the present invention is not particularly limited as long as it has good adhesion to the substrate and generates active species by applying energy such as actinic ray irradiation. it can. Specifically, a mixture of a polyfunctional monomer or a hydrophobic polymer having a polymerizable group in the molecule and a polymerization initiator can be used.

Specific examples of the hydrophobic polymer having a polymerizable group in the molecule include diene homopolymers such as polybutadiene, polyisoprene and polypentadiene, allyl (meth) acrylate, 2-allyloxyethyl. Homopolymers of allyl group-containing monomers such as methacrylene
Binary or multi-component copolymers such as styrene, (meth) acrylic acid ester, (meth) acrylonitrile and the like containing diene monomers such as butadiene, isoprene and pentadiene or allyl group-containing monomers as constituent units;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of these polymerizable compounds is preferably in the range of 10 to 100% by mass, particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

The polymerization initiation layer contains a polymerization initiator for expressing polymerization initiation ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, etc. that can exhibit polymerization initiation ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Depending on the purpose, it can be appropriately selected and used. Among these, use of photopolymerization is preferable from the viewpoint of production suitability, and therefore, it is preferable to use a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it is active with respect to irradiated actinic rays and can be subjected to surface graft polymerization from the polymerization initiation layer containing the photopolymerization initiator, and examples thereof include radical polymerization initiators and anionic polymerizations. An initiator, a cationic polymerization initiator, and the like can be used, but from the viewpoint of ease of handling and reactivity, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable.

Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Benzophenone (4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyldimethyl ketal and hydroxycyclohexyl phenyl ketone; triphenylsulfonium chloride, triphenyls Sulfonium salts such as tetraphenylphosphonium pentafluoro phosphate, diphenyl iodonium chloride, etc. iodonium salts such as diphenyliodonium sulfate and the like.
The content of the polymerization initiator is preferably in the range of 0.1 to 70% by mass, particularly preferably in the range of 1 to 40% by mass in terms of solid content in the polymerization initiator layer.

The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount when the polymerization initiating layer is formed on the substrate is, in terms of the expression after sufficient polymerization initiating ability and maintaining the film properties to prevent film peeling, in terms of the mass after drying, being 0. 1-20 g / m < ² > is preferable, 0.1-15 g / m < ² > is more preferable, and 0.1-2 g / m < ² > is still more preferable.

In the present invention, as described above, the composition for forming the polymerization initiation layer is disposed on the base material by coating or the like, and the film is formed by removing the solvent to form the polymerization initiation layer. Sometimes, it is preferable to harden by heating and / or light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that after the polymerization polymer is formed on the polymerization initiation layer, the polymerization initiation layer is removed. This is preferable because it is possible to effectively suppress such a situation.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried. However, from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

  The light irradiation performed as desired after heat-drying can use the light source used for the production | generation reaction of the graft polymer mentioned later. In the subsequent graft polymer generation step, the polymerization initiator existing in the polymerization start layer cures the polymerizable compound from the viewpoint of not inhibiting the active point of the polymerization start layer generated by energy application and the generation of the graft polymer. Even when radical polymerization is performed, it is preferable to irradiate with light so that it is not completely consumed. About light irradiation time, although it changes with the intensity | strength of a light source, generally it is preferable within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent cleaning is 80% or less and the initiator remaining rate after pre-curing is 1% or more.

In addition to the polymerization initiating layer containing the polymerizable compound and the polymerization initiator, a polymerization initiating layer using a polymer in which a polymerization initiating group described in JP-A-2004-161995 is pendant on a side chain is also preferable. 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). It is possible to form a polymerization initiating layer having a polymerization initiating group bonded to and having a polymer chain immobilized by a crosslinking reaction.
The polymerization initiating layer thus formed is also suitable as the polymerization initiating layer of the present application.

  Examples of the polymerization initiating polymer used here include those described in paragraphs [0011] to [0158] of JP-A No. 2004-161995. Specific examples of particularly preferred polymerization initiating polymers include the following.

-Formation of polymerization initiation layer-
The polymerization initiating layer using the polymerization initiating polymer in the present invention is prepared by dissolving the above-mentioned polymerization initiating polymer in an appropriate solvent, preparing a coating solution, placing the coating solution on a substrate by coating, and the like. The film is formed by removing and proceeding with the crosslinking reaction. That is, the polymerization initiating polymer is fixed by the progress of the crosslinking reaction. The immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a polymerization initiating polymer and a method using a crosslinking agent in combination, and it is preferable to use a crosslinking agent. As a method of using the self-condensation reaction of the polymerization initiating polymer, for example, when the crosslinkable group is —NCO, the property that the self-condensation reaction proceeds by applying heat is used. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

Moreover, as a crosslinking agent used for the method of using a crosslinking agent together, a conventionally well-known thing as described in Shinji Yamashita "crosslinking agent handbook" can be used.
Preferred combinations of the crosslinkable group and the crosslinker in the polymerization initiating polymer include (crosslinkable group, crosslinker) = (— COOH, polyvalent amine), (—COOH, polyvalent aziridine), (—COOH, many Polyvalent isocyanate), (—COOH, polyvalent epoxy), (—NH ₂ , polyvalent isocyanate), (—NH ₂ , aldehydes), (—NCO, polyvalent amine), (—NCO, polyvalent isocyanate), (—NCO, polyhydric alcohol), (—NCO, polyhydric epoxy), (—OH, polyhydric alcohol), (—OH, polyhalogenated compound), (—OH, polyhydric amine), (—OH , Acid anhydrides). Among these, (functional group, cross-linking agent) = (— OH, polyvalent isocyanate) is a more preferable combination in that a urethane bond is formed after the cross-linking and a high-strength cross-linking can be formed.

  Specific examples of the crosslinking agent in the present invention include the structures shown below.

  Such a crosslinking agent is added to the coating solution containing the above-mentioned polymerization initiating polymer when the polymerization initiating layer is formed. Thereafter, the crosslinking reaction proceeds by the heat during the drying of the coating film, and a strong crosslinked structure can be formed. More specifically, the following ex1. Or the dehydration reaction indicated by ex2. The cross-linking reaction proceeds by the addition reaction represented by the above, and a cross-linked structure is formed. The temperature conditions in these reactions are preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 80 ° C. or higher and 200 ° C. or lower.

  Further, the amount of the crosslinking agent added in the coating solution varies depending on the amount of the crosslinkable group introduced into the polymerization initiating polymer. However, the degree of crosslinking and the influence on the polymerization reaction due to the residual unreacted crosslinking component remain. In view of the above, it is usually preferably 0.01 to 50 equivalents, more preferably 0.01 to 10 equivalents, and 0.5 to 3 equivalents relative to the number of moles of the crosslinkable group. Further preferred.

Moreover, the solvent used when apply | coating a polymerization start layer will not be restrict | limited especially if the above-mentioned polymerization start polymer melt | dissolves. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the polymerization initiating layer using the polymerization initiating polymer is preferably 0.1 to 20 g / m ² in terms of the mass after drying from the viewpoint of the surface graft polymerization initiating ability and the film property. 15 g / m ² is preferred.

Furthermore, in the present invention, when a substrate having a layer made of an insulating resin as described above is used on the base material, a known polymerization initiator is contained in the layer made of the insulating resin to provide an insulating property. The polymerization initiation layer is preferably used. The polymerization initiator contained in this insulating polymerization initiator layer is not particularly limited. For example, the above-described thermal polymerization initiator, photopolymerization initiator (radical polymerization initiator, anionic polymerization initiator, cationic polymerization start) Agent), a polymer compound having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927, and further, a functional group having a polymerization initiating ability and a crosslinkable group in the side chain. The polymer (polymerization initiating polymer) etc. which have can be used.
In general, the amount of the polymerization initiator contained in the insulating polymerization start layer is preferably about 0.1 to 50% by mass in terms of solid content in the insulating layer, and is preferably 1.0 to 30.0. More preferably, it is about mass%.

(Generation of graft polymer)
As described above, the graft polymer is generated in the step (a1) by using a coupling reaction between the functional group present on the substrate surface and the reactive functional group of the polymer compound at the terminal or side chain. Alternatively, a photograft polymerization method can be used.
In the present invention, a substrate having a polymerization initiation layer formed on a substrate is used, and the polymerization initiation layer has a functional group (interactive group) that forms an interaction with the plating catalyst or its precursor. And the aspect [(a1-2) process] which forms the polymer layer which consists of a polymer directly chemically bonded with this polymerization start layer is preferable. More preferably, after the polymer having a polymerizable group and an interactive group is brought into contact with the polymerization initiation layer, the polymer is directly applied to the entire substrate surface (the entire polymerization initiation layer surface) by applying energy. This is a mode of chemical bonding. That is, the composition containing a compound having a polymerizable group and an interactive group is directly bonded to the active species generated on the surface of the polymerization initiation layer while contacting the surface of the polymerization initiation layer.

The contact is performed by immersing the substrate on which the polymerization initiating layer is formed in a liquid composition (the composition for forming a polymer layer of the present invention) containing a compound having a polymerizable group and an interactive group. However, from the viewpoint of handleability and production efficiency, as described later, a layer comprising a composition containing a compound having a polymerizable group and an interactive group (the composition for forming a polymer layer of the present invention). Is preferably formed on the substrate surface (polymerization initiation layer surface) by a coating method.
In addition, even when the polymer layer is formed on both sides of the resin film as in the step (a1 ″) in the third method for producing the metal film material of the present invention, it is easy to form the polymer layer on both sides simultaneously. From the viewpoint, it is preferable to use a coating method.

In the present invention, a compound having a polymerizable group and an interactive group, which is used when a graft polymer is produced by a surface graft polymerization method, will be described.
The compound having a polymerizable group and an interactive group in the present invention has a polymerizable group and an interactive group so that the polymer layer made of the generated graft polymer satisfies all the above conditions 1 to 4. It is preferable to use a compound having low water absorption and high hydrophobicity.
The interactive group in this compound is preferably a non-dissociable functional group, and the non-dissociable functional group means a functional group that does not generate a proton upon dissociation.
Such a functional group has a function of forming an interaction with the plating catalyst or its precursor, but does not have high water absorption and hydrophilicity like a dissociative polar group (hydrophilic group). The polymer layer composed of the graft polymer having this functional group can satisfy the conditions 1 to 4 described above.

  The polymerizable group in the present invention is a functional group in which compounds having a polymerizable group and an interactive group are bonded to each other, or a compound having a polymerizable group and an interactive group is bonded to a substrate by energy application. Specific examples include a vinyl group, a vinyloxy group, an allyl group, an acryloyl group, a methacryloyl group, an oxetane group, an epoxy group, an isocyanate group, a functional group containing active hydrogen, and an active group in an azo compound.

As the interactive group in the present invention, specifically, a group capable of forming a coordination with a metal ion, a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, and the like are preferable. Specifically, an imide group , Pyridine group, tertiary amino group, ammonium group, pyrrolidone group, amidino group, group containing triazine ring structure, group containing isocyanuric structure, nitro group, nitroso group, azo group, diazo group, azido group, cyano group, Nitrogen-containing functional group such as cyanate group (R—O—CN), ether group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, group containing N-hydroxy structure, etc. Oxygen-containing functional group, thioether group, thiooxy group, sulfoxide group, sulfone group, sulfite group, group containing sulfoximine structure, group containing sulfoxynium salt structure, sulfonic acid Sulfur-containing functional groups, such as groups containing ester structure, a phosphorus-containing functional groups, such as phosphine group, chlorine, a group containing a halogen atom such as bromine, and unsaturated ethylenic group and the like. In addition, an imidazole group, a urea group, or a thiourea group may be used as long as it is non-dissociative due to a relationship with an adjacent atom or atomic group.
Among them, since it has high polarity and high adsorption ability to a plating catalyst or the like, it is represented by an ether group (more specifically, —O— (CH ₂ ) _n —O— (n is an integer of 1 to 5). A cyano group is particularly preferable, and a cyano group is most preferable.

Generally, the higher the polarity, the higher the water absorption rate. However, since the cyano groups interact in the polymer layer so as to cancel each other's polarity, the film becomes dense and the entire polymer layer Therefore, the water absorption is lowered. Further, in the step (a2) to be described later, by adsorbing the catalyst with a good solvent in the polymer layer, the cyano group is solvated, the interaction between the cyano groups is eliminated, and the catalyst can interact with the plating catalyst. In view of the above, a polymer layer having a cyano group is preferable in that it exhibits low performance while interacting well with the plating catalyst while exhibiting low moisture absorption.
Further, the interactive group in the present invention is more preferably an alkyl cyano group. This is because the aromatic cyano group attracts electrons to the aromatic ring and lowers the donation of unpaired electrons, which is important for adsorptivity to the plating catalyst, but the alkyl cyano group is bonded to this aromatic ring. Therefore, it is preferable in terms of adsorptivity to the plating catalyst.

In the present invention, the compound having a polymerizable group and an interactive group may be in the form of a monomer, a macromonomer, or a polymer. Among these, from the viewpoint of the formability of the polymer layer and the ease of control, the polymer It is preferable to use (polymer having a polymerizable group and an interactive group).
Examples of the polymer having a polymerizable group and an interactive group include homopolymers and copolymers obtained using a monomer having an interactive group, such as a vinyl group, an allyl group, and a (meth) acryl group. A polymer having an ethylene addition polymerizable unsaturated group (polymerizable group) introduced therein is preferable, and the polymer having a polymerizable group and an interactive group has a polymerizable group at least at the main chain terminal or side chain. And those having a polymerizable group in the side chain are preferred.

As the monomer having an interactive group used in obtaining the polymer having a polymerizable group and an interactive group, any monomer can be used as long as it has a non-dissociable functional group as described above. For example, the following are specifically mentioned.
These may be used alone or in combination of two or more.

  In the polymer having a polymerizable group and an interactive group, the unit derived from the monomer having an interactive group is a polymerizable group and an interactive group from the viewpoint of forming an interaction with the plating catalyst or its precursor. It is preferable to contain in the range of 50-95 mol% in the polymer which has this, and it is more preferable to contain in the range of 40-80 mol%.

  In addition, when obtaining a polymer having a polymerizable group and an interactive group, in order to reduce water absorption and improve hydrophobicity, other monomers other than the monomer having the interactive group are added. It may be used. As the other monomer, a general polymerizable monomer may be used, and examples thereof include a diene monomer and an acrylic monomer. Of these, unsubstituted alkyl acrylic monomers are preferred. Specifically, tertiary butyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl methacrylate and the like can be preferably used.

Such a polymer having a polymerizable group and an interactive group can be synthesized as follows.
As synthesis methods, i) a method in which a monomer having an interactive group and a monomer having a polymerizable group are copolymerized, and ii) a monomer having an interactive group and a monomer having a double bond precursor are copolymerized. And then introducing a double bond by treatment with a base or the like, iii) reacting a polymer having an interactive group with a monomer having a polymerizable group to introduce a double bond (introducing a polymerizable group) ) Method. From the viewpoint of synthesis suitability, ii) a method in which a monomer having an interactive 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 This is a method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.

  As the monomer having an interactive group used for the synthesis of a polymer having a polymerizable group and an interactive group, the same monomers as those having the above interactive group can be used. A monomer may be used individually by 1 type and may use 2 or more types together.

Examples of the monomer having a polymerizable group to be copolymerized with a monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate, 2- (3-bromo-1-oxopropoxy) ethyl methacrylate, and the like.

  Furthermore, the polymerizability used for introducing an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in a polymer having an interactive group. Examples of the monomer having a group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

  Hereinafter, specific examples of the polymer having a polymerizable group and an interactive group that are preferably used in the present invention will be shown, but the present invention is not limited thereto.

In the present invention, the polymer having a polymerizable group and an interactive group is preferably a polymer having a cyano group as an interactive group (hereinafter referred to as “cyano group-containing polymerizable polymer”).
The cyano group-containing polymerizable polymer in the present invention is preferably a copolymer including, for example, a unit represented by the following formula (1) and a unit represented by the following formula (2).

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 single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group; L ¹ and L ² each independently represent a substituted or unsubstituted divalent organic group; To express.

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, or a methyl group substituted with a hydroxy group or a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

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, more preferably a divalent organic group having a urethane bond, and among them, one having a total carbon number of 1 to 9 is 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 formula (1-1) and formula (1-2), R ^a and R ^b each independently represent two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. A divalent organic group formed by using, preferably a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group, ethylene oxide group, diethylene oxide group, triethylene oxide group, tetraethylene oxide group, Examples include a dipropylene oxide group, a tripropylene oxide group, and a tetrapropylene oxide 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.

  As the cyano group-containing polymerizable polymer in 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 an oxygen atom, or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted C 1-5 substituent. And L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in the formula (3), the formula (1) have the same meanings as ^{R 1} and ^{R 2} in, and so 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 the cyano group-containing polymerizable polymer in the present invention, 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 an oxygen atom or NR (R Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms), and L ¹ represents a substituted or unsubstituted divalent organic group. Represents.

^{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 a divalent organic group having a urethane bond. Of these, those having 1 to 9 carbon atoms in total are particularly preferred.

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

In the above formula (5), R ⁵ represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents an oxygen atom, or NR ′ (R ′ represents a hydrogen atom or an alkyl group, preferably Represents a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms.), And L ² represents a substituted or unsubstituted divalent organic group.

R ⁵ 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 the formula (5), the linking site with the cyano group in L ² is preferably a divalent organic group having a linear, branched, or cyclic alkylene group. The organic group preferably has 1 to 10 carbon atoms.
As another preferred embodiment, it is preferable that the linkage site to the cyano group in L ² in Formula (5) is a divalent organic group having an aromatic group, and among them, the divalent organic group However, it is preferable that it is C6-C15.

The cyano group-containing polymerizable polymer in the present invention includes a unit represented by the above formulas (1) to (5), and is a polymer having a polymerizable group and a cyano group in the side chain. is there.
This cyano group-containing polymerizable polymer can be synthesized, for example, as follows.

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

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 cyano group-containing units Monomers used to form cyano 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 cyanoacetic 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 cyano group-containing units Monomers used to form cyano 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 (meta ) 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 vinyl , Allyl cyanoacetate, allyl 1-cyano-1-cyclopropanecarboxylate, N, N-dicyanomethyl (meth) acrylamide, N-cyanophenyl (meth) acrylamide, allyl cyanomethyl ether, allyl-o-cyanoethyl ether, allyl -M-cyanobenzyl ether, allyl-p-cyanobenzyl ether and the like.
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 cyano 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 cationic polymerizable group (hereinafter referred to as “reactive compound” as appropriate). It is preferable to use a method in which a cationically polymerizable group is introduced into the side chain.

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.
As specific combinations, (reactive group of polymer, 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.

The polymer having a cyano group used in the synthesis method of iii) includes a monomer used for forming the cyano group-containing unit mentioned in the above embodiment 1-2) and a reactive group for introducing a double bond. It is synthesized by radical polymerization of the monomer having it.
Examples of the monomer having a reactive group for introducing a double bond include monomers having a carboxyl group, a hydroxyl group, an epoxy group, or an isocyanate group as the reactive group.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, vinyl benzoate, Aronics M-5300, M-5400, M-5600 manufactured by Toagosei, acrylic ester PA, HH manufactured by Mitsubishi Corporation, and Kyoeisha Chemical Co., Ltd. Light acrylate HOA-HH manufactured by Nakamura Chemical Co., Ltd., NK ester SA, A-SA, etc.
As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (meth) acryloyl- 3-hydroxy-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl)-(meth) acrylate, methyl ester of 2- (hydroxymethyl)-(meth) acrylate, 3-chloro-2-hydroxypropyl (meth) ) Acrylate, 3,5-dihydroxypentyl (meth) acrylate, 1-hydroxymethyl-4- (meth) acryloylmethyl-cyclohexane, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1-methyl-2-acryl Iroxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 1-methyl-2-acryloyloxyethyl-2-hydroxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxy-3 -Chloropropyl phthalic acid, Aronics M-554, M-154, M-555, M-155, M-158, manufactured by Toagosei Co., Ltd., Bremer PE-200, PE-350, manufactured by NOF Corporation PP-500, PP-800, PP-1000, 70PEP-350B, 55PET800, lactone-modified acrylate having the following structure can be used.
_{CH 2 = CRCOOCH 2 CH 2 [} OC (= O) C 5 H 10] n OH
(R = H or Me, n = 1-5)

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and cyclomers A and M manufactured by Daicel Chemical.
As the monomer having an isocyanate group, Karenz AOI and MOI manufactured by Showa Denko can be used.
The polymer having a cyano group used in the synthesis method iii) may further contain a third copolymer component.

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, benzyl halide) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), (epoxy group, carboxyl group), etc. Can be mentioned.
Specifically, the following monomers can be used.

In the cyano group-containing polymerizable polymer in the present invention, in the case where L ¹ in the formula (1), formula (3), or formula (4) is a divalent organic group having a urethane bond, It is preferable to synthesize by a synthesis method (hereinafter referred to as synthesis method A).
That is, in the synthesis method A of the present invention, at least in a solvent, a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group are used, and the isocyanate group is added to the hydroxyl group. and forming a urethane bond in L ¹ by.

Here, as the polymer having a hydroxyl group in the side chain used in the synthesis method A, the monomer used for forming the cyano group-containing unit mentioned in the above embodiment 1-2) and the hydroxyl group-containing listed below A copolymer with (meth) acrylate is preferred. Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 1- (meth) acrylate. ) Acrylyl-3-hydroxy-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl)-(meth) acrylate, methyl ester of 2- (hydroxymethyl)-(meth) acrylate, 3-chloro-2-hydroxy Propyl (meth) acrylate, 3,5-dihydroxypentyl (meth) acrylate, 1-hydroxymethyl-4- (meth) acryloylmethyl-cyclohexane, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1- Tyl-2-acryloyloxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 1-methyl-2-acryloyloxyethyl-2-hydroxypropylphthalic acid, 2-acryloyloxyethyl- 2-hydroxy-3-chloropropylphthalic acid, Allonics M-554, M-154, M-555, M-155, M-158 manufactured by Toagosei Co., Ltd., Bremer PE-200 manufactured by NOF Corporation PE-350, PP-500, PP-800, PP-1000, 70PEP-350B, 55PET800, and lactone-modified acrylates having the following structures can be used.
_{CH 2 = CRCOOCH 2 CH 2 [} OC (= O) C 5 H 10] n OH (R = H or Me, n = 1~5)
In addition, the polymer which has a hydroxyl group in the side chain used for the synthesis method A may further contain a third copolymer component.

Among the polymers having a hydroxyl group in the side chain as described above, from the viewpoint of synthesizing a polymer having a high molecular weight, the bifunctional acrylate produced as a by-product when synthesizing a hydroxy group-containing (meth) acrylate was removed as a raw material. It is preferable to use a polymer synthesized using raw materials. As the purification method, distillation and column purification are preferred. More preferably, it is preferably synthesized using a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the following steps (1) to (4).
(1) Step (2) for dissolving a mixture containing hydroxyl group-containing (meth) acrylate and bifunctional acrylate by-produced when synthesizing the hydroxyl group-containing (meth) acrylate in water (2) obtained aqueous solution A step of separating the layer containing the first organic solvent and the bifunctional acrylate from the aqueous layer after adding the first organic solvent that separates from the water (3) In the aqueous layer, the hydroxyl group-containing A step of dissolving a compound having higher water solubility than (meth) acrylate (4) A step of adding a second organic solvent to the aqueous layer, extracting the hydroxyl group-containing (meth) acrylate, and then concentrating it.

The mixture used in the step (1) includes a hydroxyl group-containing (meth) acrylate and a bifunctional acrylate that is an impurity by-product when the hydroxyl group-containing (meth) acrylate is synthesized. It corresponds to a general commercial product of hydroxyl group-containing (meth) acrylate.
In the step (1), this commercial product (mixture) is dissolved in water to obtain an aqueous solution.

In the step (2), a first organic solvent that separates from water is added to the aqueous solution obtained in the step (1). Examples of the first organic solvent used here include ethyl acetate, diethyl ether, benzene, toluene and the like.
Thereafter, the layer (oil layer) containing the first organic solvent and the bifunctional acrylate is separated from the aqueous solution (aqueous layer).

In the step (3), a compound having higher water solubility than the hydroxyl group-containing (meth) acrylate is dissolved in the aqueous layer separated from the oil layer in the step (2).
Examples of the compound having higher water solubility than the hydroxyl group-containing (meth) acrylate used herein include alkali metal salts such as sodium chloride and potassium chloride, and inorganic salts such as alkaline earth metal salts such as magnesium sulfate and calcium sulfate. Is used.

In the step (4), the second organic solvent is added to the aqueous layer to extract the hydroxyl group-containing (meth) acrylate, followed by concentration.
Examples of the second organic solvent used here include ethyl acetate, diethyl ether, benzene, toluene and the like. The second organic solvent may be the same as or different from the first organic solvent described above.
For the concentration in the step (4), drying with anhydrous magnesium sulfate, distillation under reduced pressure, or the like is used.

The isolate containing the hydroxyl group-containing (meth) acrylate obtained by sequentially performing the steps (1) to (4) described above has a bifunctional acrylate in the total mass of 0.1% by mass or less. It is preferable to include. That is, through the steps (1) to (4), the bifunctional acrylate that is an impurity is removed from the mixture, and the hydroxyl group-containing (meth) acrylate is purified.
A more preferable range of the content of the bifunctional acrylate is 0.05% by mass or less in the total mass of the isolate, and the smaller the better.
By using the thus-purified hydroxyl group-containing (meth) acrylate, the bifunctional acrylate that is an impurity hardly affects the polymerization reaction, so a nitrile group-containing polymerizable polymer having a weight average molecular weight of 20000 or more is synthesized. can do.

  The hydroxy group-containing (meth) acrylate used in the step (1) is a hydroxyl group-containing (meth) acrylate used when synthesizing a polymer having a hydroxyl group in the side chain used in the synthesis method A described above. Those listed can be used. Among them, a monomer having a primary hydroxyl group is preferable from the viewpoint of reactivity to isocyanate, and further, from the viewpoint of increasing the polymerizable group ratio per unit weight of the polymer, a hydroxyl group containing a metal having a molecular weight of 100 to 250 (meta ) Acrylate is preferred.

  Moreover, as a compound which has an isocyanate group and a polymeric group used for the synthesis method A, 2-acryloyloxyethyl isocyanate (Karenz AOI, Showa Denko KK), 2-methacryloxy isocyanate (Karenz MOI, Showa Denko) Etc.).

Moreover, as a solvent used for the synthesis method A, those having an SP value (calculated by the Okitsu method) of 20 to 23 MPa ^1/2 are preferable. Specifically, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diester are used. Acetate, methyl acetoacetate, ethyl acetoacetate, 1,2,3-triacetoxy-propane, cyclohexanone, 2- (1-cyclohexenyl) cyclohexanone, propionitrile, N-methylpyrrolidone, dimethylacetamide, acetylacetone, acetophenone, triacetin 1,4-dioxane, dimethyl carbonate and the like.
Among these, from the viewpoint of synthesizing a high molecular weight substance, an ester solvent is more preferable, and diacetate solvents such as ethylene glycol diacetate and diethylene glycol diacetate, and dimethyl carbonate are more preferable.
Here, the SP value of the solvent in the present invention is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula. ΔF is a value described in the literature.
SP value (δ) = ΣΔF (Molar Attraction Constants) / V (molar volume)

The ratio of the polymerizable group-containing unit and the cyano group-containing unit of the cyano group-containing polymerizable polymer synthesized in the present invention as described above is preferably in the following range with respect to the entire 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 5-95 mol% with respect to the whole copolymerization component from an adsorptive viewpoint with respect to a plating catalyst, More preferably, it is 10-95 mol%.

In addition, the cyano group-containing polymerizable 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.
Specific examples of monomers used to form other units include acrylic resin skeleton, styrene resin skeleton, phenol resin (phenol-formaldehyde resin) skeleton, melamine resin (melamine and formaldehyde polycondensate) skeleton, Urea resin (polycondensate of urea and formaldehyde) skeleton, polyester resin skeleton, polyurethane skeleton, polyimide skeleton, polyolefin skeleton, polycycloolefin skeleton, polystyrene skeleton, polyacryl skeleton, ABS resin (polymer of acrylonitrile, butadiene, styrene) Skeleton, polyamide skeleton, polyacetal skeleton, polycarbonate skeleton, polyphenylene ether skeleton, polyphenylene sulfide skeleton, polysulfone skeleton, polyether sulfone skeleton, polyarylate skeleton, polyether Ether ketone skeleton, include monomers capable of forming a main chain skeleton of the polyamide-imide skeleton.
These main chain skeletons may be cyano group-containing units or main chain skeletons of polymerizable group-containing units.

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 ropyl (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 cyano group-containing polymerizable polymer in the invention is preferably from 1,000 to 700,000, more preferably from 2,000 to 200,000. In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the cyano group-containing polymerizable polymer in the present invention is preferably 20000 or more.
In addition, the polymerization degree of the cyano group-containing polymerizable polymer in the present invention is preferably a 10-mer or more, more preferably a 20-mer or more. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.
The preferred ranges of molecular weight and degree of polymerization described here are also suitable for polymers having a polymerizable group and an interactive group other than the cyano group-containing polymerizable polymer used in the present invention.

Specific examples of the cyano group-containing polymerizable polymer in the 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.

In the present invention, the compound having a polymerizable group and an interactive group, such as a cyano group-containing polymerizable polymer, has all of the above conditions 1 to 4 in addition to the polymerizable group and the interactive group. If it is the range which satisfy | fills, you may have a polar group.
By having a polar group, for example, when a protective layer is provided after a metal film is formed by a process described later, the adhesion can be improved in the contact region between the polymer layer and the protective layer. .

As described above, in order to form the polymer layer in the present invention, a liquid composition containing a compound having a polymerizable group and an interactive group such as a polymer having a polymerizable group and an interactive group, ie, A composition containing a compound having a polymerizable group and an interactive group and a solvent capable of dissolving the compound (preferably a cyano group or —O— (CH ₂ ) _n —O— (n is 1 to It is preferable to use the polymer layer-forming composition of the present invention comprising a polymer having a structure represented by an integer of 5) and a polymerizable group and a solvent capable of dissolving the polymer.
The content of the compound having a polymerizable group and an interactive group (for example, a cyano group-containing polymerizable polymer) in the composition is 2% by mass to 50% by mass with respect to the entire composition. preferable.

The solvent used in the composition is not particularly limited as long as the compound having a polymerizable group and an interactive group, which is the main component of the composition, can be dissolved. A surfactant may be further added to the solvent.
Examples of solvents that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, dimethylacetamide, Examples thereof include amide solvents such as N-methylpyrrolidone, nitrile solvents such as acetonitrile and propylonitrile, ester solvents such as methyl acetate and ethyl acetate, and carbonate solvents such as dimethyl carbonate and diethyl carbonate.
Among these, in the case of a composition using a cyano group-containing polymerizable polymer, amide-based, ketone-based, nitrile-based solvents, and carbonate-based solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, Acetonitrile, propionitrile, N-methylpyrrolidone and dimethyl carbonate are preferred.
Moreover, when apply | coating the composition containing a cyano group containing polymeric polymer, the solvent whose boiling point is 50-150 degreeC is preferable from handling ease. In addition, these solvents may be used alone or in combination.

Moreover, in this invention, when apply | coating the composition containing the compound which has a polymeric group and an interactive group on a board | substrate or a polymerization start layer, the solvent absorption rate of a board | substrate or a polymerization start layer is 5-25%. The solvent can be selected. This solvent absorption rate can be determined from the change in mass when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in the solvent and pulled up after 1000 minutes.
In addition, when a composition containing a compound having a polymerizable group and an interactive group is applied on a substrate or a polymerization initiation layer, a solvent in which the swelling rate of the substrate or the polymerization initiation layer is 10 to 45% is selected. May be. This swelling ratio can be determined from the change in thickness when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in a solvent and pulled up after 1000 minutes.

  The surfactant that can be added to the solvent as needed may be any that dissolves in the solvent. Examples of such surfactants include an anionic surfactant such as sodium n-dodecylbenzenesulfonate. Agents, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available) Examples of the product include a trade name “Tween 20” and the like, and nonionic surfactants such as polyoxyethylene lauryl ether.

  Moreover, a plasticizer can also be added as needed. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, diethyl ester, dibutyl ester, di-2-ethylhexyl ester, dinormal octyl ester, diisononyl ester, dinonyl ester, diisodecyl ester). Ester, butyl benzyl ester), adipic acid ester (dioctyl ester, diisononyl ester), azelain san dioctyl, sebacin sun ester (dibutyl ester, dioctyl ester) tricresyl phosphate, acetyl citrate tributyl, epoxidized soybean oil, trimellit High boiling solvents such as trioctyl acid, chlorinated paraffin, dimethylacetamide, and N-methylpyrrolidone can also be used.

  A polymerization inhibitor may be added to the composition containing a compound having a polymerizable group and an interactive group, if necessary. As the polymerization inhibitor that can be used, hydroquinones such as hydroquinone, ditertiary butyl hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, phenols such as p-methoxyphenol and phenol, Nitrosamines such as benzoquinones, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy free radical), free radicals such as 4-hydroxy TEMPO, phenothiazines, N-nitrosophenylhydroxyamine, and aluminum salts thereof Catechols can be used.

In addition, a curing agent and / or a curing accelerator can be added to the composition containing a compound having a polymerizable group and an interactive group, as necessary, in order to advance curing of the polymerization initiation layer. . For example, as a curing agent and / or curing accelerator in the case where an epoxy compound is contained in the polymerization initiation layer, in the polyaddition type, aliphatic polyamine, alicyclic polyamine, aromatic polyamine, polyamide, acid anhydride, phenol, phenol Examples of catalyst types such as novolak, polymercaptan, compounds having two or more active hydrogens include aliphatic tertiary amines, aromatic tertiary amines, imidazole compounds, and Lewis acid complexes.
Also, those that start curing by heat, light, moisture, pressure, acid, base, etc. include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamidoamine, mensendiamine, isophoronediamine, N-amino. Ethylpiperazine, 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, methylteto Hydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), Methylcyclohexenetetracarboxylic 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-2-ethylhexyl Lurate, 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 Examples include hydrazide, diaminomaleonitrile, melamine derivatives, imidazole derivatives, polyamine salts, amine imide compounds, aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, triallyl selenium salts, ketimine compounds and the like.

  These curing agents and / or effect accelerators may be added up to about 0 to 50% by mass of the remaining non-volatile components from which the solvent has been removed from the viewpoints of solution applicability, adhesion to substrates and plating films, and the like. preferable. Moreover, you may add a hardening | curing agent and / or a hardening accelerator to a polymerization start layer, In that case, it is preferable to satisfy | fill the said range with the quantity added to the polymerization start layer, and the total amount added in the polymer layer.

  Further, rubber components (for example, CTBN), flame retardants (for example, phosphorus flame retardants), diluents and thixotropic agents, pigments, antifoaming agents, leveling agents, coupling agents, etc. It may be added. Moreover, you may add these additives to a polymerization start layer as needed.

By using a composition in which a compound having these polymerizable group and interactive group and various additives are appropriately mixed, the physical properties of the formed polymer layer, for example, thermal expansion coefficient, glass transition temperature, Young's modulus , Poisson's ratio, breaking stress, yield stress, pyrolysis temperature, etc. can be set optimally. In particular, it is preferable that the breaking stress, yield stress, and thermal decomposition temperature be higher.
The obtained polymer layer can be measured for thermal durability by a temperature cycle test, a thermal aging test, a reflow test, and the like. For example, with respect to thermal decomposition, a mass loss when exposed to an environment of 200 ° C. for 1 hour is 20 % Or less, it can be evaluated that it has sufficient heat durability.

When a composition containing a compound having a polymerizable group and an interactive group is brought into contact, the coating amount is in terms of solid content from the viewpoint of sufficient interaction formation with the plating catalyst or its precursor. And 0.1 to 10 g / m ² is preferable, and 0.5 to 5 g / m ² is particularly preferable.
In addition, when a composition containing a compound having a polymerizable group and an interactive group is applied on a substrate and dried to form a layer containing a compound having a polymerizable group and an interactive group, Between application and drying, the remaining solvent may be removed by allowing to stand at 20 to 40 ° C. for 0.5 to 2 hours.

(Granting energy)
As a method for applying energy to the substrate surface, for example, radiation irradiation such as heating or exposure can be used. For example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
Specific examples generally used include direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The time required for applying energy is usually between 10 seconds and 5 hours, although it varies depending on the amount of the graft polymer produced and the light source.

In the case of performing the application of energy by the exposure, the exposure power, because to easily proceed the graft polymerization, addition, in order to suppress the decomposition of the produced graft ^polymer, of 10mJ / cm ² ~5000mJ / cm 2 preferably in the range, more ^preferably in the range of ^{50mJ / cm 2 ~3000mJ / cm 2} .
In addition, when a polymer having an average molecular weight of 20,000 or more and a polymerization degree of 200 or more is used as the compound having a polymerizable group and an interactive group, the graft polymerization proceeds easily with low energy exposure. Degradation of the polymer can be further suppressed.

  By the step (a1) described above, a polymer layer (graft polymer layer) composed of a graft polymer having an interactive group can be formed on the substrate.

  When the obtained polymer layer is, for example, 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, the polymer layer is washed with a highly alkaline solution. It can be carried out.

[(A1 ′) step]
In the second metal film-coated material (a1 ') step in a manufacturing method of the present invention, on a substrate, by generating a port Rimmer by directly chemically bonding a polymer having a cyano group and a polymerizable group, the polymer A polymer layer is formed. By this step, a polymer layer made of a polymer having a cyano group and directly chemically bonded to the substrate can be formed on the substrate.
This step is a method similar to the method described in step (a1) except that a compound having a polymerizable group and a cyano group is used as the compound having a polymerizable group and an interactive group in step (a1). Are also used, and preferred embodiments are also the same.
By this step (a1 ′), a polymer layer (graft polymer layer) composed of a graft polymer having a cyano group can be formed on the substrate.

  The polymer constituting the polymer layer obtained in this step has a cyano group as a functional group that forms an interaction with the plating catalyst or its precursor. As described above, this cyano group has a high polarity and a high adsorption ability to a plating catalyst or the like, but does not have high water absorption and hydrophilicity like a dissociative polar group (hydrophilic group). The polymer layer made of the graft polymer having a cyano group has low water absorption and high hydrophobicity.

[Step (a2)]
In the step (a2), a plating catalyst or a precursor thereof is applied to the polymer layer formed in the step (a1) or (a1 ′). In this step, the interactive group (cyano group) of the graft polymer constituting the polymer layer adheres (adsorbs) the applied plating catalyst or its precursor depending on its function.
Here, examples of the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in the plating step (a3) described later. Therefore, the plating catalyst or its precursor is determined by the type of plating in the (a3) plating step.
Here, the plating catalyst or its precursor used in this step is preferably an electroless plating catalyst or its precursor.

(Electroless plating catalyst)
As the electroless plating catalyst used in the present invention, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Examples thereof include metals (known as metals that can be electrolessly plated that have a lower ionization tendency than Ni), and specifically include Pd, Ag, Cu, Ni, Al, Fe, Co, and the like. Among them, those capable of multidentate coordination are preferable, and Pd is particularly preferable from the viewpoint of the number of types of functional groups capable of coordination and high catalytic ability.
This electroless plating catalyst may be used as a metal colloid. 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 protective agent used here.

(Electroless plating catalyst precursor)
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. The metal ions of the metals mentioned as the electroless plating catalyst are mainly used. 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 polymer layer and before being immersed in the electroless plating bath by changing it to a zero-valent metal by a reduction reaction. The electroplating 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.

In practice, the metal ion that is the electroless plating precursor is applied onto the polymer layer using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in an appropriate solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCn, 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, and Pd ions. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. Pd ions are preferred in terms of the number of types of groups and catalytic ability.

As a method for applying a metal that is an electroless plating catalyst or a metal salt that is an electroless plating precursor to a polymer layer, a dispersion in which a metal is dispersed in an appropriate dispersion medium or a metal salt with an appropriate solvent. A solution containing dissolved and dissociated metal ions is prepared, and the dispersion or solution is applied on the polymer layer, or the substrate on which the polymer layer is formed is immersed in the dispersion or solution.
In the step (a1) or (a1 ′), when a surface graft polymerization method is used, a composition containing a compound having a polymerizable group and an interactive group (cyano group) is brought into contact with the substrate. You may use the method of adding an electroless-plating catalyst or its precursor in this composition. By applying a surface graft polymerization method by contacting a composition containing a compound having a polymerizable group and an interactive group (cyano group) with an electroless plating catalyst or a precursor thereof on a substrate. A polymer layer containing a polymer having an interactive group (cyano group) and directly chemically bonded to the substrate, and a plating catalyst or a precursor thereof can be formed. If this method is used, the (a1) or (a1 ′) step and the (a2) step in the present invention can be performed in one step.

  In addition, when the polymer layer is formed with respect to both surfaces of the resin film by passing through the (a1 ″) step in the third surface metal film material manufacturing method of the present invention, In order to simultaneously contact the electroless plating catalyst or a precursor thereof, it is preferable to use the above immersion method.

By contacting the electroless plating catalyst or a precursor thereof as described above, an interaction group (cyano group) in the polymer layer can interact with an intermolecular force such as van der Waals force, or a lone electron. An electroless plating catalyst or a precursor thereof can be adsorbed by utilizing an interaction by a coordinate bond by a pair.
From the viewpoint of sufficiently performing such adsorption, the metal concentration in the dispersion, solution, composition, or metal ion concentration in the solution is preferably in the range of 0.001 to 50% by mass, More preferably, it is in the range of 0.005 to 30 mass%. Further, the contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.

(Other catalysts)
In the present invention, a zero-valent metal can be used as a catalyst used for direct electroplating without performing electroless plating on the polymer layer in the step (a3) described later. Examples of the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, Co, and the like. Among them, those capable of multidentate coordination are preferable, and in particular, an interaction group (cyano group) is particularly preferable. Pd, Ag, and Cu are preferred from the standpoints of adsorption (adhesion) and catalytic ability.

  Through the step (a2) described above, an interaction can be formed between the interactive group (cyano group) in the polymer layer and the plating catalyst or its precursor.

[Step (a3)]
In the step (a3), a plating film is formed by performing plating on the polymer layer to which the electroless plating catalyst or its precursor has been applied. The formed plating film has excellent conductivity and adhesion.
The type of plating performed in this step includes electroless plating, electroplating, etc., and is selected depending on the function of the plating catalyst or its precursor that forms an interaction with the polymer layer in the step (a2). can do.
That is, in this step, electroplating or electroless plating may be performed on the polymer layer provided with the plating catalyst or its precursor.
Among them, in the present invention, it is preferable to perform electroless plating from the viewpoint of improving the formability and adhesiveness of the hybrid structure that appears in the polymer layer. In order to obtain a plating layer having a desired film thickness, it is a more preferable aspect that electroplating is further performed after electroless plating.
Hereinafter, the plating suitably performed in this process will be described.

(Electroless plating)
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.
The electroless plating in this step is performed, for example, by immersing the substrate provided with the electroless plating catalyst in water and removing excess electroless plating catalyst (metal) and then immersing it 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 provided with the electroless plating catalyst precursor is immersed in the electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the polymer layer, the substrate is washed with excess precursor. After removing the body (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the plating catalyst 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 reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above. Is possible. The catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and is 0.1% to 50%, preferably 1% to 30%. . As the reducing agent, boron-based reducing agents such as sodium borohydride and dimethylamine borane, and reducing agents such as formaldehyde and hypophosphorous acid can be used.

  As a composition of a general electroless plating bath, in addition to a solvent, 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.

The solvent used in this plating bath preferably contains an organic solvent having a high affinity for a polymer layer having low water absorption and high hydrophobicity (a polymer layer satisfying all the above conditions 1 to 4). . The selection and content of the organic solvent may be prepared according to the physical properties of the polymer layer. In particular, it is preferable to reduce the content of the organic solvent as the saturated water absorption rate in the condition 1 of the polymer layer increases. Specifically, it is as follows.
That is, when the saturated water absorption in Condition 1 is 0.01 to 0.5% by mass, the content of the organic solvent in all the solvents in the plating bath is preferably 20 to 80%, and the saturated water absorption is 0. In the case of 5 to 5% by mass, the content of the organic solvent in the total solvent of the plating bath is preferably 10 to 80%, and when the saturated water absorption is 5 to 10% by mass, the total solvent of the plating bath The content of the organic solvent is preferably 0 to 60%. When the saturated water absorption is 10 to 20% by mass, the content of the organic solvent in the total solvent of the plating bath is 0 to 45%. It is preferable.
The organic solvent used in the plating bath needs to be a solvent that can be used in water, and in this respect, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.

Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath, and copper and gold are particularly preferable from the viewpoint of conductivity.
In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains CuSO ₄ as a copper salt, HCOH as a reducing agent, a chelating agent such as EDTA or Rochelle salt, which is a stabilizer of copper ions, and a trialkanolamine. . 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. These plating baths may contain components other than the above components.

The thickness of the plating film formed by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. From the viewpoint, it is preferably 0.5 μm or more, and more preferably 3 μm or more.
Further, the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.

  The electroless plating film obtained as described above has fine particles made of electroless plating catalyst and plating metal dispersed in the polymer layer by cross-sectional observation with SEM. It was confirmed that metal was deposited. Since the interface between the substrate and the plating film is a hybrid state of polymer and fine particles, the interface between the substrate (organic component) and the inorganic substance (catalyst metal or plating metal) is smooth (for example, the unevenness difference is 500 nm or less). However, the adhesion is good.

(Electroplating)
In this step, when the plating catalyst or its precursor applied in step (a2) has a function as an electrode, electroplating is performed on the polymer layer to which the catalyst or its precursor is applied. Can do.
In addition, after the above-described electroless plating, the formed plating film may be used as an electrode, and electroplating may be further performed. As a result, a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate. Thus, since electroplating is performed after electroless plating, the metal film can be formed to a thickness according to the purpose, and therefore, the metal film of the present invention is suitable for various applications.

  A conventionally known method can be used as the electroplating method in the present invention. 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 metal concentration contained in the plating bath or the current density. In addition, the film thickness in the case of using it for general electric wiring etc. is preferably 0.5 μm or more, and more preferably 3 μm or more from the viewpoint of conductivity.

In the present invention, the metal or metal salt derived from the above-described plating catalyst, plating catalyst precursor, and / or metal deposited in the polymer layer by electroless plating is used as a fractal microstructure in the layer. By being formed, the adhesion between the metal film and the polymer layer can be further improved.
The amount of metal present in the polymer layer is 5-50% by area of the metal in the region from the outermost surface of the polymer layer to a depth of 0.5 μm when the substrate cross section is photographed with a metal microscope. When the arithmetic average roughness Ra (JIS B0633-2001) between the polymer layer and the metal interface is 0.05 μm to 0.5 μm, a stronger adhesion is exhibited.

<Surface metal film material>
The surface metal film material of the present invention can be obtained through the steps of the method for producing the surface metal film material of the present invention. In addition, if the 3rd surface metal film material preparation method of this invention is applied, the surface metal film material in which the metal film was formed in both surfaces can be obtained.
The surface metal film material obtained by the method for producing a surface metal film material of the present invention has an effect that there is little fluctuation in the adhesion of the metal film even under high temperature and high humidity. This surface metal film material can be applied to various uses such as an electromagnetic wave prevention film, a coating film, a two-layer CCL material, and an electric wiring material.

The manufacturing method of the metal pattern material of this invention has the process of etching the plating film of the surface metal film material of this invention obtained through the process of (a1)-(a3) in pattern shape.
This (a4) etching step will be described below.

[Step (a4)]
In the step (a4), the plating film (metal film) formed in the step (a3) is etched into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the plating film formed on the entire substrate surface by etching.
Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.

  With the subtractive method, a dry film resist layer is provided on the formed plating film, the same pattern as the metal pattern part is formed by pattern exposure and development, the plating film is removed with an etching solution using the dry film resist pattern as a mask, This is a method of forming a metal pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like ones can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable because the apparatus is simple. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.

  The semi-additive method is to provide a dry film resist layer on the formed plating film, form the same pattern as the non-metallic pattern part by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask. In this method, quick etching is performed after removing the dry film resist pattern, and the plating film is removed in a pattern to form a metal pattern. The dry film resist, etching solution, etc. can use the same material as the subtractive method. Further, as the electroplating technique, the technique described above can be used.

  Through the above steps (a1) to (a4), a metal pattern material having a desired metal pattern is produced.

On the other hand, the polymer layer obtained in the step (a1) or (a1 ′) is formed into a pattern, and the metal pattern material is produced by performing the steps (a2) and (a3) on the pattern-like polymer layer. (Full additive method).
As a method for forming the polymer layer obtained in the step (a1) or (a1 ′) into a pattern, specifically, the energy applied when forming the polymer layer may be made into a pattern, A pattern-like polymer layer can be formed by removing a portion to which energy is not applied by development.
The developing method is carried out by immersing a material used for forming a polymer layer such as a compound having a polymerizable group and an interactive group (cyano group) in a solvent capable of dissolving. The immersion time is preferably 1 to 30 minutes.
In addition, the polymer layer (a1) or (a1 ′) is directly patterned by a known coating method such as a gravure printing method, an ink jet method, or a spray coating method using a mask, then given energy, and then developed. It may be formed.
Steps (a2) and (a3) for forming a plating film on the patterned polymer layer are the same as those described above.

<Metal pattern material>
The metal pattern material of the present invention is obtained by the above-described method for producing a metal pattern material of the present invention.
As described above, since the polymer layer constituting the obtained metal pattern material has low water absorption and high hydrophobicity, the exposed portion of the polymer layer (the region where the metal pattern is not formed) is excellent in insulation reliability. .

  The metal pattern material of the present invention is preferably one in which a metal film (plating film) is provided on the entire surface or locally on a substrate having a surface irregularity of 500 nm or less (more preferably 100 nm or less). Moreover, it is preferable that the adhesiveness of a board | substrate and a metal pattern is 0.2 kN / m or more. That is, it is characterized in that the substrate surface is smooth and the adhesion between the substrate and the metal pattern is excellent.

The unevenness of the substrate surface is a value measured by cutting the substrate perpendicular to the substrate surface and observing the cross section with an SEM.
More specifically, Rz measured in accordance with JIS B 0601, that is, “the difference between the average value of the Z data of the peak from the maximum to the fifth in the designated plane and the average value of the valley from the minimum to the fifth. ”Is preferably 500 nm or less.
Further, the adhesion value between the substrate and the metal film was determined by attaching a copper plate (thickness: 0.1 mm) to the surface of the metal film (metal pattern) with an epoxy-based adhesive (Araldite, manufactured by Ciba-Geigy). After drying for 4 hours, a 90 degree peeling experiment is performed based on JIS C 6481, or the edge of the metal film itself is directly peeled off and a 90 degree peeling experiment is performed based on JIS C 6481. is there.

  The metal pattern material obtained by the method for producing a metal pattern material of the present invention is applied to various uses such as a semiconductor chip, various electric wiring boards, FPC, COF, TAB, antenna, multilayer wiring board, motherboard and the like. be able to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Unless otherwise specified, “%” and “part” are based on mass.

[Example 1]
[Production of substrate]
An epoxy insulating film GX-13 (film thickness: 45 μm) manufactured by Ajinomoto Fine Techno Co., Ltd. is heated and pressurized on a glass epoxy substrate as an electrical insulating layer, and 100 to 110 ° C. at a pressure of 0.2 MPa using a vacuum laminator. The base material was obtained by bonding under the above conditions.
Next, an insulating composition containing a polymerization initiator having the following composition was applied onto the substrate by spin coating so as to have a thickness of 3 microns, and the solvent was removed by leaving it at 30 ° C. for 1 hour. Thereafter, it was dried at 140 ° C. for 30 minutes to form a polymerization initiation layer (insulating polymerization initiation layer).

(Insulating composition containing a polymerization initiator)
20 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.), cresol novolac type epoxy resin (epoxy equivalent 215, Epiklon N-673 manufactured by Dainippon Ink & Chemicals, Inc.) 45 30 parts by mass of phenol novolac resin (phenolic hydroxyl group equivalent 105, phenolite manufactured by Dainippon Ink & Chemicals, Inc.) in 20 parts by mass of ethyl diglycol acetate and 20 parts of solvent naphtha are heated and dissolved with stirring. After cooling to room temperature, 30 parts by mass of cyclohexanone varnish of phenoxy resin consisting 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- Phenyl-4,5 0.8 parts by mass of bis (hydroxymethyl) imidazole, 2 parts by mass of finely pulverized silica, and 0.5 parts by mass of a silicon-based antifoaming agent were added, and polymerization initiator polymer P synthesized by the following method was added to this mixture. 10 parts was added to obtain an insulating composition containing a polymerization initiator.

(Synthesis of polymerization initiating polymer P)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. [2- (Acryloyloxy) ethyl] (4-benzoylbenzoyl) dimethyl ammonium bromide 8.1g, 2-Hydroxyethylmethacrylate 9.9-g, isopropymethylmethayl 2-methyl-2-azomethylate-2-azomethyl-2'-methyl-2 ) A solution of 0.43 g and MFG 30 g was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain a polymer P having a polymerization initiating group.

  After the polymerization initiation layer as described above was formed, a curing treatment was performed at 180 ° C. for 30 minutes. Thereby, a substrate A1 was obtained. The surface roughness (Rz) of this substrate A1 was 0.2 μm.

[Formation of polymer layer]
(Synthesis of Polymer A having Polymerizable Group and Interactive Group)
First, a polymer A having a polymerizable group and an interactive group was synthesized as follows.
A 1000 ml three-necked flask was charged with 35 g of N, N-dimethylacetamide and heated to 75 ° C. under a nitrogen stream. There, a solution of 6.60 g of 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry), 28.4 g of 2-cyanoethyl acrylate, 0.65 g of V-601 (manufactured by Wako Pure Chemical Industries), 35 g of N, N-dimethylacetamide For 2.5 hours. 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 (weight average molecular weight: 15,000).

(Preparation of coating solution)
Polymer A having a polymerizable group and an interactive group: 10.5 parts by mass, 73.3 parts by mass of acetone, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide were mixed and stirred. A solution was prepared.

(Generation of graft polymer)
The prepared coating solution was applied on the polymerization initiation layer of the substrate A1 by a spin coating method so as to have a thickness of 1 μm, dried at 80 ° C. for 30 minutes, and then a UV exposure machine manufactured by Mitsunaga Electric. (Model number: UVF-502S, lamp: UXM-501MD), with an irradiation power of 1.5 mW / cm ² (measurement of irradiation power with Ushio's UV integrated light meter UIT150-light receiving sensor UVD-S254) for 660 seconds Irradiation was performed to form a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1. Here, the integrated exposure amount was 990 mJ.

Thereafter, the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, and then washed with distilled water.
Thereby, a substrate A2 having a polymer layer was obtained.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 1.2% by mass
・ Saturated water absorption at 25 ° C.-95% relative humidity: 3.4% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.5% by mass
-Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment and allowing to stand for 15 seconds: 70.3 degrees

[Applying plating catalyst]
The substrate A2 having a polymer layer was immersed in a 1% acetone solution of palladium nitrate for 30 minutes and then immersed in acetone for cleaning.
Subsequently, a 1% dimethylborane-water / methanol (water / methanol = 1/3) mixed solution was used as a catalyst activation liquid (reducing liquid), and a substrate A2 having a polymer layer was immersed in this solution for 15 minutes. Then, it was immersed in acetone for cleaning.

[Electroless plating]
As described above, electroless plating was performed on the substrate A2 having the polymer layer provided with the plating catalyst at 60 ° C. for 5 minutes using an electroless plating bath having the following composition. The thickness of the obtained electroless copper plating film was 0.3 μm.

(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 7.1g
・ 37% formaldehyde aqueous solution 9.8g
The pH of the plating bath having the above composition was adjusted to 12.5 (60 ° C.) with sodium hydroxide and sulfuric acid.

[Electroplating]
Subsequently, electroplating was performed for 20 minutes under the conditions of 3 A / dm ² using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the following composition. 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

(Adhesion evaluation)
With respect to the obtained plating film, a 90 ° peel strength is measured at a tensile strength of 10 mm / min for a width of 5 mm using a tensile testing machine (RTM-100 manufactured by A & D Co., Ltd.). As a result, it was 0.7 kN / mm.

[Metal pattern formation and insulation reliability test]
On the surface of the obtained plating film, an etching resist was formed in a region to be left as a metal pattern (wiring pattern), and the plating film in a region without the resist was removed with an etching solution made of FeCl ₃ / HCl. Thereafter, the etching resist was removed with an alkaline stripping solution made of 3% NaOH solution to form a comb-like wiring (metal pattern material) for measuring the insulation reliability between lines and spaces = 100 μm / 100 μm.
This comb-shaped wiring was allowed to stand at 125 ° C.-85% relative humidity (unsaturated), applied voltage 10 V, 2 atm for 200 hours with an ESPEC HAST tester (AMI-150S-25), between the wiring There was no insulation failure.

[Example 2]
The surface metal film material was produced as follows using the substrate A1 formed with the polymerization initiation layer produced in Example 1.

[Formation of polymer layer]
(Synthesis of Polymer B having Polymerizable Group and Interactive Group)
First, a polymer B having a polymerizable group and an interactive group was synthesized as follows.
In a 1000 ml three-necked flask, 42 g of N, N-dimethylacetamide was placed and heated to 75 ° C. under a nitrogen stream. There, 5.6 g of 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry), 36.1 g of 2- (2-ethoxyethoxy) ethyl acrylate, 0.55 g of N, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) A solution of 42 g of N-dimethylacetamide was added dropwise over 2.5 hours. 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 0.24 g, dibutyltin dilaurate 0.30 g, Karenz AOI (manufactured by Showa Denko KK) 15.5 g, N, N-dimethylacetamide 16 g are added to the above reaction solution, and 55 ° C. for 4 hours. Reaction was performed. Thereafter, 3.1 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 distilled water, and the solid matter was taken out to obtain 30 g of polymer B having a polymerizable group and an interactive group (weight average molecular weight 17,000).

(Adjustment of coating solution)
Polymer B having polymerizable group and interacting group: 7.9 parts by mass, 73.3 parts by mass of isopropanol, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide were mixed and stirred. A solution was prepared.

(Generation of graft polymer)
The prepared coating solution was applied by spin coating so as to have a thickness of 1 μm on the polymerization initiation layer of the substrate A1, and dried at 80 ° C. for 30 minutes. Using UV exposure machine (model number: UVF-502S, lamp: UXM-501MD), with an irradiation power of 1.5 mW / cm ² (measurement of irradiation power with Ushio UV integrated light meter UIT150-light receiving sensor UVD-S254) Then, irradiation was performed for 660 seconds to generate a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1. Here, the integrated exposure amount was 990 mJ.

Thereafter, the substrate on which the graft polymer was produced was immersed in stirred methanol for 5 minutes, and then washed with distilled water.
Thereby, a substrate A3 having a polymer layer was obtained.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 0.8% by mass
・ Saturated water absorption at 25 ° C.-95% relative humidity: 3.0% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 5.5% by mass
-Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment and allowing to stand for 15 seconds: 83.9 degrees

  Subsequently, the application of a plating catalyst, electroless plating, and electroplating were performed on the substrate A3 having the polymer layer in the same manner as in Example 1.

(Adhesion evaluation)
With respect to the obtained plating film, a 90 ° peel strength is measured at a tensile strength of 10 mm / min for a width of 5 mm using a tensile testing machine (RTM-100 manufactured by A & D Co., Ltd.). As a result, it was 0.67 kN / mm.

[Metal pattern formation and insulation reliability test]
On the surface of the obtained plating film, an etching resist was formed in a region to be left as a metal pattern (wiring pattern), and the plating film in a region without the resist was removed with an etching solution made of FeCl ₃ / HCl. Thereafter, the etching resist was removed with an alkaline stripping solution made of 3% NaOH solution to form a comb-like wiring (metal pattern material) for measuring the insulation reliability between lines and spaces = 100 μm / 100 μm.
This comb-shaped wiring was allowed to stand at 125 ° C.-85% relative humidity (unsaturated), applied voltage 10 V, 2 atm for 200 hours with an ESPEC HAST tester (AMI-150S-25), between the wiring There was no insulation failure.

Example 3
[Production of substrate]
The following polymerization initiation layer coating solution was applied using a rod bar No. 18 on a substrate made of a polyimide film (product name: Kapton 500H, manufactured by Toray DuPont), and dried and crosslinked at 110 ° C. for 10 minutes. . The film thickness of the obtained polymerization initiation layer was 9.3 μm. The substrate thus obtained was designated as substrate B1. The surface roughness (Rz) of the obtained substrate B1 was 0.3 μm.

(Polymerization initiation layer coating solution)
・ Polymerization initiation polymer P 0.4 g
・ TDI (Tolylene-2,4-diisocyanate) 0.16g
・ Methyl ethyl ketone (MEK) 1.6g

[Formation of polymer layer]
(Preparation of coating solution)
Polymer A having polymerizable group and interacting group: 10.5 parts by mass, 73.3 parts by mass of methyl ethyl ketone (MEK), 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide Stir to prepare a coating solution.

(Generation of graft polymer)
The prepared coating solution was spin-coated on the polymerization initiation layer of the substrate B1 in the same manner as in Example 1, then dried, and a UV exposure machine (model number: UVF-502S, lamp: manufactured by Mitsunaga Electric). UXM-501MD) was used for irradiation for 800 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 polymerization of substrate B1 was started. A graft polymer was formed on the entire surface of the layer. Here, the integrated exposure amount was 1200 mJ.

Thereafter, the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, and then washed with distilled water.
Thereby, a substrate B2 having a polymer layer was obtained.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 1.4% by mass
・ Saturated water absorption rate in a 25 ° C.-95% relative humidity environment: 3.9% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.8% by mass
-Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment and allowing to stand for 15 seconds: 72.6 degrees

  Subsequently, [Application of plating catalyst], [Electroless plating], and [Electroplating] were performed on the substrate B2 having this polymer layer in the same manner as in Example 1.

(Adhesion evaluation)
When the adhesiveness of the obtained plated film was evaluated by the same method as in Example 1, the 90 ° peel strength was 0.68 kN / mm.

[Metal pattern formation and insulation reliability test]
A substrate having a plating film obtained as described above was subjected to an insulation reliability test by forming a comb-like wiring (metal pattern material) in the same manner as in Example 1. There was no defect.

Example 4
[Production of substrate]
Kapton EN (produced by Toray DuPont Co., Ltd.) having a thickness of 25 μm was used as a base material. The saturated water absorption of this substrate at 25 ° C.-50% relative humidity was 1.0% by mass.
An insulating resin composition having a polymerization initiating ability having the following composition is applied to both surfaces of this base material (resin film) using a dip method, dried at 100 ° C. for 5 minutes, and then heated at 250 ° C. for 30 minutes for polymerization. An initiation layer (insulating polymerization initiation layer) was formed. The saturated water absorption of the polymerization initiation layer at 25 ° C.-50% relative humidity was 1.2% by mass.
The obtained substrate was designated as substrate C1. The surface roughness of this substrate C1 was 0.1 μm when (Ra) was measured using Surfcom 3000A (manufactured by Tokyo Seimitsu Co., Ltd.) based on Ra of JIS B0601 (revised in 2010120).

(Insulating composition containing polymerization initiating ability)
-Synthesis of polyimide precursor (polyamic acid)-
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 and stirred for 5 hours at 0 ° C. The reaction solution was reprecipitated to initiate polymerization. The molecular weight (Mw) by GPC was 28,000, and the structure was further confirmed by ¹ H-NMR and FT-IR.
The obtained polyimide precursor was dissolved in DMAc (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a 10% by mass solution.

[Formation of polymer layer]
(Preparation of coating solution)
Polymer A having polymerizable group and interacting group: 10.5 parts by mass, 73.3 parts by mass of methyl ethyl ketone (MEK), 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide Stir to prepare a coating solution.

(Generation of graft polymer)
The prepared coating solution was applied on the polymerization initiation layers on both sides of the substrate C1 to a thickness of 1 μm using the dipping method, dried at 80 ° C. for 30 minutes, and then UV manufactured by Mitsunaga Electric. Using an exposure machine (model number: UVF-502S, lamp: UXM-501MD), with an irradiation power of 1.5 mW / cm ² (measurement of irradiation power with Ushio UV integrated light meter UIT150-light receiving sensor UVD-S254) Irradiation was performed for 660 seconds to generate a graft polymer on the polymerization initiation layer of the substrate C1. Here, the integrated exposure amount was 990 mJ.

Thereafter, the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, and then washed with distilled water.
Thus, a substrate C2 having a polymer layer with a thickness of 0.8 μm on both surfaces was obtained.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 1.2% by mass
・ Saturated water absorption at 25 ° C.-95% relative humidity: 3.4% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.5% by mass
-Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment and allowing to stand for 15 seconds: 70.3 degrees

[Applying plating catalyst]
The substrate C2 having the polymer layer was immersed in 1% acetone solution of palladium nitrate for 30 minutes, and then immersed in acetone for cleaning.
Subsequently, the substrate B2 having a 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.

[Electroless plating]
As described above, the substrate C2 having the polymer layer provided with the plating catalyst was subjected to electroless plating at 60 ° C. for 5 minutes using the same electroless plating bath as in Example 1. The thickness of the obtained electroless copper plating film on both sides was 0.3 μm.

[Electroplating]
Subsequently, electroplating was performed for 20 minutes under the condition of 3 A / dm ² using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the same composition as in Example 1 above. The thicknesses of the obtained electrolytic copper plating films on both sides were 18 μm.

(Adhesion evaluation)
When the 90 ° peel strength of the obtained plated film was measured at a tensile strength of 10 mm / min for a width of 5 mm in the same manner as in Example 1, it was 0.68 kN / m.

[Metal pattern formation and insulation reliability test]
Comb wiring (metal pattern) was formed on the substrate having a plating film obtained as described above using the same method as in Example 1.
Thereafter, an insulation reliability test was performed using this comb-like wiring in the same manner as in Example 1. As a result, no insulation failure was found between the wirings.

Example 5
In Example 1, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was replaced with a polymer C having a polymerizable group and an interactive group synthesized by the following method. Furthermore, a polymer layer was formed in the same manner as in Example 1 except that the exposure conditions were changed to irradiation with an irradiation power of 10 mW / cm ² for 100 seconds. Here, the integrated exposure amount was 1000 mJ.
Thereby, a substrate A4 having a polymer layer was obtained.
In addition, when forming a polymer layer, it turned out that the same polymer layer is formed even if it is a case where integrated exposure amount is 500 mJ.

(Synthesis of Polymer C having Polymerizable Group and Interactive Group)
200 mL of a commercial product of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 600 mL of water. 400 mL of ethyl acetate was added to the obtained aqueous solution, and the oil layer was separated. Next, 100 g of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in the aqueous layer, and then extracted twice using 200 mL of ethyl acetate. Thereafter, the extract was dried over anhydrous magnesium sulfate, 0.04 g of p-methoxyhydroquinone was added, and ethyl acetate was distilled off under reduced pressure. After distillation under reduced pressure, 6.5% by mass of ethyl acetate remained as confirmed by NMR.
In addition, when the content of the bifunctional acrylate in the commercially available product of hydroxyethyl acrylate was measured by liquid chromatography (HPLC), it was 0.28% by mass, but when the content purified as described above was measured, the bifunctional acrylate was measured. The acrylate content was below the detection limit.

In a 500 mL three-necked flask, 20 mL of N-methylpyrrolidone, 2.32 g of hydroxyethyl acrylate purified by the above method, and 10.01 g of cyanoethyl acrylate were added, and the temperature was raised to 75 ° C., and V-601 was contained therein. : A mixed solution of 0.23 g and 5 mL of N-methylpyrrolidone was added dropwise over 1 hour. One hour after the completion of the dropping, the temperature was raised to 80 ° C. and the reaction was carried out for 1 hour.
In the above reaction solution, 0.29 g of ditertiary butyl hydroquinone, 0.29 g of dibutyltin dilaurate, 18.56 g of Karenz AOI (manufactured by Showa Denko KK), and N-methylpyrrolidone (SP value: 22.94 MPa ^1/2) ) 19 g was added and reacted at 55 ° C. for 6 hours. 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 carried out with water, the solid was taken out, and 25 g of polymer C having a polymerizable group and an interactive group was obtained.

(Identification of structure)
The synthesized polymer C having a polymerizable group and an interactive group was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to cyano group-containing units are broadly observed at 4.3-4.05 ppm (2H min), 2.9-2.8 ppm (2H min), 2.5-1.3 ppm (3H min), Peaks corresponding to the polymerizable group-containing units are 7.2 to 7.3 ppm (1 H min), 6.4 to 6.3 ppm (1 H min), 6.2 to 6.1 ppm (1 H min), 6.0 − 5.9ppm (1H min), 4.3-4.05ppm (6H min), 3.3-3.2ppm (2H min), 2.5-1.3ppm (3H min) broadly observed and polymerized It was found that the functional group-containing unit: cyano group-containing unit = 20: 80 (mol ratio).

(Measurement of molecular weight)
The synthesized polymer C having a polymerizable group and an interactive group was dissolved in THF, and the molecular weight was measured using Tosoh high-speed GPC (HLC-8220GPC). As a result, a peak appeared at 23.75 minutes, and it was found that Mw = 22000 (Mw / Mn = 2.1) in terms of polystyrene.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 1.3% by mass
・ Saturated water absorption at 25 ° C.-95% relative humidity: 3.5% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 8.3 mass%
・ Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment for 15 seconds: 71.6 degrees

  Subsequently, [Apply plating catalyst], [Electroless plating], and [Electroplating] were performed on the substrate A4 having the polymer layer in the same manner as in Example 1. Furthermore, after-heating was performed at 170 ° C. for 30 minutes.

(Adhesion evaluation)
When the adhesion of the obtained plated film was evaluated by the same method as in Example 1, the 90 ° peel strength was 0.75 kN / mm.

[Metal pattern formation and insulation reliability test]
A substrate having a plating film obtained as described above was subjected to an insulation reliability test by forming a comb-like wiring (metal pattern material) in the same manner as in Example 1. There was no defect.

Example 6
In Example 1, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was replaced with a polymer D having a polymerizable group and an interactive group synthesized by the following method. Furthermore, a polymer layer was formed in the same manner as in Example 1 except that the exposure conditions were changed to irradiation with an irradiation power of 10 mW / cm ² for 100 seconds. Here, the integrated exposure amount was 1000 mJ.
Thereby, a substrate A5 having a polymer layer was obtained.
In addition, when forming a polymer layer, it turned out that the same polymer layer is formed even if it is a case where integrated exposure amount is 500 mJ.

(Synthesis of Polymer D having Polymerizable Group and Interactive Group)
11 mL of ethylene glycol diacetate was placed in a 500 mL three-necked flask and heated to 75 ° C., and 1.39 g of hydroxyethyl acrylate purified by the method described in Example 5, 6.00 g of cyanoethyl acrylate, A mixed solution of V-601: 0.1382 g and ethylene glycol diacetate 11 mL was added dropwise over 2.5 hours. After completion of dropping, the temperature was raised to 80 ° C. and reacted for 3 hours.
Ditertiary butyl hydroquinone 0.06 g, U-600 (manufactured by Nitto Kasei) 0.13 g, Karenz AOI (manufactured by Showa Denko KK) 3.84 g, and ethylene glycol diacetate (SP value: 20) .79 MPa ^1/2 ) 3.8 g was added and reacted at 55 ° C. for 6 hours.
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 water, and the solid matter was taken out to obtain 3 g of polymer D having a polymerizable group and an interactive group.

(Identification of structure)
The synthesized polymer D having a polymerizable group and an interactive group was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (AV-300) manufactured by Bruker. Peaks corresponding to nitrile group-containing units are broadly observed at 4.3-4.05 ppm (2H min), 2.9-2.8 ppm (2H min), 2.5-1.3 ppm (3H min), Peaks corresponding to the polymerizable group-containing units are 7.2 to 7.3 ppm (1 H min), 6.4 to 6.3 ppm (1 H min), 6.2 to 6.1 ppm (1 H min), 6.0 − 5.9ppm (1H min), 4.3-4.05ppm (6H min), 3.3-3.2ppm (2H min), 2.5-1.3ppm (3H min) broadly observed and polymerized It was found that the functional group-containing unit: nitrile group-containing unit = 21: 79 (mol ratio).

(Measurement of molecular weight)
The synthesized polymer D having a polymerizable group and an interactive group was dissolved in THF, and the molecular weight was measured using Tosoh high speed GPC (HLC-8220GPC). As a result, a peak appeared at 23.75 minutes, and it was found that Mw = 84000 (Mw / Mn = 2.9) in terms of polystyrene.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 1.2% by mass
・ Saturated water absorption at 25 ° C.-95% relative humidity: 3.6% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.7% by mass
・ Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment for 15 seconds: 70.8 degrees

  Subsequently, [Application of plating catalyst], [Electroless plating], and [Electroplating] were performed on the substrate A5 having the polymer layer in the same manner as in Example 1. Furthermore, after-heating was performed at 170 ° C. for 30 minutes.

(Adhesion evaluation)
When the adhesiveness of the obtained plated film was evaluated by the same method as in Example 1, the 90 ° peel strength was 0.76 kN / mm.

[Metal pattern formation and insulation reliability test]
A substrate having a plating film obtained as described above was subjected to an insulation reliability test by forming a comb-like wiring (metal pattern material) in the same manner as in Example 1. There was no defect.

Example 7
In Example 1, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was replaced with a polymer E having a polymerizable group and an interactive group synthesized by the following method. Furthermore, a polymer layer was formed in the same manner as in Example 1 except that the exposure conditions were changed to irradiation with an irradiation power of 10 mW / cm ² for 100 seconds. Here, the integrated exposure amount was 1000 mJ.
Thereby, a substrate A6 having a polymer layer was obtained.
In addition, when forming a polymer layer, it turned out that the same polymer layer is formed even if it is a case where integrated exposure amount is 500 mJ.

(Synthesis of Polymer E having Polymerizable Group and Interactive Group)
10 mL of ethylene glycol diacetate was placed in a 500 mL three-necked flask and heated to 80 ° C., and 3.72 g of hydroxyethyl acrylate purified by the method described in Example 5, 16.01 g of cyanoethyl acrylate, A mixture of V-601: 0.3684 g and ethylene glycol diacetate 10 mL was added dropwise over 4 hours. After completion of dropping, the reaction was further continued for 3 hours.
In the above reaction solution, 0.16 g ditertiary butyl hydroquinone, 0.32 g U-600 (manufactured by Nitto Kasei), 9.6 g Karenz AOI (manufactured by Showa Denko KK), and ethylene glycol diacetate (SP value: 20) .79 MPa ^1/2 ) 9.6 g was added and reacted at 55 ° C. for 6 hours. 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 carried out with water, the solid matter was taken out, and 18 g of polymer E having a polymerizable group and an interactive group was obtained.

(Identification of structure)
When the synthesized polymer E having a polymerizable group and an interactive group was subjected to NMR measurement in the same manner as in Example 2, the polymerizable group-containing unit: nitrile group-containing unit = 23: 77 (mol ratio). I understood.

(Measurement of molecular weight)
The synthesized polymer E having a polymerizable group and an interactive group was dissolved in THF, and the molecular weight was measured using a high-speed GPC (HLC-8220GPC) manufactured by Tosoh Corporation. As a result, a peak appeared at 23.75 minutes, and it was found that Mw = 66000 (Mw / Mn = 2.8) in terms of polystyrene.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.
・ Saturated water absorption at 25 ° C.-50% relative humidity: 1.2% by mass
・ Saturated water absorption at 25 ° C.-95% relative humidity: 3.4% by mass
-Water absorption after immersion in boiling water at 100 ° C for 1 hour: 8.1% by mass
・ Surface contact angle after dropping 5 μL of distilled water in a 25 ° C.-50% relative humidity environment and allowing to stand for 15 seconds: 70.0 degrees

  Subsequently, [Apply plating catalyst], [Electroless plating], and [Electroplating] were performed on the substrate A6 having this polymer layer in the same manner as in Example 1. Furthermore, after-heating was performed at 170 ° C. for 30 minutes.

(Adhesion evaluation)
When the adhesiveness of the obtained plated film was evaluated by the same method as in Example 1, the 90 ° peel strength was 0.76 kN / mm.

[Metal pattern formation and insulation reliability test]
A substrate having a plating film obtained as described above was subjected to an insulation reliability test by forming a comb-like wiring (metal pattern material) in the same manner as in Example 1. There was no defect.

Example 8
A metal pattern material was produced as follows using the substrate A1 formed with the polymerization initiation layer produced in Example 1.

[Formation of polymer layer]
As in Example 1, a coating solution using a polymer A having a polymerizable group and an interactive group was prepared.

(Graft polymer pattern formation)
The prepared coating solution was applied by spin coating so as to have a thickness of 1 μm on the polymerization initiation layer of the substrate A1, and dried at 80 ° C. for 5 minutes. Using an UV exposure machine (model number: UVF-502S, lamp: UXM-501MD) at an irradiation power of 10 mW / cm ² (measurement of irradiation power by Ushio's UV integrated light meter UIT150-light receiving sensor UVD-S254). Irradiated for 100 seconds. At that time, a mask A in which a pattern having a width of 5 mm and a length of 50 mm is arranged at intervals of 0.1 mm on a substrate A1 on which a coating solution is applied and dried, or a mask of a line and space = 100 μm / 100 μm comb type wiring By placing B and exposing, a graft polymer was formed in a pattern on the polymerization initiation layer of the substrate A1. Here, the integrated exposure amount was 1000 mJ.

Thereafter, the substrate on which the graft polymer was formed was immersed in acetonitrile in a stirred state for 5 minutes, and then washed with distilled water.
As a result, substrates A7 (using mask A) and A8 (using mask B) having a polymer layer with a thickness of 5 mm and a length of 50 mm and a thickness of 0.5 μm were obtained.

(Measurement of polymer layer properties)
The physical properties of the obtained polymer layer were the same as in Example 1.

[Applying plating catalyst]
Substrate A7 having a polymer layer was immersed in a 0.1 wt% acetone solution of palladium nitrate for 30 minutes, and then immersed in acetone for cleaning.

[Electroless plating]
As described above, electroless plating was performed on the substrate A7 having the polymer layer provided with the plating catalyst at 60 ° C. for 15 minutes using an electroless plating bath having the following composition. The thickness of the obtained electroless copper plating film was 0.50 μm.

(Composition of electroless plating bath)
・ Distilled water 1700g
・ 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 7.1g
・ 37% formaldehyde aqueous solution 9.8g
The pH of the plating bath having the above composition was adjusted to 12.5 (60 ° C.) with sodium hydroxide and sulfuric acid.

[Electroplating]
Subsequently, electroplating was performed by using the electroless copper plating film as a power feeding layer in the same manner as in Example 1 so that the substrate A7 had a thickness of 18 μm and the substrate A8 had a thickness of 10 μm.
After completion of electroplating, baking was performed at 100 ° C. for 30 minutes and 170 ° C. for 1 hour.

(Adhesion evaluation)
With respect to the metal pattern plating film of the substrate A7 obtained as described above, using a tensile tester (manufactured by A & D Co., Ltd., RTM-100) at a tensile strength of 10 mm / min, The 90 ° peel strength was measured and found to be 0.65 kN / mm.

[Insulation reliability test]
When the insulation reliability test was performed on the metal pattern of the substrate A8 obtained as described above by the method according to the method of Example 1, no insulation failure was observed between the wirings (between the metal patterns). It was.

Claims (20)

(A1) on a substrate, the plating catalyst or a functional group that interacts with a precursor thereof, and, by generating a port Rimmer By a polymer having a polymerizable group directly chemically bonded, a polymer layer composed of the polymer Forming a step;
(A2) applying a plating catalyst or a precursor thereof to the polymer layer;
(A3) a step of plating the plating catalyst or its precursor;
A method for producing a surface metal film material, wherein the polymer layer satisfies all of the following conditions 1 to 4.
Condition 1: Saturated water absorption is 0.01 to 10% by mass in a 25 ° C.-50% relative humidity environment.
Condition 2: Saturated water absorption in a relative humidity environment at 25 ° C. to 95% is 0.05 to 20% by mass.
Condition 3: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 30% by mass
Condition 4: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 50 to 150 degrees. The method for producing a surface metal film material according to claim 1, wherein the polymer layer satisfies all of the following conditions 1 ′ to 4 ′.
Condition 1 ′: Saturated water absorption in a relative humidity environment at 25 ° C.-50% is 0.01 to 5% by mass
Condition 2 ′: Saturated water absorption at 0.05 ° C. to 95% relative humidity is 0.05 to 10% by mass
Condition 3 ′: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 20% by mass
Condition 4 ′: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 55 to 150 degrees.   The step (a1) includes a step (a1-1) of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; 2) A step of directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or a precursor thereof to the polymerization initiating layer. Item 3. A method for producing a surface metal film material according to Item 2. The functional group that forms an interaction with the plating catalyst or its precursor, and the polymer having a polymerizable group include a unit represented by the following formula (1) and a unit represented by the following formula (2). It is a copolymer, The preparation method of the surface metal film material of any one of Claims 1-3 characterized by the above-mentioned.


(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 Represents a single bond or a substituted or unsubstituted divalent organic group, ester group, amide group or ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group Represents a group.) The weight average molecular weight of the polymer having a functional group that forms an interaction with the plating catalyst or its precursor and a polymerizable group is 20000 or more, according to any one of claims 1 to 4. The manufacturing method of the surface metal film material of description. The surface according to any one of claims 1 to 5 , wherein the polymer has a functional group that interacts with a plating catalyst or a precursor thereof, and is a polymer that is directly chemically bonded to the substrate. A method for producing a metal film material. (A1 ') on a substrate, comprising the steps of by generating a port Rimmer by directly chemically bonding a polymer having a cyano group and a polymerizable group, to form a polymer layer made of the polymer,
(A2) applying a plating catalyst or a precursor thereof to the polymer layer;
(A3) a step of plating the plating catalyst or its precursor;
A method for producing a surface metal film material characterized by comprising: The step (a1 ′) includes a step (a1-1 ′) of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed; The method for producing a surface metal film material according to claim 7, further comprising: a1-2 ′) direct chemical bonding of a polymer having a cyano group and a polymerizable group to the polymerization initiation layer. Method of manufacturing a surface metal film material of claim 7 or claim 8 weight average molecular weight of the polymer having the cyano group and a polymerizable group is characterized in that 20,000 or more. The method for producing a surface metal film material according to any one of claims 7 to 9, wherein the polymer is a polymer having a cyano group and directly chemically bonded to the substrate. The method for producing a surface metal film material according to any one of claims 1 to 10, wherein in the step (a3), electroless plating is performed. The method for producing a surface metal film material according to claim 11, wherein electroplating is further performed after the electroless plating. The method for producing a surface metal film material according to any one of claims 1 to 12, wherein the plating catalyst is palladium. Surface metal film material obtained by the method of manufacturing a surface metal film material according to any one of claims 1 to 13. It contains a polymer having a cyano group and a polymerizable group and a solvent capable of dissolving the polymer, and is used in the method for producing a surface metal film material according to any one of claims 1 to 13. A composition for forming a polymer layer. A structure having a structure represented by —O— (CH ₂ ) _n —O— (n is an integer of 1 to 5) and a polymerizable group, and a solvent capable of dissolving the polymer, A composition for forming a polymer layer, which is used in the method for producing a surface metal film material according to any one of claims 1 to 3 and claims 11 to 13 . (A4) A metal pattern comprising the step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material according to any one of claims 1 to 13 into a pattern. Material production method. A metal pattern material obtained by the method for producing a metal pattern material according to claim 17 . (A1 ") against both sides of the resin film having a plating catalyst or a functional group that interacts with a precursor thereof, and, by generating a port Rimmer which directly chemically bonded with the resin film, from the polymer Forming a polymer layer comprising:
(A2) applying a plating catalyst or a precursor thereof to the polymer layer;
(A3) a step of plating the plating catalyst or its precursor;
A method for producing a surface metal film material, wherein the polymer layer satisfies all of the following conditions 1 to 4.
Condition 1: Saturated water absorption is 0.01 to 10% by mass in a 25 ° C.-50% relative humidity environment.
Condition 2: Saturated water absorption in a relative humidity environment at 25 ° C. to 95% is 0.05 to 20% by mass.
Condition 3: Water absorption after immersion in boiling water at 100 ° C. for 1 hour is 0.1 to 30% by mass
Condition 4: 5 μL of distilled water was dropped in a 25 ° C.-50% relative humidity environment, and the surface contact angle after standing for 15 seconds was 50 to 150 degrees. The surface metal according to claim 19 , wherein the step (a1 ″), the step (a2), and the step (a3) are performed simultaneously on both sides of the resin film for each step. A method for producing a film material.