JP2012214895A - Production method for laminate having patterned metal films, and plating layer-forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for a laminate having patterned metal films, capable of readily plasma etching a plating layer and of obtaining a laminate having excellent insulating properties between the patterned metal films.SOLUTION: The production method for the laminate having patterned metal films includes: a plating layer-forming step in which a plating layer is formed on top of a substrate, using a plating layer-forming composition including a polymer having a prescribed unit; a catalyst application step in which a plating catalyst or a precursor thereof is applied to the plating layer; a plating step in which plating is performed and a metal film is formed on top of the plating layer; a pattern-forming step in which an etching fluid is used to form the patterned metal film; an acidic solution contacting step in which the substrate having the patterned metal film and an acidic solution are brought in contact with each other; and a plating layer-removal step in which the plating layer in an area in which no patterned metal film is formed, is removed by plasma etching.

Description

  The present invention relates to a method for producing a laminate having a patterned metal film, and a composition for forming a plating layer used in the production method.

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

  As a means for solving this problem, a polymer layer having high adhesion to the substrate is formed on the substrate, and the polymer layer is plated to form a metal layer having excellent adhesion without making the substrate uneven. It can be formed (Patent Document 1). According to this method, the adhesion between the substrate and the metal film can be improved without roughening the surface of the substrate. Further, in relation to the method, a composition for forming a layer to be plated that can form a layer to be plated that is excellent in adsorptivity to the plating catalyst or its precursor is known (Patent Documents 2 and 3).

JP 2009-007662 A JP 2010-248464 A JP 2009-10336 A

On the other hand, in recent years, fine wiring such as printed wiring boards has been required to further improve insulation reliability between wirings as wiring (metal patterns) is highly integrated. At the same time, from the economical point of view, there is an increasing need for methods (semi-additive method and subtractive method) in which the entire surface is plated and wiring is formed by etching.
The present inventors considered that the polymer containing the predetermined unit described in Patent Document 2 is to be applied to a semi-additive method or a subtractive method in which needs are increasing, and a layer to be plated is formed using the polymer. Then, a patterned metal film (plating film) was produced thereon. In that case, it discovered that the to-be-plated layer which remain | survives between metal wiring was related with the insulation reliability between metal wiring. That is, it has been found that if the layer to be plated remains between the wiring patterns after the pattern-like metal film is formed, the insulation between the pattern-like metal films may be reduced.

  Therefore, the present inventors performed a plasma etching process in order to remove the layer to be plated existing in the region where the patterned metal film is not provided, and it took a long time to remove the layer to be plated. It has been found that there is a problem that processing time is required or the plated layer cannot be sufficiently removed.

  In view of the above circumstances, the present invention provides a patterned metal film that can easily perform a plasma etching treatment of a layer to be plated and can obtain a laminate having excellent insulation between the patterned metal films. It aims at providing the manufacturing method of the laminated body which has, and the composition for to-be-plated layer forming used for this manufacturing method.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a polymer having a predetermined unit and providing a contact step with a predetermined acidic solution.
That is, the present inventors have found that the above object can be achieved by the following means.

(1) A composition for forming a layer to be plated, including a unit represented by the formula (A) described later, a unit represented by the formula (B) described later, and a polymer represented by the formula (C) described later. An object is brought into contact with the substrate, and then energy is applied to the composition for forming a layer to be plated on the substrate to form a layer to be plated on the substrate;
A catalyst application step for applying a plating catalyst or a precursor thereof to the layer to be plated;
A plating step of performing a plating treatment on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal film on the layer to be plated;
After the plating step, a pattern forming step of forming a patterned metal film using an etching solution containing a metal component or hydrogen peroxide,
An acidic solution contact step in which a substrate having a patterned metal film is contacted with an acidic solution substantially free of a metal component or hydrogen peroxide;
A method for producing a laminate having a patterned metal film, comprising: a plated layer removal step of removing a plated layer in a region where the patterned metal film is not formed by plasma etching.

(2) The manufacturing method of the laminated body which has a patterned metal film as described in (1) whose etching liquid is acidic.
(3) The manufacturing method of the laminated body which has a patterned metal film as described in (1) or (2) whose metal component is a copper ion or an iron ion.
(4) The manufacturing method of the laminated body which has a patterned metal film in any one of (1)-(3) whose acidic solution is hydrochloric acid aqueous solution, sulfuric acid aqueous solution, or nitric acid aqueous solution.
(5) A wiring comprising a laminate having a patterned metal film produced by the production method according to any one of (1) to (4), and an insulating layer provided on the laminate having the patterned metal film substrate.

(6) A composition for forming a layer to be plated, including a unit represented by formula (A) described later, a unit represented by formula (B) described later, and a unit represented by formula (C) described later. object.
(7) The composition for forming a plated layer according to (6), wherein the unit represented by the formula (A) is a unit represented by the formula (A-1) described later.
(8) The plated layer according to (7), wherein L ¹ is a divalent linear hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a methyl group, an ethyl group, or a propyl group. Forming composition.
(9) The units represented by the formula (B) are units represented by the formula (B-1) described later, or units represented by the formula (B-2) described later (6) to ( The composition for forming a plated layer according to any one of 8).

  ADVANTAGE OF THE INVENTION According to this invention, the plasma etching process of a to-be-plated layer can be implemented easily, and the laminated body which was excellent in the insulation between patterned metal films can be obtained. A production method and a composition for forming a plated layer used in the production method can be provided.

(A)-(E) are typical sectional drawings which show in order each manufacturing process in the manufacturing method of the laminated body which has a patterned metal film of this invention, respectively. (A)-(C) are each process drawing which shows one suitable aspect of a pattern formation process. (A)-(E) are each process drawing which shows the other suitable aspect of a pattern formation process.

  Below, the suitable embodiment of the manufacturing method of the laminated body which has a patterned metal film of this invention, and the composition for to-be-plated layer formation used for this method is demonstrated.

First, the feature point compared with the prior art of this invention is explained in full detail.
When the present inventors examined the problem at the time of removing the to-be-plated layer in the laminated body obtained from the invention of a prior art (the said patent documents 1-3), it remains in a to-be-plated layer. It was found that the metal component to be affected. That is, it has been found that the more the metal component remains, the more it affects the subsequent plasma etching process of the layer to be plated.
One way to reduce the metal component in the layer to be plated is to reduce the adsorption amount of the plating catalyst. In this case, obtain a metal film (plating film) with sufficient thickness in a certain time during the plating process. In addition, the adhesion of the resulting metal film is inferior.

As a result of intensive studies based on the above findings, the present inventors have found that a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof are mutually contained without substantially including a functional group such as a cyano group. By using a polymer having an active group and having a predetermined alkyl group, etching the metal film with a predetermined etching solution, and further bringing the plating layer into contact with the acidic solution before the plasma etching process The inventors have found that the desired effect can be obtained.
More specifically, the interactive group such as the carboxylic acid group has a property of adsorbing to the plating catalyst, but when the hydrogen ion is supplied from an acidic solution, the plating catalyst is easily desorbed. That is, it has been found that the metal component in the layer to be plated is removed by the acidic solution, and the plasma etching process proceeds better. In the case of a cyano group or the like, desorption of the plating catalyst due to hydrogen ions hardly occurs, and a desired effect cannot be obtained.

  First, the constituent components (polymer, etc.) of the composition for forming a layer to be plated of the present invention will be described in detail, and then a method for producing a laminate having a patterned metal film using the composition will be described in detail.

<Composition for plating layer formation>
(polymer)
The polymer used in the present invention has at least a unit represented by the formula (A), a unit represented by the formula (B), and a unit represented by the formula (C).
By including the unit represented by the formula (A) in the polymer, cross-linking between the polymers and chemical bonds are formed between the substrate and the polymer, and the adhesion of the resulting metal film is further improved. Furthermore, since it has a (meth) acrylamide group, a film with high alkali resistance can be formed. In addition, the carboxylic acid group, sulfonic acid group, phosphoric acid group, or salt thereof in the unit represented by the formula (B) can adsorb the plating catalyst, thereby performing electroless plating described later. It can be carried out. At the same time, the plating catalyst adsorbed in the layer to be plated or its precursor can be desorbed by the acidic solution described later, so that the plating catalyst remains in the exposed layer to be plated after the metal film etching process. Hard to do. Therefore, the plated layer can be more efficiently removed during the plasma etching process. Furthermore, the inclusion of the unit represented by the formula (C) improves the hydrophobicity of the polymer and makes it difficult to be damaged by the alkaline solution during electroless plating.

In formula (A) to formula (C), R ¹ , R ² , R ⁴ , and R ⁶ each independently represent a hydrogen atom or a methyl group. Preferably it is a hydrogen atom.
R ³ represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group. Among these, a hydrogen atom is preferable from the viewpoint of increasing the polymerization sensitivity by increasing the amount of the polymerizable group per unit weight and the polymerizability of the (meth) acrylamide group.

V represents a single bond, an ester group, an amide group, or a phenylene group. Among these, a single bond, an ester group, or a phenylene group is preferable from the viewpoint of ease of synthesis and the effect of the present invention, and an ester group is more preferable.
W represents a single bond, an ester group, an amide group, or a phenylene group. Among these, a single bond is preferable from the viewpoint of increasing the content of X per unit weight.

L ¹ represents a divalent hydrocarbon group. Although carbon number in particular of a hydrocarbon group is not restrict | limited, C1-C6 is preferable and C1-C3 is more preferable at the point which the effect of this invention is more excellent. As a kind of hydrocarbon group, any of a bivalent aliphatic hydrocarbon group (for example, a methylene group, ethylene group) or a bivalent aromatic hydrocarbon group (for example, phenylene group) may be sufficient. The aliphatic hydrocarbon group may be linear, branched or cyclic, and may be substituted with an oxygen atom or an alkyl group.
Among these, L ¹ may be substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a propyl group from the viewpoint of improving the polymerization sensitivity by increasing the amount of the polymerizable group per unit weight. A divalent linear hydrocarbon group having 1 to 3 carbon atoms is preferable.

L ² represents a single bond or a divalent organic group.
Examples of the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), -O —, —S—, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, alkylene Oxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.).
As a substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, or a butylene group, or these groups are substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like Those are preferred.
As the substituted or unsubstituted aromatic hydrocarbon group, an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.
Among these, L ² is a divalent linear chain having 1 to 6 carbon atoms which may be substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a propyl group from the viewpoint of the hydrophilicity of the polymer. A hydrocarbon group, an ethylene oxide group, a propylene oxide group, a divalent hydrocarbon group having 2 to 8 carbon atoms having an ester group (—COO—), or a single bond is preferable, and a single bond is most preferable.

  X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof. Of these, carboxylic acid groups and sulfonic acid groups are preferable from the viewpoint of ease of synthesis, and carboxylic acid groups are more preferable from the viewpoint of stability of the compound.

Z represents a —OR ⁷ group or a —N (R ⁸ ) ₂ group. Of these, —N (R ⁸ ) ₂ is preferred from the viewpoint of alkali resistance.
R ⁷ represents an alkyl group, a phenyl group, or a group obtained by combining them. R ⁷ may contain —O— (oxygen atom). Examples of the alkyl group include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, and 2-ethyl-hexyl group. Of these, isopropyl group and t-butyl group are preferable from the viewpoint of alkali resistance.
R ⁸ each independently represents a hydrogen atom or an alkyl group which may contain —O—. Examples of the alkyl group include a methyl group and an ethyl group. R ⁸ may be bonded to each other to form a ring. Among these, an ethyl group and a morpholine group are preferable in that the polymer becomes more hydrophobic and the alkali resistance is further improved.

(Preferred embodiment)
As a suitable aspect of the unit represented by Formula (A), the unit represented by Formula (A-1) is mentioned.

In formula (A-1), the definitions of R ¹ , R ² , R ³ , and L ¹ are as described above.
In formula (A-1), Y represents an oxygen atom or a —NR ⁵ — group. Y is preferably an oxygen atom from the viewpoint of ease of synthesis.
R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group. Of these, a hydrogen atom is preferable from the viewpoint of increasing the amount of the polymerizable group per unit weight.

  As a suitable aspect of the unit represented by Formula (B), the unit represented by Formula (B-1) or the unit represented by Formula (B-2) is mentioned.

In formula (B-1), the definitions of R ⁴ , L ² , and X are as described above.
In formula (B-1), Y represents an oxygen atom or a —NR ⁵ — group. R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group. Among these, an oxygen atom is preferable from the viewpoint of ease of synthesis.
In formula (B-2), the definitions of R ⁴ and X are as described above.
In addition, in Formula (B-1) and Formula (B-2), Formula (B-2) is a more preferable aspect.

  As a suitable aspect of the unit represented by Formula (C), the unit represented by Formula (C-1) is mentioned.

In formula (C-1), the definitions of R ⁶ and R ⁸ are as described above.

  Below, an example of the unit represented by Formula (A) is shown.

  Moreover, an example of the unit represented by Formula (B) is shown below.

  Moreover, an example of the unit represented by Formula (C) is shown below.

Although the content rate of the unit represented by the formula (A) in the polymer is not particularly limited, from the viewpoint of reactivity (curability, polymerizability) and suppression of gelation during synthesis, with respect to all polymer units, It is preferably 5 to 60 mol%, more preferably 5 to 40 mol%.
Further, the content of the unit represented by the formula (B) in the polymer is not particularly limited, but is 20 to 80 mol% with respect to the total polymer unit from the viewpoint of adsorptivity to the plating catalyst or its precursor. It is preferably 30 to 80 mol%.
In addition, the content of the unit represented by the formula (C) in the polymer is not particularly limited, but it is 5 to 75 mol% with respect to all polymer units from the viewpoint of controlling the hydrophilicity / hydrophobicity of the layer to be plated. Preferably, it is 5-50 mol%.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, 20000 or more is preferable, and from the viewpoint of suppressing gelation during synthesis, 100,000 or less is preferable.
Further, the degree of polymerization of the polymer is not particularly limited, but it is preferable to use a polymer of 10-mer or more, and more preferably a polymer of 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.

  Although content of the polymer in the composition for to-be-plated layer forming is not restrict | limited in particular, 2-50 mass% is preferable with respect to the composition whole quantity, and 5-30 mass% is more preferable. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

<Other optional components in the composition for forming a layer to be plated>
(solvent)
The composition for forming a layer to be plated may contain a solvent as necessary.
Solvents that can be used are not particularly limited, for example, alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, Amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and others In addition, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like can be mentioned.
Among these, amide solvents, ketone solvents, nitrile solvents, and carbonate solvents are preferable, and specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, and dimethyl carbonate are preferable. .

  When a solvent is contained in the composition for forming a layer to be plated, the content of the solvent is preferably 50 to 98% by mass and more preferably 70 to 95% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

(Other additives)
In the composition for forming a layer to be plated of the present invention, other additives (for example, polymerization initiator, monomer, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler) Particles, flame retardants, surfactants, lubricants, plasticizers, etc.) may be added as necessary.

<Method for Producing Laminate Having Patterned Metal Film>
By using the above-mentioned composition for forming a layer to be plated, a laminate having a patterned metal film can be produced. The manufacturing method mainly includes the following six steps.
(Plating layer forming step) After contacting the composition for forming a layer to be plated on a substrate, energy is applied to the composition for forming a layer to be plated on the substrate to form a layer to be plated on the substrate. Step of applying (catalyst applying step) Step of applying a plating catalyst or precursor thereof to the layer to be plated (plating step) Plating treatment is applied to the layer of plating to which the plating catalyst or precursor thereof has been applied. Step of forming a metal film (pattern formation step) After the plating step, forming a pattern metal film using an etching solution containing a metal component or hydrogen peroxide (acid solution contact step) having a pattern metal film A step of bringing the substrate into contact with an acidic solution substantially free of a metal component or hydrogen peroxide (plating layer removal step) A layer to be plated in a region where a patterned metal film is not formed The following step of removing by Zuma etching process, the material to be used in each step, and will be described in detail the method of operation.

<Plating layer forming process>
The to-be-plated layer forming step is a step of forming the to-be-plated layer on the substrate by bringing the above-mentioned to-be-plated layer forming composition into contact with the substrate and then applying energy to the to-be-plated layer forming composition. is there. Depending on the function of the carboxylic acid group, phosphoric acid group, sulfonic acid group, etc. in the unit represented by the formula (B), the layer to be plated formed by this step is a plating catalyst or The precursor is adsorbed (attached). That is, the layer to be plated functions as a good receiving layer for the plating catalyst or its precursor. Moreover, the bipolymer bonding group in the unit represented by the formula (A) is used for bonding between polymers and chemical bonding with a substrate (or a close adhesion auxiliary layer described later). As a result, excellent adhesion appears between the metal film (plating film) formed on the surface of the layer to be plated and the substrate. In addition, the preferable aspect in this process is an aspect in which the to-be-plated layer and the board | substrate are couple | bonded through a chemical bond.
More specifically, in this step, a layer 12 to be plated is formed on the substrate 10 as shown in FIG. As will be described later, the substrate 10 may have a close adhesion auxiliary layer on its surface. In this case, the layer to be plated 12 is formed on the close adhesion auxiliary layer.

  First, the materials (substrate, adhesion auxiliary layer, etc.) used in this step will be described in detail, and then the procedure of the step will be described in detail.

(substrate)
As the substrate used in the present invention, any conventionally known substrate can be used as long as it has shape retention. Moreover, it is preferable that the surface has a function which can be chemically bonded with the polymer mentioned later. Specifically, the substrate itself can form a chemical bond with the polymer by applying energy (for example, exposure), or an intermediate layer on the substrate that can form a chemical bond with the layer to be plated by applying energy. (For example, an adhesion auxiliary layer described later) may be provided.

  The material of the substrate is not particularly limited. For example, polymer materials (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polyvinyl acetal, Polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), metal material (eg, metal alloy, metal-containing material, pure metal, or the like, specifically aluminum , Zinc, copper and other mixtures, alloys, and alloys thereof), other materials (eg, paper, paper laminated with plastic), combinations thereof, or the like.

In addition, the laminate of the present invention can be applied to semiconductor packages, various electric wiring boards, and the like. When used in such applications, a substrate containing an insulating resin as shown below, specifically, a substrate made of an insulating resin (insulating substrate) or an insulating resin layer (insulating resin layer) ) On the surface (substrate with an insulating resin layer) is preferably used.
In addition, the board | substrate which has a metal wiring layer and an insulating resin layer alternately on the surface, and the insulating resin layer is arrange | positioned in the outermost layer may be sufficient as the board | substrate.

When obtaining a substrate made of an insulating resin or a layer made of an insulating resin, a known insulating resin composition is used.
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 ABS resins.
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 thereof include pentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, and alicyclic epoxy resins. These may be used alone or in combination of two or more.

  Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.

(Adhesion auxiliary layer)
The adhesion auxiliary layer is an arbitrary layer that may be provided on the surface of the substrate, and plays a role of assisting adhesion between the substrate and a layer to be plated described later. This layer may have an affinity between the substrate and the layer to be plated, and may react with the polymer during curing to form a chemical bond.
In addition, if a board | substrate is a plate-shaped object, you may form a close_contact | adherence auxiliary | assistant layer on both surfaces. As the adhesion auxiliary layer, a layer that causes a chemical bond when the polymer is cured (particularly during photocuring) is preferable. It is preferable to introduce a polymerization initiator into the adhesion auxiliary layer that generates such a chemical bond. In addition, the adhesion auxiliary layer is preferably formed using water-dispersed latex from the viewpoint of workability.

The adhesion auxiliary layer is preferably formed using a resin composition having good adhesion to the substrate and a compound capable of generating radicals upon exposure (a polymerization initiator). In addition, when the resin which comprises a resin composition has the site | part which can generate a radical, it is not necessary to add the compound which can generate a radical separately.
In addition, a conventionally well-known photoinitiator is used as a compound which can generate | occur | produce a radical by exposure. Examples of the photopolymerization initiator include p-tert-butyltrichloroacetophenone and 2,2′-diethoxyacetophenone.
The amount of the photopolymerization initiator (compound capable of generating radicals upon exposure) to be contained in the adhesion auxiliary layer is preferably 0.1% by mass to 50% by mass in terms of solid content, and 1.0% by mass to 30% by mass. % Is more preferable.

As the adhesion auxiliary layer in the present invention, for example, when the substrate is made of a known insulating resin that has been used as a material for a multilayer laminate, a build-up substrate, or a flexible substrate, the adhesion with the substrate From the viewpoint, an insulating resin composition is preferably used as the resin composition used when forming the adhesion assisting layer.
Hereinafter, a mode in which the substrate is made of an insulating resin and the adhesion auxiliary layer is formed of an insulating resin composition will be described.

  The insulating resin composition used when forming the adhesion auxiliary layer may contain the same or different one as the electrically insulating resin constituting the substrate, but may have a glass transition point or elastic modulus. It is preferable to use a material having close thermal properties such as a linear expansion coefficient. Specifically, for example, it is preferable to use the same type of insulating resin as the insulating resin constituting the substrate in terms of adhesion.

The insulating resin used for the adhesion auxiliary layer means a resin having an insulation property that can be used for a known insulating film, and even if it is not a perfect insulator, Any resin having appropriate insulating properties 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 thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin. The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.

  The thickness of the adhesion auxiliary layer in the present invention is generally in the range of 0.1 to 10 μm, and preferably in the range of 0.2 to 5 μm. When the adhesion auxiliary layer is provided, if the thickness is in the above range, sufficient adhesion strength with the adjacent base material or the layer to be plated can be obtained, and the thickness is smaller than that of using a general adhesive. Nevertheless, adhesion similar to the adhesive layer is achieved.

The adhesion auxiliary layer is formed on the substrate surface by applying a known layer forming method such as a coating method, a transfer method, or a printing method.
The adhesion auxiliary layer may be formed by a printing method (for example, gravure printing method, screen printing method, flexographic printing method, ink jet printing method, imprinting method, etc.) or a developing method (for example, wet etching, dry etching, ablation, light). It may be patterned by curing / plasticizing (negative type / positive type) or the like.

  Further, after the adhesion auxiliary layer is formed on the substrate, it may be cured by applying some energy. Examples of the energy to be applied include light, heat, pressure, electron beam, etc., and heat or light is general. In the case of heat, it is preferable to add heat at 100 ° C. to 300 ° C. for 5 minutes to 120 minutes. .

  This curing treatment may be performed immediately after the formation of the adhesion assisting layer. If a preliminary curing treatment is performed for about 5 minutes to 10 minutes after the formation of the adhesion assisting layer, all the other processes performed after the formation of the adhesion assisting layer are performed. You may implement after performing the process of.

(Process procedure)
The method for bringing the composition for forming a layer to be plated into contact with the substrate (or on the adhesion auxiliary layer) is not particularly limited, and the method for laminating the composition for forming a layer to be plated directly on the substrate or the formation of the layer to be plated When the composition for use is a liquid containing a solvent, a method of coating the composition on a substrate can be mentioned. From the viewpoint of easily controlling the thickness of the obtained layer to be plated, a method of applying the composition on the substrate is preferable.
The method of application is not particularly limited, and specific methods include spin coater, dip coater, double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, Known methods such as a reverse roll coater, a transfer roll coater, an extrusion coater, a curtain coater, a die coater, a gravure roll coating method, an extrusion coating method, and a roll coating method can be used.
From the viewpoint of handleability and production efficiency, the composition for forming a layer to be plated is applied and dried on the substrate (or adhesion auxiliary layer) to remove the remaining solvent to form a composition layer containing a polymer. Embodiments are preferred.

When the composition for forming a layer to be plated is brought into contact with the substrate, the coating amount is 0.1 g / m ^{2 in} terms of solid content from the viewpoint of sufficient interaction formation with a plating catalyst or a precursor thereof described later. preferably 10 g / m ^2, especially 0.5g / m ² ~5g / m ² is preferred.
In addition, when forming a to-be-plated layer in this process, you may leave at 20-40 degreeC for 0.5 to 2 hours between application | coating and drying, and you may remove the remaining solvent.

(Granting energy)
The method for applying energy to the composition for forming a layer to be plated on the substrate is not particularly limited, but for example, heating or exposure is preferably used.
For the exposure, light irradiation with a UV lamp, visible light, or the like is used. 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 scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The exposure time varies depending on the reactivity of the polymer and the light source, but is usually between 10 seconds and 5 hours. The exposure energy may be about 10 to 8000 mJ, and is preferably in the range of 100 to 3000 mJ.

  In addition, when using heating as energy provision, a ventilation dryer, oven, an infrared dryer, a heating drum, etc. can be used.

Although the thickness of the to-be-plated layer obtained is not restrict | limited in particular, 0.01-10 micrometers is preferable from the point of the adhesiveness to the board | substrate of a metal film, and 0.05-5 micrometers is more preferable.
The dry film is preferably 0.05 to 20 g / m ² in thickness, especially 0.1 to 6 g / m ² preferably.
Furthermore, the surface roughness (Ra) of the layer to be plated is preferably 0.01 to 0.3 [mu] m, more preferably 0.02 to 0.15 [mu] m, from the viewpoint of wiring shape and adhesion strength. In addition, the surface roughness (Ra) was measured using Surfcom 3000A (manufactured by Tokyo Seimitsu Co., Ltd.) based on Ra described in JIS B 0601 (Revision of 201010120) by non-contact interference method.

  By contacting the plating catalyst or a precursor thereof as described above, the functional group X derived from the unit represented by the formula (B) in the layer to be plated interacts with an intermolecular force such as van der Waals force. The plating catalyst or its precursor can be adsorbed by utilizing electrostatic interaction such as ionic bonding, or interaction by coordination bonding by a lone pair of electrons.

<Catalyst application step>
A catalyst provision process is a process of providing a plating catalyst or its precursor to the to-be-plated layer obtained at the said process. In this step, the functional group X (carboxylic acid group or the like) derived from the unit represented by the formula (B) in the layer to be plated adheres a given plating catalyst or its precursor depending on its function ( Adsorb).
Here, as a plating catalyst or its precursor, what functions as a catalyst or an electrode of a plating process in the plating process mentioned later is mentioned. Therefore, although a plating catalyst or its precursor is determined by the kind of plating process in a plating process, it is preferable that it is an electroless-plating catalyst or its precursor.
First, the material (electroless plating catalyst or its precursor etc.) used at this process is explained in full detail, and the procedure of this process is explained in full detail after that.

(Electroless plating catalyst)
As the electroless plating catalyst used in this step, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal (Ni) having catalytic ability for autocatalytic reduction reaction. And those known as metals capable of electroless plating with a lower ionization tendency). Specific examples include Pd, Ag, Cu, Ni, Pt, Au, and Co. Among these, Ag, Pd, Pt, and Cu are particularly preferable because of their high catalytic ability.
A metal colloid may be used as the electroless plating catalyst. Generally, 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 controlled 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. After the metal ion which is an electroless plating catalyst precursor is imparted to the layer to be plated, it may be converted into a zero-valent metal by a separate reduction reaction before being immersed in the electroless plating bath. Alternatively, the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

The metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. For example, Ag ion, Cu ion, Ni ion, Co ion, Pt ion, Pd ion can be mentioned. Among these, Ag ions, Pd ions, and Cu ions are preferable in terms of catalytic ability.

One preferred example of the electroless plating catalyst or precursor thereof used in the present invention is a palladium compound. This palladium compound acts as a plating catalyst (palladium) or a precursor thereof (palladium ions), which serves as an active nucleus during plating treatment and serves to precipitate a metal. Palladium (Pd) has an advantage that it is highly active and can be electrolessly plated in a small amount, so that it hardly remains in the polymer layer by the time of plasma etching.
The palladium compound is not particularly limited as long as it contains palladium and acts as a nucleus in the plating process, and examples thereof include a palladium (II) salt, a palladium (0) complex, and a palladium colloid.

Moreover, as an electroless-plating catalyst or its precursor, silver or silver ion is mentioned as another preferable example.
When silver ions are used, those obtained by dissociating silver compounds as shown below can be suitably used. Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples include silver p-toluenesulfonate. Among these, silver nitrate is preferable from the viewpoint of water solubility.
Of the above, palladium compounds are most preferred.

(Other catalysts)
In the present invention, a zero-valent metal can be used as a catalyst used for performing direct electroplating without electroless plating on the layer to be plated.

(Plating catalyst solution)
The plating catalyst or a precursor thereof as described above is preferably applied to the layer to be plated as a dispersion or solution (plating catalyst solution).
Water or an organic solvent is used as a solvent for the plating catalyst solution. By containing the organic solvent, the permeability of the plating catalyst or its precursor to the layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the functional group X.

  The water used in the plating catalyst solution preferably does not contain impurities. From such a viewpoint, it is preferable to use RO water, deionized water, distilled water, purified water, and the like. It is particularly preferred to use water.

There is no restriction | limiting in particular as an organic solvent used for a plating catalyst liquid, if it is a solvent which can osmose | permeate a to-be-plated layer. For example, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone , Dimethyl carbonate, dimethyl cellosolve, etc. can be used.
In particular, a water-soluble organic solvent is preferable from the viewpoint of compatibility with a plating catalyst or a precursor thereof and permeability to a layer to be plated. Acetone, dimethyl carbonate, dimethyl cellosolve, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether is preferred.

  Further, the dispersion or solution may contain other additives depending on the purpose. Examples of other additives include swelling agents and surfactants.

(Process procedure)
The method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
For example, a plating catalyst solution (a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a solution containing metal ions dissolved in an appropriate solvent and dissociated metal ions) is prepared, and the plating catalyst solution is applied to the layer to be plated. And a method of immersing a substrate on which a layer to be plated is formed in a plating catalyst solution.
The contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 20 minutes, and more preferably about 1 minute to 10 minutes.
The temperature of the plating catalyst solution at the time of contact is preferably about 10 to 60 ° C, and more preferably about 10 to 30 ° C.

The adsorption amount (applied amount) of the plating catalyst or its precursor in the layer to be plated is not particularly limited, but is preferably 100 mg / m ² or less from the viewpoint that the layer to be plated removal step described later proceeds better. ˜70 mg / m ² is more preferred.

  By contacting the plating catalyst or a precursor thereof as described above, the functional group X derived from the unit represented by the formula (B) in the layer to be plated interacts with an intermolecular force such as van der Waals force. The plating catalyst or its precursor can be adsorbed by utilizing electrostatic interaction such as ionic bonding, or interaction by coordination bonding by a lone pair of electrons.

<Plating process>
A plating process is a process of performing a plating process with respect to the to-be-plated layer to which the plating catalyst or its precursor was provided in the said process, and forming a metal film on a to-be-plated layer. The metal film formed by this process has excellent conductivity and adhesion. More specifically, as shown in FIG. 1B, a metal film 14 is formed on the layer to be plated 12, and a laminate is obtained.
Examples of the plating treatment performed in this step include electroless plating and electrolytic plating. In the above step, the plating treatment is selected depending on the function of the plating catalyst or its precursor that forms an interaction with the layer to be plated. be able to.
Especially, it is preferable to perform electroless plating from the point of the adhesive improvement of a metal film. Moreover, in order to obtain the metal film 14 with a desired film thickness, it is a more preferable aspect that electrolytic plating is further performed after the 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 rinsing the substrate provided with the electroless plating catalyst to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. As the electroless plating bath used, a known electroless plating bath can be used. In addition, as an electroless-plating bath, the case where an alkaline electroless-plating bath (pH is preferable about 9-14) is preferable from the point of availability.
In addition, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the layer to be plated, the substrate is washed with water to remove excess. After removing the precursor (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 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 the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1-30 mass% is more preferable. As the reducing agent, it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid.
When dipping, keep the concentration of the electroless plating catalyst or its precursor near the surface of the layer to be plated in contact with the electroless plating catalyst or its precursor, and soak it with stirring or shaking. Is preferred.

  As a composition of a general electroless plating bath, in addition to a solvent (for example, water), 1. 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 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.

  As the types of metals used in the electroless plating bath, for example, copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. preferable. Moreover, the optimal reducing agent and additive are selected according to the said metal.

The film thickness of the metal 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 0.1 μm or more, and more preferably 0.2 to 2 μm.
However, when performing electroplating to be described later using a metal film formed by electroless plating as a conductive layer, it is preferable that a film of at least 0.1 μm or more is uniformly applied.
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.

(Electrolytic plating (electroplating))
In this step, when the plating catalyst or its precursor applied in the above step has a function as an electrode, electrolytic plating can be performed on the layer to be plated to which the catalyst or its precursor is applied. it can.
Further, after the above-described electroless plating, the formed metal film may be used as an electrode, and further electrolytic plating may be 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. As described above, by performing electroplating after electroless plating, the metal film can be formed to a thickness according to the purpose, which is suitable for applying the metal film to various applications.

  As a method of electrolytic plating, a conventionally known method can be used. In addition, as a metal used for electrolytic plating, copper, chromium, lead, nickel, gold | metal | money, silver, tin, zinc etc. are mentioned, Copper, gold | metal | money, silver is preferable from a conductive viewpoint, and copper is more preferable.

Moreover, the film thickness of the metal film obtained by electrolytic plating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
In addition, when applying to general electrical wiring etc., it is preferable that the film thickness of a metal film is 0.5 micrometer or more from a viewpoint of electroconductivity, and 1-30 micrometers is more preferable.
In addition, the thickness of the electrical wiring is reduced in order to maintain the aspect ratio as the line width of the electrical wiring is reduced, that is, as the size is reduced. Therefore, the layer thickness of the metal film formed by electrolytic plating is not limited to the above, and can be arbitrarily set.

<Pattern formation process>
The pattern forming step is a step of forming a patterned metal film using an etching solution containing a metal component or hydrogen peroxide after the plating step. By this step, a metal pattern material having a patterned metal film on the surface is obtained. More specifically, as shown in FIG. 1C, the etching solution is brought into contact with an unnecessary portion of the metal film 14 so that the portion is removed and the patterned metal film 16 is obtained.

(Etching solution)
First, the etching solution used in this step will be described below.
The etching solution used in this step dissolves the metal component of the metal film.
The etching solution is preferably acidic from the viewpoint of the removability of the metal film. Specifically, the pH is preferably 5 or less, and more preferably 3 or less. The lower limit is not particularly limited, but is preferably 0 or more from the viewpoint of damage to the layer to be plated.
In addition, the reagent used in particular for adjusting pH is not restrict | limited, For example, hydrochloric acid, a sulfuric acid, etc. are mentioned.

  The solvent used in the etching solution is not particularly limited, and water, an organic solvent, or the like can be used. From the viewpoints of handleability and etching performance, water is preferred.

The etching solution used contains a metal component or hydrogen peroxide. By including these components, the metal film (plating film) can be removed.
The metal component preferably contains a metal ion. As for the type of metal ion, an optimum metal is appropriately selected depending on the metal constituting the metal film, but is preferably a metal ion having a higher ionization tendency than the metal constituting the metal film, for example, when etching copper Examples include copper ions and iron ions.

  Examples of the etching solution include a ferric chloride solution, a sulfuric acid-hydrogen peroxide mixed solution, and the like, and preferably a ferric chloride solution.

  The contact time between the etching solution and the metal film is not particularly limited, but is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 3 minutes, from the viewpoints of productivity and metal film etching properties.

(Processing method)
(First embodiment)
Although the method of forming the patterned metal film 16 using the etching solution is not particularly limited, the first embodiment shown in FIG. 2 is preferable from the viewpoint of productivity. This method is based on a so-called subtractive method.
As shown in FIG. 2A, first, a mask 20 is provided at a predetermined position on the metal film 14. Thereafter, as shown in FIG. 2B, the metal film 14 in a region where the mask 20 is not provided (a region where the mask 20 is not formed) is removed with an etching solution, whereby a patterned metal film 16 is obtained. A known resist material can be used as the mask 20. Thereafter, as shown in FIG. 2C, the mask 20 is removed.

The type of the resist material is not particularly limited, and a negative type, a positive type, a liquid type, and a film type can be used. The method for removing the resist layer is not particularly limited, and a known method (removal with an alkaline solution, dry etching) can be used.
The method for bringing the etching solution into contact with the metal film 14 is not particularly limited, and there are a method for applying the etching solution to the metal film 14 (for example, spray coating), a method for immersing a substrate having the metal film 14 in the etching solution, and the like. Can be mentioned.

(Second Embodiment)
Moreover, the 2nd embodiment shown in FIG. 3 is mentioned as another suitable aspect of a processing method preferably. This method is based on a so-called semi-additive method.
In the case of this method, first, after performing electroless plating in the plating step, a patterned mask is provided on the metal film obtained by electroless plating, and a metal is further formed in the region where the mask is not provided. Electrolytic plating is performed so that a film is formed. More specifically, as shown in FIG. 3A, after forming a metal film 14a on the layer 12 to be plated by electroless plating, a patterned mask 20 is provided on the metal film 14a (see FIG. B)). Thereafter, as shown in FIG. 3C, by performing electroplating, a metal film is further provided in a region where the mask 20 is not provided (a region where the mask 20 is not formed), and includes a convex portion 22 and a concave portion 24. The uneven metal film 14b is obtained. After electrolytic plating, the mask 20 is removed as shown in FIG.

  Next, the obtained metal film 14b having the concavo-convex structure is subjected to quick etching using the above etching solution, thereby removing the recesses 24 other than the protrusions 22 corresponding to the wiring portions in the metal film 14b. Thus, the patterned metal film 16 is obtained.

<Acid solution contact process>
The acidic solution contact step is a step of bringing a substrate having a patterned metal film into contact with an acidic solution that does not substantially contain a metal component or hydrogen peroxide. By performing this step, the layer to be plated in the region where the patterned metal film is not formed and the acidic solution are in contact with each other, and the metal component (for example, the plating catalyst or the metal film) contained in the layer to be plated is contacted. The constituent metal component) is removed. By passing through this process, the removal efficiency of a to-be-plated layer improves in the plasma etching process mentioned later.
In addition, it is preferable to obtain the to-be-plated layer which does not contain a metal component substantially in the area | region in which the pattern shape metal film is not formed through this process, Specifically, the metal in a to-be-plated layer It is preferable to reduce the component to about 3 mg / m ² or less.
First, the acidic solution used at this process is explained in full detail, and the procedure of the subsequent process is explained in full detail.

(Acid solution)
The acidic solution used in this step exhibits acidity. Especially, it is preferable that the pH of an acidic solution is 5 or less, and it is more preferable that it is 0-3 at the point which the removal performance of the metal component in a to-be-plated layer is more excellent.
The solvent contained in the acidic solution is usually water. Moreover, the organic solvent (For example, ethanol, methanol, propylene glycol monomethyl ether, isopropyl alcohol) may contain.

The acidic solution is substantially free of metal components or hydrogen peroxide. That is, an acidic solution substantially free of metal components and an acidic solution substantially free of hydrogen peroxide are used. By using the acidic solution, the pattern property of the formed patterned metal film is maintained while removing the metal component contained in the layer to be plated.
Here, “substantially not containing” means that the content of the metal component (or hydrogen peroxide) is 1% by mass or less with respect to the total amount of the acidic solution, and is 0.1% by mass or less. Preferably there is. The content is most preferably 0.

  The acid component contained in the acidic solution is not particularly limited, and known acid components such as hydrochloric acid, sulfuric acid, and nitric acid can be used. For example, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous nitric acid solution, or the like can be used.

(Process procedure)
The method for contacting the substrate having the patterned metal film with the acidic solution is not particularly limited, and examples thereof include a method of applying the acidic solution on the substrate and a method of immersing the substrate in the acidic solution.
The contact time between the substrate and the acidic solution is appropriately selected depending on the type of the acidic solution used. From the viewpoint of the removal of the metal component in the layer to be plated, the contact time is 10 seconds to 10 minutes. Preferably, 1 to 5 minutes is more preferable.

<Plating layer removal process>
The to-be-plated layer removing step is a step of removing the to-be-plated layer in the region where the patterned metal film is not formed by plasma etching. More specifically, the substrate having the patterned metal film is subjected to plasma etching, and as shown in FIGS. 1C and 1D, the substrate in the region 30 where the patterned metal film 16 is not formed. The plating layer 12 is removed. By removing the layer to be plated between the patterned metal films, the insulation performance between the wirings (between the metal films) is further improved.
In addition, when a to-be-plated layer is arrange | positioned on a board | substrate through the adhesion | attachment auxiliary | assistant layer mentioned above, not only a to-be-plated layer but the adhesion | attachment auxiliary | assistant layer may be removed together by the plasma etching process of this process.

As the plasma etching process, a known processing method can be carried out, and examples thereof include a reduced pressure plasma process or an atmospheric plasma process performed under atmospheric pressure.
The plasma etching process will be described in detail. For example, the substrate on which the wiring pattern after the pattern formation step is formed is housed in a chamber of a plasma processing apparatus, and plasma is generated in the chamber to generate ions and ions. This is done by causing neutral particles called radicals to collide with the substrate surface.

  In this step, the formed patterned metal film itself (wiring pattern) functions as an etching resist. Therefore, the plasma etching process causes a layer to be plated that remains exposed between the wirings, and adheres between the wirings. It is possible to effectively remove impurities such as organic matter. Note that it is preferable to perform the plasma etching process under processing conditions that do not affect the formed wiring pattern.

As a plasma generation method, either a low-pressure plasma method or an atmospheric plasma method can be applied, but a general-purpose low-pressure plasma method is preferably used.
The atmospheric pressure when performing the plasma etching treatment is preferably 100 Pa or less, and more preferably 10 Pa or less, from the viewpoint of the etching rate.
Note that if the atmospheric pressure plasma method is used, there is no need for depressurization, which is an advantage that in-line processing is possible, and this can be expected to improve production efficiency.

In the treatment, an inert gas selected from helium, argon, krypton, and xenon, O ₂ , CF ₄ , C ₂ F ₄ , N ₂ , CO ₂ , SF ₆ , CHF ₃ , at least O, N, F or Any one or more kinds of gases selected from the group consisting of reactive gases containing Cl can be used. These may be used alone or in combination. The gas to be used can be appropriately selected according to various conditions such as the influence on the substrate surface state after the processing, the control of the processing speed and the substrate temperature, and the like.

For example, from the viewpoint of processing speed, oxygen gas, argon gas, CF ₄ , and a mixed gas of oxygen gas and argon gas are preferable, and a mixed gas of argon gas, oxygen gas, and argon gas is more preferable.
In addition, when oxygen gas is used as the plasma gas, since the oxygen gas can generate hydroxyl groups on the treatment surface, for example, a solder resist mainly composed of an epoxy resin is disposed on the wiring board, In the case of thermally polymerizing the substrate surface and the solder resist, the adhesion between the substrate surface and the solder resist can be improved.
Further, regarding the case of using a CF-based gas as the plasma gas, the CF-based gas can improve the hydrophobicity of the processing surface. For example, in the case of forming a laminated substrate formed by laminating wiring substrates. In addition, the insulation reliability between the wirings can be further improved, such as the intrusion of moisture and the like from the interface between the substrates can be effectively prevented.

In this step, in particular, the atmospheric pressure when performing the plasma etching process is 100 Pa or less from the viewpoint of the etching rate, that is, the amount of plasma generated. In this process, oxygen gas, argon gas, CF ₄ gas, and C ₂ It is preferable to use at least one gas selected from the group consisting of F ₄ gas.

<Laminated body having a patterned metal film>
Through the above steps, a laminate having a patterned metal film from which the layer to be plated between the patterned metal films is removed can be obtained (FIG. 1D).
The obtained laminated body can be used for various uses. For example, it can be applied to various uses such as semiconductor chips, various electric wiring boards (printed wiring boards, etc.), FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, and the like. Especially, it can utilize suitably as a wiring board. Moreover, when using with a wiring board, you may provide the insulating layer 40 on the laminated body 18 as needed (FIG.1 (E)).
The wiring substrate 50 including the laminate 18 and the insulating layer 40 of the present invention can form a wiring having excellent adhesion to a smooth substrate, has good high-frequency characteristics, and is a fine high-density wiring. Excellent insulation reliability between wires.
A known material can be used for the insulating layer 40, and examples thereof include a known interlayer insulating film and a solder resist.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

(Synthesis Example 1: Polymer 1)
1 L of ethyl acetate and 159 g of 2-aminoethanol were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto was added dropwise 150 g of 2-bromoisobutyric acid bromide so that the internal temperature was 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
Next, the raw material A (47.4g), pyridine (22g), and ethyl acetate (150mL) were put into a 500 mL three necked flask, and it cooled in the ice bath. Thereto, 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, ethyl acetate was distilled off, and monomer A was purified by column chromatography to obtain 20 g.

  In a 500 mL three-necked flask, 21 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, monomer A obtained above: 26.8 g, acrylic acid (manufactured by Tokyo Chemical Industry) 15.6 g, acrylamide 3.1 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.59 g of N, N-dimethylacetamide 34 g The solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 35 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.17g and DBU105g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 104 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain polymer 1 (weight average molecular weight 42,000) (21 g). When the acid value of the obtained polymer 1 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 1 was It was 4.2 mmol / g.

  The obtained polymer 1 was neutralized with sodium hydrogencarbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2- Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 2.5-. A peak derived from an acrylamide unit was observed at 0.7 ppm (3H min), and a peak derived from an acrylamide unit was observed at 2.5-0.7 ppm (3H min) broadly. A unit having a (meth) acrylamide group, a carboxylic acid group It was confirmed that a polymer composed of units having acrylamide and units derived from acrylamide was produced.

(Synthesis Example 2: Polymer 2)
In a 500 mL three-necked flask, 21 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, monomer A obtained above: 27.9 g, acrylic acid (manufactured by Tokyo Chemical Industry) 13.1 g, N, N-dimethylacrylamide 3.3 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.59 g N, A solution of 35 g of N-dimethylacetamide was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 37 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.18g and DBU109g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 108 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction solution. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain polymer 2 (weight average molecular weight: 40,000) (20 g). When the acid value of the obtained polymer 2 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 2 was It was 4.1 mmol / g.

  The obtained polymer 2 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2- Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 2.5-. Broadly observed at 0.7 ppm (3H min), peaks derived from dimethylacrylamide units are observed broadly at 3.0-2.7 ppm (6H min), 2.5-0.7 ppm (3H min), It was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from N, N-diethylacrylamide was produced.

(Synthesis Example 3: Polymer 3)
In a 500 mL three-necked flask, 21 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. The monomer A obtained above: 25.4 g, acrylic acid (Tokyo Kasei) 12.9 g, N, N-diethylacrylamide (Tokyo Kasei) 5.7 g, V-601 (Wako Pure Chemical Industries) 0 .59 g of N, N-dimethylacetamide 36 g solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 37 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.17g and DBU105g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 104 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain polymer 3 (weight average molecular weight 41,000) (23 g). When the acid value of the obtained polymer 3 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 3 was It was 4.2 mmol / g.

  The obtained polymer 3 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2- Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 2.5-. Broadly observed at 0.7 ppm (3H minutes), peaks derived from diethylacrylamide units are observed broadly at 3.4-3.0 ppm (4H minutes), 2.5-0.7 ppm (9H minutes), It was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from acrylamide was produced.

(Synthesis Example 4: Polymer 4)
In a 500 mL three-necked flask, 23 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, monomer A obtained above: 28.1 g, acrylic acid (manufactured by Tokyo Chemical Industry) 12.9 g, acryloylmorpholine (manufactured by Kojin Co., Ltd.) 5.0 g, V-601 (manufactured by Wako Pure Chemical Industries) 59 g of N, N-dimethylacetamide (Tokyo Kasei) 37 g solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 38 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.18g and DBU108g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 108 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain polymer 4 (weight average molecular weight 43,000) (24 g). When the acid value of the obtained polymer 4 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 4 was It was 4.1 mmol / g.

  The obtained polymer 4 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2- Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 2.5-. A broad peak is observed at 0.7 ppm (3 H min), and a peak derived from the acryloylmorpholine unit is observed at 3.7-3.5 ppm (8 H min), 2.8-0.7 ppm (3 H min) broad, It was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from acryloylmorpholine was produced.

(Synthesis Example 5: Polymer 5)
1 L of ethyl acetate and 400 g of ethylenediamine were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto was added dropwise 200 g of 2-bromoisobutyric acid bromide so that the internal temperature was 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed 4 times with 300 mL of distilled water, dried over magnesium sulfate, and ethyl acetate was distilled off and purified by column chromatography to obtain 50 g of a raw material B in which only one terminal amino group had reacted. .

  Next, the raw material B (45g), pyridine (22g), and ethyl acetate (150mL) were put into a 500 mL three necked flask, and it cooled in the ice bath. Thereto, 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, ethyl acetate was distilled off, and monomer B was purified by column chromatography to obtain 30 g.

  In a 500 mL three-necked flask, 22 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, monomer B: 28.3 g obtained above, acrylic acid (manufactured by Tokyo Chemical Industry) 12.1 g, diethylacrylamide (manufactured by Tokyo Chemical Industry) 5.7 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.59 g N , N-dimethylacetamide 37 g solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 38 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.19g and DBU105g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 104 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain polymer 5 (weight average molecular weight 38,000) (19 g). When the acid value of the obtained polymer 5 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 5 was It was 4.4 mmol / g.

  The obtained polymer 5 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (2H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 3.5- A broad peak is observed at 3.3 ppm (4H min) and 2.5-0.7 ppm (6H min), and a peak corresponding to a carboxylic acid group unit is observed broad at 2.5-0.7 ppm (3H min). , Peaks derived from diethylacrylamide units are observed broadly at 3.4-3.0 ppm (4H minutes), 2.5-0.7 ppm (9H minutes), units having (meth) acrylamide groups, carboxylic acid groups It was confirmed that a polymer comprising a unit having a unit and a unit derived from diethylacrylamide was produced.

(Synthesis Example 6: Polymer 6)
1 L of ethyl acetate and 446 g of 3-aminomethyl-3,5,5-trimethylcyclohexanol were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto was added dropwise 150 g of 2-bromoisobutyric acid bromide so that the internal temperature was 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, ethyl acetate was distilled off, and purified by column chromatography to obtain 120 g of raw material C.

  Next, the raw material C (72g), pyridine (22g), and ethyl acetate (150mL) were put into a 500 mL three necked flask, and it cooled in the ice bath. The acrylic acid chloride 25g was dripped and adjusted so that it might become 20 degrees C or less of internal temperature there. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, ethyl acetate was distilled off, and monomer C was purified by column chromatography to obtain 25 g.

  In a 500 mL three-necked flask, 13 g of N, N-dimethylacetamide was added and heated to 60 ° C. under a nitrogen stream. Thereto, monomer C: 18.6 g obtained above, acrylic acid (manufactured by Tokyo Chemical Industry) 6 g, diethylacrylamide (manufactured by Tokyo Chemical Industry) 2.1 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.28 g of N, N -A 21 g solution of dimethylacetamide was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 22 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.09g and DBU50.1g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 51 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain polymer 6 (weight average molecular weight 44,000) (9 g). When the acid value of the obtained polymer 6 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 6 was It was 4.5 mmol / g.

  The obtained polymer 6 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.4- It was observed broadly at 4.1 ppm (2H min), 3.5-3.3 ppm (2H min), 2.5-0.7 ppm (21H min), and a peak corresponding to the carboxylic acid group unit was 2.5- Broadly observed at 0.7 ppm (3H minutes), peaks derived from diethylacrylamide units are observed broadly at 3.4-3.0 ppm (4H minutes), 2.5-0.7 ppm (9H minutes), It was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from diethylacrylamide was produced.

(Synthesis Example 7: Polymer 7)
1 L of ethyl acetate and 274 g of 2- (2-aminoethoxy) ethanol were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto was added dropwise 150 g of 2-bromoisobutyric acid bromide so that the internal temperature was 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 90 g of raw material D was obtained by distilling off ethyl acetate.

  Next, the raw material D (57g), pyridine (22g), and ethyl acetate (150mL) were put into a 500 mL three necked flask, and it cooled in the ice bath. The acrylic acid chloride 25g was dripped and adjusted so that it might become 20 degrees C or less of internal temperature there. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, ethyl acetate was distilled off, and monomer D was purified by column chromatography to obtain 22 g.

  In a 500 mL three-necked flask, 16 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto monomer D: 20.5 g obtained above, acrylic acid (Tokyo Kasei) 8.1 g, diethylacrylamide 2.8 g, V-601 (Wako Pure Chemical Industries) 0.37 g N, N-dimethylacetamide A 25 g solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 26 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.11g and DBU68g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 67 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain polymer 7 (weight average molecular weight 39,000) (14 g). When the acid value of the obtained polymer 7 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 7 was It was 4.4 mmol / g.

  The obtained polymer 7 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by 300 MHz NMR (AV-300) manufactured by Bruker. Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2- A broad peak at 3.9 ppm (2H min), 3.8-3.3 ppm (6H min), and 2.5-0.7 ppm (6H min) was observed, and a peak corresponding to a carboxylic acid group unit was 2.5- Broadly observed at 0.7 ppm (3H minutes), peaks derived from diethylacrylamide units are observed broadly at 3.4-3.0 ppm (4H minutes), 2.5-0.7 ppm (9H minutes), It was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from diethylacrylamide was produced.

(Synthesis Example 8: Polymer 8)
1 L of ethyl acetate and 350 g of 4-vinylphenyl-methylamine were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto was added dropwise 150 g of 2-bromoisobutyric acid bromide so that the internal temperature was 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 100 g of raw material E was obtained by distilling off ethyl acetate.

  Next, a raw material E (57 g), pyridine (24 g), and ethyl acetate (170 mL) were placed in a 500 mL three-necked flask and cooled in an ice bath. The acrylic acid chloride 28g was dripped and adjusted so that it might become 20 degrees C or less of internal temperature there. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and ethyl acetate was distilled off, followed by purification by column chromatography to obtain 27 g of monomer E.

  In a 500 mL three-necked flask, 16 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, monomer E: 22 g obtained above, acrylic acid (manufactured by Tokyo Chemical Industry) 8 g, diethylacrylamide (manufactured by Tokyo Chemical Industry) 2.8 g, V-601 (manufactured by Wako Pure Chemical Industries) 0.37 g of N, N-dimethyl A solution of 26 g of acetamide was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 27 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.11g and DBU (67.7g) were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 68 g of a 70% by mass methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain polymer 8 (weight average molecular weight 38,000) (13 g). When the acid value of the obtained polymer 8 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 8 was It was 4.3 mmol / g.

  The obtained polymer 8 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 8.1 to 7.8 ppm (1 H min), 7.5 to 7.0 ppm (4 H), 5.8 to 5.6 ppm (1 H min), 5.4-5 .2 ppm (1H min), 4.6-4.4 ppm (2H min), 2.5-0.7 ppm (6H min) broadly observed, and a peak corresponding to a carboxylic acid group unit is 2.5-0. .7 ppm (3 H min.) Broadly observed, and peaks derived from diethylacrylamide units were observed at 3.4-3.0 ppm (4 H min.), 2.5-0.7 ppm (9 H min.) Broad ( It was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from diethylacrylamide was produced.

(Synthesis Example 9: Polymer 9)
A 500 mL three-necked flask was charged with 35 g of N, N-dimethylacetamide and heated to 60 ° C. under a nitrogen stream. The monomer A obtained in Synthesis Example 1: 28.1 g, 37 g of acrylamide-2-methylpropanesulfonic acid (manufactured by Tokyo Chemical Industry), 5.0 g of acryloylmorpholine (manufactured by Kojin Co., Ltd.), V-601 (Japanese) A solution of 0.59 g of N, N-dimethylacetamide (61 g) was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 58 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.18g and DBU109g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 108 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction solution. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain polymer 9 (weight average molecular weight: 40,000) (45 g). When the acid value of the obtained polymer 9 was measured using a potentiometric automatic titration apparatus (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 9 was It was 3.5 mmol / g.

  The obtained polymer 9 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). The peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), 2.5-0.7 ppm (6H min), and a peak corresponding to the sulfonic acid group unit was 8.1- Broad peaks were observed at 7.8 ppm (1H min), 3.1-2.7 ppm (2H min), and 2.5-0.7 ppm (9H min), and a peak derived from the acryloylmorpholine unit was 3.7-3. .5 ppm (8H min), 2.8-0.7 ppm (3H min) broadly observed, producing a polymer composed of units having (meth) acrylamide groups, units having sulfonic acid groups, and units derived from acryloylmorpholine It was confirmed that.

(Synthesis Example 10: Polymer 10)
In a 500 mL three-necked flask, 49 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, monomer A obtained in Synthesis Example 1: 28.1 g, Phosmer M (manufactured by Unichemical) 66 g, acryloylmorpholine (manufactured by Kojin Co., Ltd.) 5.0 g, V-601 (manufactured by Wako Pure Chemical Industries) 59 g of N, N-dimethylacetamide 90 g solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 82 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.18g and DBU109g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 108 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction solution. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain polymer 10 (weight average molecular weight 48,000) (81 g). When the acid value of the obtained polymer 10 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 10 was It was 2.0 mmol / g.

  The obtained polymer 10 was neutralized with sodium hydrogen carbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). The peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and a peak corresponding to a phosphate group unit was 4.3-. 3.8 ppm (4H min), 2.5-0.7 ppm (5H min) are observed broadly, and peaks derived from acryloylmorpholine units are 3.7-3.5 ppm (8H min), 2.8-0. It was observed broadly at 0.7 ppm (3H), and it was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a phosphate group, and a unit derived from acryloylmorpholine was produced.

(Synthesis Example 11: Polymer 11)
A 500 mL three-necked flask was charged with 36 g of N, N-dimethylacetamide and heated to 60 ° C. under a nitrogen stream. There, monomer A obtained in Example 1: 28.0 g, NK ester A-SA (manufactured by Shin-Nakamura Chemical) 38.6 g, acryloylmorpholine (manufactured by Kojin Co., Ltd.) 5.0 g, V-601 (Japanese) A solution of 0.59 g of N, N-dimethylacetamide 60 g was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 62 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.18g and DBU108g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 108 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain polymer 11 (weight average molecular weight 43,000) (35 g). When the acid value of the obtained polymer 11 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 11 was It was 3.2 mmol / g.

  The obtained polymer 11 was neutralized with sodium hydrogencarbonate, dissolved in heavy water, and measured by Bruker 300 MHz NMR (AV-300). The peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 4.2. A broad peak observed at 3.9 ppm (4H min), 2.8-0.7 ppm (7H min) and a peak derived from the acryloylmorpholine unit is 3.7-3.5 ppm (8H min), 2.8-0. It was observed broadly at 0.7 ppm (3H min), and it was confirmed that a polymer composed of a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from acryloylmorpholine was produced.

(Synthesis Example 12: Comparative polymer 1)
18 g of poly (acrylic acid-co-dimethylacrylamide-co-2-hydroxyethyl acrylate) (average molecular weight 25,000, molar ratio of each unit is 62:16:22) is dissolved in DMAc 300 g, hydroquinone 0.41 g and 2 -19.4 g of methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate were added and reacted at 65 ° C for 4 hours. The acid value of the obtained polymer was 4.2 meq / g. Thereafter, the carboxyl group was neutralized with a 1N aqueous sodium hydroxide solution, and the polymer was precipitated in addition to ethyl acetate and washed well to obtain comparative polymer 1.
The polymer does not contain a unit represented by the formula (A).

(Synthesis Example 13: Comparative polymer 2)
A 500 mL three-necked flask was charged with 8 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. Thereto, monomer A: 14.3 g obtained above, 3.0 g acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.5 g acrylic acid (manufactured by Tokyo Chemical Industry), V-65 (manufactured by Wako Pure Chemical Industries) 4 g of N, N-dimethylacetamide 8 g solution was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 41 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.09g and DBU54.8g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 54 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 12 g of Comparative Polymer 2 (weight average molecular weight 53,000) having the following structural formula was obtained. The acid value of the obtained comparative polymer 2 was measured using a potentiometric automatic titrator (manufactured by Kyoto Denshi Kogyo Co., Ltd.) and a 0.1M aqueous sodium hydroxide solution as the titrant. The value was 3.9 mmol / g.

The obtained comparative polymer 2 was identified using an IR measuring machine (manufactured by Horiba, Ltd.). The measurement was performed by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm ⁻¹ , and it was found that acrylonitrile as a nitrile unit was introduced into the polymer. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Moreover, it melt | dissolved in heavy DMSO (dimethyl sulfoxide), and measured by NMR (AV-300) of Bruker 300MHz. 4. A peak corresponding to a cyano group-containing unit is broadly observed at 2.5 to 0.7 ppm (5 H min), and a peak corresponding to a polymerizable group containing unit is 7.8 to 8.1 ppm (1 H min). 8-5.6 ppm (for 1H), 5.4-5.2 ppm (for 1H), 4.2-3.9 ppm (for 2H), 3.3-3.5 ppm (for 2H), 2.5- A broad peak is observed at 0.7 ppm (6H min), and a peak corresponding to a carboxylic acid group unit is observed broadly at 2.5-0.7 ppm (3H min), a polymerizable group-containing unit, a cyano group-containing unit, It was also confirmed that a polymer composed of carboxylic acid group units was produced.
The polymer does not contain a unit represented by the formula (C). The polymer contains a cyano group.

<Example 1>
(Preparation of base insulating substrate)
An epoxy insulating film (GX-13, 45 μm) manufactured by Ajinomoto Fine Techno Co. on a glass epoxy substrate (trade name: FR-4, manufactured by Matsushita Electric Works Co., Ltd.) at a pressure of 0.2 MPa. An electrical insulating layer was formed on the substrate by heating and pressing using a vacuum laminator under the condition of 110 ° C. for adhesion. Thereafter, heat treatment was performed at 170 ° C. for 1 hour, and the electrically insulating layer was formed into a thermal layer.

(Formation of adhesion auxiliary layer)
On the formed electrical insulating layer, a composition for forming an adhesion auxiliary layer having the following composition is applied by a spin coating method so as to have a thickness of 1.5 μm, and then dried at 140 ° C. for 30 minutes to form an adhesion auxiliary layer. Formed.
The substrate after the adhesion auxiliary layer was formed was further subjected to a curing treatment at 180 ° C. for 30 minutes to produce a substrate A1.

(Adhesion auxiliary layer forming composition)
25 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) (hereinafter, all the compounding amounts are expressed in parts by mass), cresol novolac type epoxy resin (epoxy equivalent 215, Dainippon Ink 45 parts of Chemical Industry Co., Ltd. Epicron N-673), 30 parts of phenol novolak resin (phenolic hydroxyl group equivalent 105, Phenolite manufactured by Dainippon Ink & Chemicals, Inc.), 20 parts of ethyl diglycol acetate, solvent naphtha 20 The mixture was heated and dissolved with stirring, and cooled to room temperature. Thereafter, 30 parts of phenoxy resin cyclohexanone varnish (YL6747H30 manufactured by Yuka Shell Epoxy Co., Ltd., nonvolatile content 30 mass%, weight average molecular weight 47000) composed of the above Epicoat 828 and bisphenol S, 2-phenyl-4,5- 0.8 parts of bis (hydroxymethyl) imidazole, 2 parts of finely pulverized silica, and 0.5 part of a silicon-based antifoaming agent were added to prepare a composition for forming an adhesion auxiliary layer.

(Formation of plated layer)
Next, the composition 1 for forming a layer to be plated, which will be described later, was applied on the substrate A1 by a spin coating method so as to have a thickness of 1.5 μm, and then dried at 80 ° C.

Next, the entire surface of the applied composition layer was exposed to ultraviolet light having a wavelength of 254 nm at room temperature for 2.5 minutes using an exposure machine (ultraviolet irradiation device, UVX-02516S1LP01, manufactured by USHIO INC.). (Energy amount at 254 nm: 1500 mJ). After the entire surface exposure, the substrate was sufficiently washed with 0.8 wt% sodium bicarbonate solution in order to remove unnecessary composition for forming a layer to be plated.
As a result, a substrate A2 having a layer to be plated (thickness after cleaning: 0.7 μm) on the substrate A1 was obtained.

(Composition 1 for plating layer formation)
・ Polymer 1 3.1g
・ Baking soda 0.8g
・ Water 25.9g
・ 13.0 g of 1-methoxy-2-propanol

(Addition of plating catalyst)
Substrate A2 was dipped in an aqueous solution (liquid temperature: 25 ° C.) of 0.1% by mass of palladium nitrate for 10 minutes, and then washed with distilled water. The amount of palladium ion adsorbed at this time was 0.1 g / m ² when measured with an ICP emission analyzer (manufactured by Shimadzu Corporation).

(Electroless plating treatment)
The substrate after the plating catalyst (metal salt) was applied was immersed in an electroless plating bath (alkaline: pH 12.5) having the following composition for 1 hour to form an electroless copper plating layer having a thickness of 0.4 μm.

(Electroless plating bath component)
・ Copper sulfate 0.35g
・ NaK tartrate 1.75g
-Sodium hydroxide 0.75g
・ Formaldehyde 0.25g
・ Water 47.8g

(Electrolytic plating)
The substrate on which the electroless copper plating layer was formed was immersed in an electrolytic copper plating bath having the following composition, and electroplating was performed for about 20 minutes under a current density of 3 A / dm ² . The thickness of the copper plating layer (metal film) after the electrolytic plating was about 18 μm.

(Electrolytic plating bath component)
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Cover Grime PCM (Meltex Co., Ltd.) 3.5mL
・ Water 500g

(Pattern formation process)
The substrate after electrolytic plating was subjected to a heat treatment at 170 ° C. for 1 hour, and then a dry resist film (RY3315 manufactured by Hitachi Chemical Co., Ltd., film thickness 30 μm) was laminated on the surface of the substrate. Next, a glass mask capable of forming a comb pattern of L / S = 40 μm / 40 μm was adhered to the substrate on which the dry resist film was laminated by a subtractive method, and the photosensitive region of the resist was exposed. After the exposure, an aqueous NaHCO ₃ solution was applied at a spray pressure of ² kg / m ² to perform development processing. Thereafter, the substrate was washed with water and dried to form a resist pattern on the copper plating layer.

The metal film is etched by showering an FeCl ₂ / HCl aqueous solution (temperature: 37 ° C.) (pH: 1.5) for 90 seconds with respect to the substrate on which the resist pattern is formed, and exists in the resist pattern non-formation region. The copper plating was removed. Thereafter, a resist pattern was peeled off by forming a 4 mass% NaOH aqueous solution on the substrate at a spray pressure of ² kg / m ² .

(Acid solution treatment)
Then, it was immersed in hydrochloric acid aqueous solution (pH: 0.5) for 10 minutes, and the metal component in a to-be-plated layer was removed. The amount of palladium ion adsorbed in the plated layer at this time was measured with an ICP emission analyzer (manufactured by Shimadzu Corporation), and was below the detection limit (3 mg / m ² or less).

(Plating layer removal)
A substrate having a patterned metal film (wiring pattern) is placed in a chamber of a plasma etching apparatus (manufactured by SAMCO, parallel plate type plasma processing apparatus, PC-1000), and the wiring pattern forming surface faces the plasma irradiation surface. Arranged. The inside of the chamber was depressurized to 4 × 10 ⁻¹ Pa (3 × 10 ⁻³ Torr), and plasma treatment was performed in an oxygen atmosphere for 1.5 minutes. When the cross section of the treated substrate surface was observed with an SEM image, it was confirmed that the layer to be plated and the adhesion auxiliary layer between the wires were removed.

(Attaching solder resist)
Solder resist (PFR800; manufactured by Taiyo Ink Mfg. Co., Ltd.) is vacuum-laminated on the plasma-treated substrate under conditions of 110 ° C. and 0.2 MPa, and light energy of 420 mJ is irradiated with an exposure machine having a central wavelength of 365 nm. did.
Next, the substrate was subjected to a heat treatment at 80 ° C./10 minutes, and then developed by applying a NaHCO ₃ : 10% aqueous solution to the substrate surface at a spray pressure of 2 kg / m ² and dried. Thereafter, the substrate was again irradiated with light energy of 1000 mJ with an exposure machine having a center wavelength of 365 nm. Finally, a heat treatment at 150 ° C./1 hr was performed to obtain a wiring board coated with a solder resist.

<Example 2>
A wiring board was obtained according to the same procedure as in Example 1 except that polymer 2 was used instead of polymer 1.

<Example 3>
A wiring board was obtained according to the same procedure as in Example 1 except that polymer 3 was used instead of polymer 1.

<Example 4>
A wiring board was obtained according to the same procedure as in Example 1 except that polymer 4 was used instead of polymer 1.

<Example 5>
A wiring board was obtained according to the same procedure as in Example 1 except that the procedure of (application of plating catalyst) in Example 1 was changed to the procedure described below.

(Addition of plating catalyst)
The substrate A2 was immersed in an aqueous solution (liquid temperature: 60 ° C.) of palladium nitrate of 0.1% by mass for 10 minutes and then washed with distilled water. The amount of palladium ion adsorbed onto the layer to be plated at this time was 0.2 g / m ² when measured with an ICP issuing analyzer (manufactured by Shimadzu Corporation).

<Example 6>
According to the same procedure as in Example 1, except that the etching process of the metal film using the FeCl ₂ / HCl aqueous solution in (Pattern forming step) in Example 1 was changed to the procedure described below. Got.

(Pattern formation process)
Etching of the metal film is performed by showering the substrate on which the resist pattern is formed with Cu (NH ₃ ) ₄ Cl ₂ aqueous solution (temperature 37 ° C.) (pH: 8.5) for 90 seconds, so that the resist pattern is not formed. The copper plating present in the area was removed.

<Example 7>
For the substrate having the electrical insulating layer prepared in (Preparation of base insulating substrate) without carrying out the step (Formation of adhesion auxiliary layer) in Example 1 above (Formation of layer to be plated) A wiring board was obtained according to the same procedure as in Example 1 except that the step was performed and a layer to be plated was formed on the electrically insulating layer.
In Example 7, the layer to be plated is disposed on the substrate without using the adhesion auxiliary layer.

<Example 8>
The same procedure as in Example 1 except that the polymer 5 was used instead of the polymer 1, and the entire surface was exposed to ultraviolet light having a wavelength of 254 nm in (formation of a layer to be plated) at room temperature for 3 minutes (energy amount at 254 nm: 1800 mJ). A wiring board was obtained.

<Example 9>
The same procedure as in Example 1 except that the polymer 6 was used instead of the polymer 1 and the entire surface was exposed to ultraviolet light having a wavelength of 254 nm in (formation of a layer to be plated) at room temperature for 4 minutes (energy amount at 254 nm: 2400 mJ). A wiring board was obtained.

<Example 10>
The same procedure as in Example 1 except that the polymer 7 was used instead of the polymer 1, and the entire surface was exposed to ultraviolet light having a wavelength of 254 nm in (formation of a layer to be plated) at room temperature for 4 minutes (energy amount at 254 nm: 2400 mJ). A wiring board was obtained.

<Example 11>
The same procedure as in Example 1 except that the polymer 8 was used instead of the polymer 1, and the entire surface was exposed to ultraviolet light having a wavelength of 254 nm in (formation of a layer to be plated) at room temperature for 4 minutes (energy amount at 254 nm: 2400 mJ). A wiring board was obtained.

<Example 12>
In place of polymer 1, polymer 9 was used, and ultraviolet light having a wavelength of 254 nm in (formation of a layer to be plated) was exposed for 10 minutes at room temperature (energy amount at 254 nm: 6000 mJ). A wiring board was obtained according to the same procedure as in Example 1 except that the amount of baking soda was changed from 0.8 g to 0.65 g.

<Example 13>
In place of polymer 1, polymer 10 was used, and ultraviolet light with a wavelength of 254 nm in (formation of the layer to be plated) was exposed for 10 minutes at room temperature (energy amount at 254 nm: 6000 mJ). A wiring board was obtained according to the same procedure as in Example 1 except that the amount of baking soda was changed from 0.8 g to 0.38 g.

<Example 14>
Using polymer 11 instead of polymer 1, the entire surface was exposed to ultraviolet light having a wavelength of 254 nm in (formation of the layer to be plated) at room temperature for 10 minutes (energy amount at 254 nm: 6000 mJ). A wiring board was obtained according to the same procedure as in Example 1 except that the amount of baking soda was changed from 0.8 g to 0.6 g.

<Comparative Example 1>
A wiring board was obtained according to the same procedure as in Example 1 except that the comparative polymer 2 was used instead of the polymer 1.

<Comparative example 2>
The following (Composition 2 for Plating Layer Formation) is used instead of (Composition 1 for Plating Layer Formation), and the steps of (acidic solution treatment) and (removal of plating layer) are not performed. A wiring board was manufactured according to the same procedure as in Example 1.
When the cross section of the substrate surface after removal of the plated layer was observed with an SEM image, it was confirmed that the plated layer between the wirings remained.
(Composition 2 for plating layer formation)
・ Comparative polymer 1 0.25g
・ Water 5g
・ Acetonitrile 3g

<Comparative Example 3>
A wiring board was manufactured according to the same procedure as in Example 1 except that (acidic solution treatment) in Example 1 was not performed.

<Comparative example 4>
A wiring board was obtained according to the same procedure as in Example 1 except that the step (removal of plated layer) in Example 1 was not performed.

<Evaluation method>
(Insulation evaluation)
The insulation reliability test of the wiring board obtained as described above was performed using an electrochemical migration evaluation apparatus (manufactured by Espec Corporation, an electrochemical migration apparatus AMI and a high-temperature and high-humidity tank Platinum PR-3K). The test conditions were a bias voltage of 30 V, a temperature and humidity environment of 85 ° C., 85% RH, and distilled water having a resistance value of 13 M was used as the humidified water, and evaluation was performed up to 1000 hours. Evaluation was made according to the following criteria. The results are shown in Table 1.

“D”: When the resistance value of the wiring board falls below 1 MΩ in the evaluation up to less than 500 hours. “C”: When the resistance value of the wiring board falls below 1 MΩ in the evaluation from 500 hours to less than 750 hours. B ”: When the resistance value of the wiring board falls below 1 MΩ in the evaluation from 750 hours to less than 1000 hours.“ A ”: When the evaluation is made up to 1000 hours and the resistance value of the wiring board does not fall below 1 MΩ.

(Plasma etching rate)
Table 1 shows the etching rate (μm / min) of plasma etching when removing the layer to be plated and the adhesion auxiliary layer in Examples 1 to 14 and Comparative Examples 1 and 3 (removal of the layer to be plated). Shown together.

(Adhesion evaluation)
After performing the baking process for 100 minutes at 100 degreeC with respect to the board | substrate (laminated body) which has the metal film obtained after the electroplating obtained in Examples 1-4, autograph AGS-J (Manufactured by Shimadzu Corporation), 90 ° peel strength was measured at a tensile strength of 10 mm / min for a metal film width of 5 mm. The results are summarized in Table 1.

In Table 1 above, “A” in the “Plating catalyst adsorption condition” column indicates that when the temperature of the 0.1 wt% palladium nitrate aqueous solution used in (application of plating catalyst) is 25 ° C., “B” indicates nitric acid. This means that the liquid temperature of the palladium 0.1 mass% aqueous solution is 60 ° C.
“A” in the “Type of etchant” column indicates that the etchant used in the (pattern formation step) is an FeCl ₂ / HCl aqueous solution, and “B” indicates that the etchant is a Cu (NH ₃ ) ₄ Cl ₂ aqueous solution. Means the case.
In Table 1, “-” means not implemented.

As shown in Examples 1 to 14, the wiring board obtained by carrying out the method for producing a laminate having a patterned metal film of the present invention showed excellent insulating performance. Furthermore, in Examples 1-14, the plasma etching rate of the to-be-plated layer was also excellent.
In addition, compared with Example 1 and 5, Example 1 with little adsorption amount of the palladium ion in a to-be-plated layer was more excellent in insulation. This is because the smaller the amount of the metal component in the layer to be plated, the better the etching property of the layer to be plated.
Further, from comparison between Examples 1 and 6, it was confirmed that the use of an acidic etching solution (FeCl ₂ / HCl aqueous solution) as the etching solution was superior in insulation. This can be said to be because the metal component in the layer to be plated is easily removed when the etching solution is used.
In addition, from the comparison of Examples 1 to 4, the use of a more hydrophobic unit having higher alkali hydrolysis resistance as the unit represented by the formula (C) reduces the damage to the plated layer and improves the adhesion. It was stronger.

On the other hand, in Comparative Example 1 using a polymer having a CN group, the layer to be plated was not efficiently removed, and as a result, the insulation performance between the wirings was inferior.
Further, even in Comparative Example 2 in which a polymer having a polymerizable group unit that is not a predetermined functional group is used, and the acidic solution treatment and the plasma etching treatment are not performed, the layer to be plated is not efficiently removed. The insulation performance was inferior.
Furthermore, as shown in Comparative Examples 3 and 4, when the acidic solution treatment or the plasma etching treatment was not performed, the insulation performance between the wirings was inferior.
The reason why the effects were inferior in Comparative Examples 1 to 4 is considered to be due to the metal component contained in the layer to be plated.

(Moisture resistance evaluation)
A substrate (laminated body) having a metal film obtained after the (electrolytic plating) step of Example 1 and Comparative Example 2 was left at 80 ° C. and 90 RH% for one week, and then JIS-K5600-5-6: 1999. A cross-cut peel test was performed. Evaluation was made according to the following criteria.
“A”: When 95 or more of 100 eyes remain “B”: When less than 95 of 100 eyes remain

In Example 1, the moisture resistance evaluation was “A”, but in Comparative Example 2, it was “B”.
This is because in the production method of the present invention, the unit represented by the formula (A) has a (meth) acrylamide group, so that it is not easily hydrolyzed, and as a result, the adhesion of the metal film is further improved. it is conceivable that.

10: Substrate 12: Plated layers 14, 14a, 14b: Metal film 16: Patterned metal film 18: Laminated body 18: Patterned metal film 20: Mask 22: Convex part 24: Concave part 30: Patterned metal film formed Unused region 40: insulating layer 50: wiring board

Claims (9)

After contacting the composition for forming a layer to be plated on the substrate, including the unit represented by the formula (A), the unit represented by the formula (B), and the polymer having the unit represented by the formula (C) A layer to be plated forming step for forming a layer to be plated on the substrate by applying energy to the composition for forming a layer to be plated on the substrate;
A catalyst application step of applying a plating catalyst or a precursor thereof to the layer to be plated;
A plating process for performing a plating treatment on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal film on the layer to be plated;
After the plating step, a pattern forming step of forming a patterned metal film using an etching solution containing a metal component or hydrogen peroxide,
An acidic solution contact step in which the substrate having the patterned metal film is contacted with an acidic solution substantially free of a metal component or hydrogen peroxide;
A method for producing a laminate having a patterned metal film, comprising: a plated layer removing step of removing the plated layer in a region where the patterned metal film is not formed by plasma etching.

(In Formula (A) to Formula (C), R ¹ , R ² , R ⁴ , and R ⁶ each independently represents a hydrogen atom or a methyl group. R ³ represents a hydrogen atom, a methyl group, or an ethyl group. Represents a group, t-butyl group or n-butyl group, V and W each independently represents a single bond, an ester group, an amide group or a phenylene group, and L ¹ represents a divalent hydrocarbon group. L ² represents a single bond or a divalent organic group, X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof, Z represents an —OR ⁷ group, or , —N (R ⁸ ) ₂ group, R ⁷ represents an alkyl group, a phenyl group, or a combination thereof, and R ⁷ includes —O— (oxygen atom). which may .R ⁸ each independently represent a hydrogen atom or an alkyl group which may contain -O-,. Incidentally R ⁸ may be bonded to each other to form a ring.)   The manufacturing method of the laminated body which has a patterned metal film of Claim 1 whose said etching liquid is acidic.   The manufacturing method of the laminated body which has a patterned metal film of Claim 1 or 2 whose said metal component is a copper ion or an iron ion.   The manufacturing method of the laminated body which has a patterned metal film in any one of Claims 1-3 whose said acidic solution is hydrochloric acid aqueous solution, sulfuric acid aqueous solution, or nitric acid aqueous solution.   A wiring board provided with the laminated body which has the patterned metal film manufactured by the manufacturing method in any one of Claims 1-4, and the insulating layer provided on the laminated body which has the said patterned metal film. The composition for to-be-plated layer forming containing the polymer which has a unit represented by the unit represented by Formula (A), the unit represented by Formula (B), and Formula (C).

(In Formula (A) to Formula (C), R ¹ , R ² , R ⁴ , and R ⁶ each independently represents a hydrogen atom or a methyl group. R ³ represents a hydrogen atom, a methyl group, or an ethyl group. Represents a group, t-butyl group or n-butyl group, V and W each independently represents a single bond, an ester group, an amide group or a phenylene group, and L ¹ represents a divalent hydrocarbon group. L ² represents a single bond or a divalent organic group, X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof, Z represents an —OR ⁷ group, or , —N (R ⁸ ) ₂ group, R ⁷ represents an alkyl group, a phenyl group, or a combination thereof, and R ⁷ includes —O— (oxygen atom). which may .R ⁸ each independently represent a hydrogen atom or an alkyl group which may contain -O-,. Incidentally R ⁸ may be bonded to each other to form a ring.) The composition for forming a plated layer according to claim 6, wherein the unit represented by the formula (A) is a unit represented by the formula (A-1).

(In formula (A-1), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. Y represents an oxygen atom or a —NR ⁵ — group. R ⁵ represents hydrogen. Represents an atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group, and L ¹ represents a divalent hydrocarbon group.) L ¹ is a divalent linear hydrocarbon group having 1 to 6 methyl, ethyl and carbon atoms may be substituted with a group selected from the group consisting of propyl,, according to claim 7 A composition for forming a layer to be plated. The unit represented by the formula (B) is a unit represented by the formula (B-1) or a unit represented by the formula (B-2). A composition for forming a layer to be plated.

(In formulas (B-1) and (B-2), R ⁴ each independently represents a hydrogen atom or a methyl group. Y represents an oxygen atom or a —NR ⁵ — group. R ⁵ represents Represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group, and L ² may be substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a propyl group. A divalent linear hydrocarbon group having 1 to 6 carbon atoms, an ethylene oxide group, a propylene oxide group, or a divalent hydrocarbon group having 2 to 8 carbon atoms having an ester group, where X is a carboxylic acid group. Represents a sulfonic acid group, a phosphoric acid group, or a salt thereof.