JP2013028772A - Composition for forming layer to be plated, and method for producing laminate including metal layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a layer to be plated, which has satisfactory resistance to an aqueous alkali solution, and a method for producing a laminate including a metal layer excellent in uniformity of plating.SOLUTION: The composition for forming a layer to be plated includes a polymer having a hydrophobic functional group which turns hydrophilic under heat, an acid or radiation, and at least one crosslinkable group selected from the group consisting of a carboxyl group, a hydroxyl group, an isocyanate group, an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group, a primary amino group, a secondary amino group, a tertiary amino group, an epoxy group, an oxetanyl group, a (meth)acrylamide group, an allyl group, a styryl group, a maleimide group and a cinnamoyl group.

Description

  The present invention relates to a composition for forming a layer to be plated, a method for producing a laminate having a metal layer using the composition, and a novel polymer useful for the composition.

2. Description of the Related Art Conventionally, a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
A “subtractive method” is mainly used as a method for manufacturing such a metal wiring board. In this subtractive method, a photosensitive layer that is exposed to actinic rays is provided on a metal layer formed on the surface of the substrate, this photosensitive layer is subjected to pattern exposure, and then developed to form a resist image, In this method, the metal layer 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 layer 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 means for solving this problem, Patent Document 1 discloses that a polymer layer (layer to be plated) having a crosslinkable group and an interactive group is formed on a substrate, and the layer to be plated is treated with an alkaline aqueous solution. Then, a method for plating the layer to be plated is disclosed. According to Patent Document 1, the method can form a metal layer having excellent adhesion between the substrate and the metal layer and having high uniformity of plating without roughening the surface of the substrate. It is disclosed that it can be done.

JP 2010-77509 A

  On the other hand, in recent years, in order to meet the demand for miniaturization and high functionality of electronic devices, wirings are further miniaturized and highly integrated. Accordingly, it has become an important issue to further suppress plating unevenness in the plating process when forming the metal layer. When the metal layer has uneven plating, when forming the fine wiring by patterning the metal layer, it is difficult to obtain a fine wiring having a uniform thickness, and there is a concern that the performance of the printed wiring board itself is deteriorated.

  When the present inventors examined the plating method disclosed in Patent Document 1, the uniformity of the plating layer thickness of the plating layer (metal layer) obtained by this method does not necessarily reach the level required recently. It became clear that it was not.

From the viewpoint of productivity and the like, usually, the plating solution used in the plating process is continuously used for a plurality of layers to be plated. Therefore, when using the plating solution, it is important that the solution stability is maintained for a long time without being contaminated.
On the other hand, when the plating method described in Patent Document 1 was carried out and the liquid stability of the plating solution used at that time was examined, insoluble matter was generated in the plating solution, and the liquid stability was It was not always enough.

  The present inventors have further studied the above-mentioned problems, and the polymer component in the layer to be plated is decomposed and eluted during the alkaline aqueous solution treatment of the layer to be plated. It was found that the liquid stability of the liquid was lowered.

In view of the above circumstances, the present invention has a layer to be plated that has sufficient resistance to an alkaline aqueous solution and that can form a layer to be plated in which plating unevenness and plating solution contamination are suppressed during plating. An object is to provide a forming composition.
Another object of the present invention is to provide a method for producing a laminate having a metal layer with excellent adhesion, in which generation of plating unevenness and contamination of the plating solution are suppressed, using the composition for forming a layer to be plated. And

  As a result of intensive studies on the above problems, the present inventors have improved the resistance to an aqueous alkali solution by using a polymer having a functional group capable of converting hydrophilicity and hydrophobicity and a crosslinkable group having a high resistance to an aqueous alkali solution. The inventors have found that the affinity for the plating catalyst can be ensured, and have completed the present invention.

That is, the present inventors have found that the above problem can be solved by the following configuration.
(1) Functional group that changes from hydrophobic to hydrophilic by heat, acid or radiation, carboxyl group, hydroxyl group, isocyanate group, alkoxysilyl group, acetoxysilyl group, chlorosilyl group, primary amino group, secondary amino group A polymer having at least one crosslinkable group selected from the group consisting of a group, a tertiary amino group, an epoxy group, an oxetanyl group, a (meth) acrylamide group, an allyl group, a styryl group, a maleimide group, and a cinnamoyl group A composition for forming a layer to be plated.

(2) The composition for forming a layer to be plated according to (1), wherein the functional group is a functional group that generates carboxylic acid, sulfonic acid, or sulfinic acid when heated, supplied with acid, or irradiated with radiation.
(3) The composition for forming a plated layer according to (1) or (2), wherein the functional group has a group represented by any one of the following general formulas (1) to (4).
(4) Furthermore, the composition for to-be-plated layer forming in any one of (1)-(3) containing a crosslinking agent.

(5) A laminate having a substrate and a layer to be plated formed on the substrate using the composition for forming a layer to be plated according to any one of (1) to (4).
(6) Step (A) of forming a layer to be plated on the substrate using the composition for forming a layer to be plated according to any one of (1) to (4);
After the step (A), the step (B) for bringing the layer to be plated into contact with the alkaline aqueous solution;
(C) after the step (B), heating, supplying acid or irradiating with radiation to convert the functional group from hydrophobic to hydrophilic;
A step (D) of applying a plating catalyst or a precursor thereof to the layer to be plated after the step (C);
After the step (D), a plating process is performed on the plating layer to which the plating catalyst or its precursor is applied, and a metal layer is formed on the plating layer (E),
The manufacturing method of the laminated body which has a metal layer containing this.

(7) The manufacturing method of the laminated body which has a metal layer as described in (6) further equipped with the process (H) which etches the said metal layer in a pattern shape, and forms a patterned metal layer.
(8) A laminate having a metal layer obtained from the production method according to (6) or (7).
(9) A wiring board comprising the laminate according to (8).
(10) A polymer containing a unit represented by the general formula (D) described later and a unit represented by the general formula (A) described later.

ADVANTAGE OF THE INVENTION According to this invention, the composition for to-be-plated layer formation which can form the to-be-plated layer which has sufficient tolerance with respect to alkaline aqueous solution, and the generation | occurrence | production of plating nonuniformity and the contamination of a plating solution is suppressed in the case of a plating process. Can provide.
Moreover, according to this invention, the manufacturing method of the laminated body which has generation | occurrence | production of plating nonuniformity and the contamination of a plating solution using this composition for to-be-plated layer formation, and which has a metal layer excellent in adhesiveness can be provided.

(A)-(D) are typical sectional drawing which shows each manufacturing process in the 1st embodiment of the manufacturing method of the laminated board of this invention in order, respectively. (A)-(E) are typical sectional drawings which show in order each manufacturing process in the 2nd embodiment of the manufacturing method of the layered product of the present invention, respectively.

Below, the composition for to-be-plated layer formation of this invention and the manufacturing method of the laminated body which has a metal layer are demonstrated.
First, the feature point compared with the prior art of this invention is explained in full detail.

In the present invention, the composition for forming a layer to be plated is a specific functional group (hereinafter also referred to as a polar conversion group) that changes from hydrophobic to hydrophilic by heat, acid or radiation, and a highly resistant to alkaline aqueous solution. It is characterized in that it contains a polymer having a crosslinkable group (hereinafter, also simply referred to as a specific crosslinkable group). Moreover, the manufacturing method of the laminated body which has a metal layer has the characteristics in the point which provided the process of converting the polarity of this functional group after making it contact with alkaline aqueous solution.
As described above, a conventionally known layer to be plated cannot be said to have sufficient resistance to an aqueous alkali solution, and part or most of the polymer in the layer to be plated is decomposed and eluted when brought into contact with the aqueous alkali solution. In addition, if a more hydrophobic layer to be plated is formed in order to increase the resistance to an alkaline aqueous solution, the layer to be plated has a low affinity for a plating catalyst solution or a plating solution and has sufficient adhesion. Can't get a layer.

In contrast, in the present invention, a specific crosslinkable group having high resistance to an aqueous alkali solution is introduced, and when the contact with the aqueous alkali solution is performed, the polarity of the polarity converting group in the layer to be plated is made hydrophobic. In addition, the hydrophobicity of the layer to be plated is increased, and resistance to an alkaline aqueous solution is imparted. After contact with the alkaline aqueous solution, the polarity of the polarity conversion group is changed from hydrophobic to hydrophilic by a predetermined treatment, and the layer to be plated is made more hydrophilic, and the affinity for subsequent plating catalyst solution and plating solution is increased. Increase. As a result, a laminate having a metal layer with little plating unevenness can be obtained while suppressing contamination of the plating solution.
Below, the composition for to-be-plated layer forming is explained in full detail first.

<Composition for plating layer formation>
The composition for forming a layer to be plated contains a polymer having a polarity converting group and a specific crosslinkable group. As will be described later, the layer to be plated formed from the composition changes the hydrophilicity / hydrophobicity of the polarity conversion group from hydrophobic to hydrophilic by heating, supply of acid, or irradiation of radiation, and as a result, the layer to be plated The hydrophilicity / hydrophobicity of the layer also changes from hydrophilic to hydrophobic. That is, the layer to be plated is a wettability changing layer in which the contact angle with water is reduced by heating, acid supply, or irradiation with radiation.
First, the aspect of the polymer contained in the composition will be described in detail, and then the aspect of the composition will be described in detail.

[Polymer having polar conversion group and crosslinkable group]
The polymer has a polarity converting group and a specific crosslinkable group.
First, the polar conversion group will be described in detail, and then the crosslinkable group will be described in detail.

(Polarity conversion group)
The polarity converting group is a functional group that changes from hydrophobic to hydrophilic by heat, acid, or radiation. As the group, a known functional group can be used. However, in terms of being able to further suppress the occurrence of uneven plating and contamination of the plating solution, a carboxylic acid group or sulfone can be obtained by heating, supplying acid, or irradiating with radiation. It is preferably a functional group that generates an acid group or a sulfinic acid group, more preferably a functional group that generates a carboxylic acid group or a sulfonic acid group, and a carboxylic acid group that is superior in adhesion of the metal layer. More preferably, the resulting functional group.
The polar conversion group includes (A) a functional group that changes from hydrophobic to hydrophilic by heat or acid (hereinafter also referred to as polar conversion group A), and (B) from hydrophobic to hydrophilic by radiation (light). Examples thereof include functional groups that change (hereinafter, also referred to as polarity conversion groups B), which will be described in detail below.

(A) Polarity converting group A
Examples of the polarity converting group A include known functional groups described in literatures. For example, alkylsulfonic acid ester groups, disulfone groups, sulfonimide groups (described in JP-A-10-282672), alkoxyalkyl ester groups (described in EP0652483, WO92 / 9934), t-butyl ester groups, other silyl esters And carboxylic acid ester groups protected by acid-decomposable groups described in the literature such as vinyl groups and the like (described in H. Ito et al., Macromolecules, vol. 21, pp. 1477).

  Also, Masahiro Tsunooka, “Surface” vol. 133 (1995), p. 374, an iminosulfonate group described by Masahiro Tsunooka, Polymer preprints, Japan vol. 46 (1997), p. Examples thereof also include β ketone sulfonate esters described in 2045, nitrobenzyl sulfonate compounds described in JP-A No. 63-257750, and functional groups described in JP-A No. 2001-117223.

Among these, a group represented by the general formula (1) (for example, a tertiary carboxylic acid ester group) and a group represented by the general formula (2) (for example, aryl) in that the polarity conversion efficiency is more excellent. Preferably an alkyl ester group), a group represented by the general formula (3) (for example, an alkoxyalkyl ester group), or a group represented by the general formula (4) (for example, a secondary alkyl sulfonate group). It is done. Especially, the group represented by General formula (1) or General formula (2) is more preferable at the point which plating unevenness is suppressed more and adhesion with a metal layer is more excellent, and it represents with General formula (1). More preferred are groups.
Below, each group is explained in full detail.

  As a preferable aspect of the polarity conversion group A, an aspect having a group represented by the following general formula (1) is exemplified. * Indicates a binding position.

In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent an alkyl group that may have a substituent or an aryl group that may have a substituent.
The number of carbon atoms of the alkyl group is preferably 1 to 22 carbon atoms, and more preferably 1 to 8 carbon atoms, from the viewpoint of further suppressing the occurrence of uneven plating and contamination of the plating solution. More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned.
Examples of the aryl group include a carbocyclic aryl group (aromatic hydrocarbon group) and a heterocyclic aryl group (aromatic heterocyclic group). Preferred examples of the carbocyclic aryl group include groups having 6 to 19 carbon atoms (for example, a phenyl group, a naphthyl group, an anthracenyl group, and a pyrenyl group) from the viewpoint that the effects of the present invention are more excellent. Moreover, as a heterocyclic aryl group, in the point which the effect of this invention is more excellent, C3-C20 and heteroatoms 1-5 (for example, the quinolyl group which the benzene ring condensed, pyridyl group, a furyl group, Preferred examples include benzofuryl group, thioxanthone group, and carbazole group.

Two or all of R ₁ , R ₂ and R ₃ may be bonded to form a ring. The type of ring formed is not particularly limited, but an aliphatic hydrocarbon ring is preferable and a 4- to 6-membered ring is particularly preferable in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed.
Furthermore, the ring formed may form a ring via an —O— group, an —S— group, a —CO— group, or a —NR ₄ — group. R ₄ represents a hydrogen atom or an alkyl group (preferably having 8 or less carbon atoms. For example, a methyl group, an ethyl group, a propyl group, etc.).

  When the alkyl group or aryl group has a substituent, the type of the substituent is not particularly limited as long as the effects of the present invention are not impaired. For example, alkyl groups such as methyl and ethyl groups (preferably having 1 to 20 carbon atoms); aryl groups such as phenyl and naphthyl groups (preferably having 6 to 16 carbon atoms); sulfonamide groups and N-sulfonylamides Group, acyloxy group such as acetoxy group (preferably 1 to 6 carbon atoms); alkoxy group such as methoxy group and ethoxy group (preferably 1 to 6 carbon atoms); dimethylamino group, diethylamino group, t-butylamino Alkylamino groups such as groups (preferably having 1 to 8 carbon atoms); halogen atoms such as chlorine and bromine; alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups (preferably having 2 to 2 carbon atoms) 7); cyano group; carbonate group such as t-butyl carbonate.

As a preferred embodiment of R _1, R ₂ and R _3, the efficiency of the polarity conversion is more excellent, in terms of adhesion to the metal layer is more excellent, R ₁ is an alkyl group having 1 to 8 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, R ₃ is an alkyl group having 1 to 8 carbon atoms, a carbocyclic aryl group having 6 to 19 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. 19 carbocyclic aryl groups, 6 to 19 carbocyclic aryl groups having 1 to 6 carbon alkoxy groups, 3 to 20 heterocyclic aryl groups, or alkyl having 1 to 6 carbon atoms The aspect which is a C3-C20 heterocyclic aryl group which has group is mentioned.
R ₂ and R ₃ may be bonded to form a 4- to 6-membered aliphatic hydrocarbon ring.

  As a preferable aspect of the polar conversion group A, an aspect having a group represented by the following general formula (2) is exemplified. * Indicates a binding position.

In General Formula (2), R ₅ and R ₆ represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and at least one of R ₅ and R ₆ Represents an aryl group.
The definition and preferred range of the alkyl group are the same as those of the alkyl group represented by R ₁ , R ₂ and R ₃ described above. Examples of the aryl group include the aryl groups represented by R ₁ , R ₂ , and R ₃ described above. The types of substituents that may be substituted on the alkyl group and aryl group are also as described above.
R ₅ and R ₆ may combine to form a ring. Examples of the ring formed include the rings formed by R ₁ , R ₂ , and R ₃ described above.

As a preferred embodiment of R ₅ and R _6, the efficiency of the polarity conversion is more excellent, in terms of adhesion to the metal layer is more excellent, R ₅ is an alkyl group having 1 to 8 carbon atoms, carbon atoms 6 to 19 A carbocyclic aryl group, a C6-C19 carbocyclic aryl group having a C1-C6 alkyl group, a C6-C19 carbocyclic aryl group having a C1-C6 alkoxy group , A heterocyclic aryl group having 3 to 20 carbon atoms, or a heterocyclic aryl group having 3 to 20 carbon atoms having an alkyl group having 1 to 6 carbon atoms, and R ₆ is a carbocyclic ring having ₆ to 19 carbon atoms. C6-C19 carbocyclic aryl group having a C1-C6 alkyl group, C6-C19 carbocyclic aryl group having a C1-C6 alkoxy group, carbon number 3-20 heterocyclic aryl group or alkyl having 1 to 6 carbon atoms Aspect is a heterocyclic aryl group having 3 to 20 carbon atoms having the like.
R ₅ and R ₆ may be bonded to form a 4- to 6-membered aliphatic hydrocarbon ring.

  As a preferable aspect of the polarity conversion group A, an aspect having a group represented by the following general formula (3) is exemplified. * Indicates a binding position.

In General Formula (3), R ₇ represents a hydrogen atom or an alkyl group which may have a substituent. The definition and preferred range of the alkyl group are the same as those of the alkyl group represented by R ₁ , R ₂ and R ₃ described above. The types of substituents that may be substituted on the alkyl group are also as described above.
R ₈ represents an alkyl group which may have a substituent. The definition and preferred range of the alkyl group are the same as those of the alkyl group represented by R ₁ , R ₂ and R ₃ described above. The types of substituents that may be substituted on the alkyl group are also as described above.
R ₇ and R ₈ may combine to form a ring. Examples of the ring formed include the rings formed by R ₁ , R ₂ , and R ₃ described above.

A preferred embodiment of R ₇ and R ₈ is an alkyl group substituted with an electron-withdrawing group such as an alkoxy group, an alkoxycarbonyl group, or a halogen group in view of better stability over time and alkali resistance. preferable.
Further, as other preferred embodiments of R ₇ and R ₈ , R ₇ is an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 6 carbon atoms, or 2 to 7 carbon atoms. Or an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms having a halogen group, and R ₈ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. And an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms having an alkoxycarbonyl group having 2 to 7 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having a halogen group. .
R ₇ and R ₈ may combine to form a 4- to 6-membered aliphatic hydrocarbon ring.

  As a preferable aspect of the polar conversion group A, an aspect having a group represented by the following general formula (4) is exemplified. * Indicates a binding position.

In general formula (4), R ₉ and R ₁₀ represent an alkyl group which may have a substituent or an aryl group which may have a substituent. As an alkyl group, C1-C25 is preferable and the C1-C8 is more preferable at the point which the effect of this invention is more excellent. More specifically, a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a cyclohexyl group can be mentioned.
Examples of the aryl group include the aryl groups represented by R ₁ , R ₂ , and R ₃ described above.

R ₉ and R ₁₀ may combine to form a ring. Examples of the ring formed include the rings formed by R ₁ , R ₂ , and R ₃ described above.

When the alkyl group or aryl group has a substituent, the type of the substituent is not particularly limited as long as the effects of the present invention are not impaired. For example, the alkyl represented by the above-described R ₁ , R ₂ , and R ₃ Examples include a substituent substituted with a group or an aryl group.

As a preferable embodiment of R ₉ and R ₁₀ , an alkyl group substituted with an electron-withdrawing group such as an alkoxy group, a carbonyl group, an alkoxycarbonyl group, a cyano group, a halogen group, or a cyclohexyl group is preferable in terms of stability over time. A cyclic alkyl group such as a norbornyl group is particularly preferable. As a physical property value, a compound in which the chemical shift of secondary methine hydrogen in proton NMR in a deuterated chloroform appears in a magnetic field lower than 4.4 ppm is preferable, and a compound that appears in a magnetic field lower than 4.6 ppm is more preferable. Thus, an alkyl group substituted with an electron-withdrawing group is particularly preferred because the carbocation that appears to be formed as an intermediate during the thermal decomposition reaction is destabilized by the electron-withdrawing group and decomposition is suppressed. This is considered to be because of this. Specifically, the structure represented by the following formula is particularly preferable as the structure of —CHR ₉ R ₁₀ .

In addition, the polarity conversion group may have groups other than the group represented by any of the general formulas (1) to (4) described above. For example, a linking group -L- may be further bonded to * in the general formulas (1) to (4).
The linking group is not particularly limited, and examples thereof include a divalent to tetravalent linking group. For example, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Examples include groups consisting of atoms. More specific examples of the linking group include the following structural units and groups constituted by combining them.
In addition, these coupling groups may have a substituent. The type of the substituent is not particularly limited, and examples thereof include a substituent substituted with the alkyl group or aryl group represented by R ₁ , R ₂ , and R ₃ described above.

(B) Polarity converting group Y
As the polarity conversion group Y, a known functional group can be used. For example, a functional group whose hydrophilicity / hydrophobicity is changed by irradiation with light of 700 nm or less can be used. In this way, functional groups that undergo polarity conversion upon irradiation with light of 700 nm or less can directly undergo decomposition, ring opening, or dimerization reaction upon irradiation with light of a predetermined wavelength, regardless of long-wavelength exposure such as infrared rays or heat. And, it is characterized by high sensitivity and a change in hydrophobicity from hydrophobicity.
As the functional group, for example, functional groups represented by general formulas (a) to (i) described in JP-A No. 2004-175098 can be used.

  Specific examples of the polarity converting group are shown below.

(Crosslinkable group)
The crosslinkable group contained in the polymer is a crosslinkable group highly resistant to an alkaline aqueous solution described later. Specifically, a carboxyl group (—COOH), a hydroxyl group, an isocyanate group, an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group. Group, primary amino group (—NH ₂ ), secondary amino group (—NHR _a , where R _a represents a substituent (preferably a hydrocarbon group)), tertiary amino group (—NR _b R) _c , wherein R _b and R _c represent a substituent (preferably a hydrocarbon group)), an epoxy group, an oxetanyl group, a (meth) acrylamide group, an allyl group, a styryl group, a maleimide group, and a cinnamoyl group. Is at least one selected from the group consisting of By having these crosslinkable groups, a to-be-plated layer having high resistance to an alkaline aqueous solution can be obtained, and plating unevenness and plating solution contamination during plating are suppressed.
Among these, an epoxy group, an oxetanyl group, a hydroxyl group, or an alkoxysilyl group is preferable in that the occurrence of uneven plating can be further suppressed.

The alkoxysilyl group is a silyl group having an alkoxy group. In other words, it means a group in which an alkoxy group is bonded to a silicon atom (—Si—OR _d (R _d : alkyl group), specifically, a trialkoxysilyl group, an alkyldialkoxysilyl group, etc. A silyl group means a group in which an acetoxy group is bonded to a silicon atom, and a chlorosilyl group means a group in which a chlorine atom is bonded to a silicon atom.

  In addition, when an acryloyloxy group or a methacryloyloxy group is used as the crosslinkable group, a plating layer having low resistance to an alkaline aqueous solution is formed, and as a result, generation of plating unevenness and contamination of the plating solution proceed.

  The type of the skeleton of the polymer having the polar functional group and the crosslinkable group is not particularly limited. For example, polyimide resin, epoxy resin, urethane resin, polyethylene resin, polyester resin, urethane resin, novolac resin, cresol resin, acrylic resin, A methacrylic resin, a styrene resin, etc. are mentioned. Of these, acrylic resins and methacrylic resins are preferable in terms of availability of materials and film formability.

(Preferred embodiment of polymer having polar conversion group and specific crosslinkable group)
As a suitable aspect of the polymer which has a polar conversion group and a specific crosslinkable group, the polymer containing the unit represented by the following general formula (A) is mentioned as a unit which has a polar conversion group. When the polymer has a unit represented by the general formula (A), the occurrence of uneven plating and contamination of the plating solution can be further suppressed.

In general formula (A), R ₁₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group and an ethyl group.
In general formula (A), L ₁ represents a single bond or a divalent organic group. As the divalent organic group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, for example, a phenylene group), —O—, —S—, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like) can be given. Especially, a single bond and an aromatic hydrocarbon group are preferable at the point which the effect of this invention is more excellent.

  In general formula (A), Y represents the polar conversion group mentioned above. Especially, it is preferable that it is group represented by either of General formula (1)-(4) at the point which can suppress generation | occurrence | production of plating nonuniformity and contamination of a plating solution more.

  As one of the preferred embodiments of the unit represented by the general formula (A), there is a unit represented by the following general formula (A-1) in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. Can be mentioned.

In general formula (A-1), the definitions of R ₁₁ and Y are as described above.
L ₂ represents a single bond, an amide group (—CONH—), an ester group, or a phenylene group. L ₃ represents a single bond or an aliphatic hydrocarbon group. When L ₂ is an amide group or an ester group, L ₃ represents an aliphatic hydrocarbon group.

  The content of the unit represented by the general formula (A) in the polymer (or the unit represented by the general formula (A-1)) is not particularly limited, but it further suppresses the occurrence of uneven plating and contamination of the plating solution. In the point which can do, 10-95 mol% is preferable in all polymer units, and 55-90 mol% is more preferable.

  As another suitable aspect of the polymer which has a polar conversion group and a specific crosslinkable group, the polymer containing the unit represented by the following general formula (B) is mentioned as a unit which has a crosslinkable group. When the polymer has a unit represented by the general formula (B), the occurrence of uneven plating and contamination of the plating solution can be further suppressed.

In the general formula (B), R ₁₂ is a hydrogen atom or, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group and an ethyl group.
In the general formula (B), L ₄ represents a single bond or a divalent organic group. Definition of the organic groups are the same as those defined organic group represented by L _1.
In general formula (B), Z is a carboxyl group, hydroxyl group, isocyanate group, alkoxysilyl group, acetoxysilyl group, chlorosilyl group, primary amino group, secondary amino group, tertiary amino group, epoxy group, oxetanyl group. , An allyl group, a styryl group, a maleimide group, a cinnamoyl group, or a group represented by the general formula (C).

In general formula (C), R < ₁₃ > -R < ₁₅ > represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group each independently. Examples of the alkyl group include a methyl group and an ethyl group.

In the general formula (C), R ₁₆ is a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an alkenyl group (preferably having 1 to 8 carbon atoms), an alkynyl group (preferably having 1 to 8 carbon atoms), Or represents an aryl group. Especially, an alkyl group and an aryl group are more preferable at the point which the effect of this invention is more excellent.

  As a preferred embodiment of the unit represented by the general formula (B), there is a unit represented by the following general formula (B-1) in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. Can be mentioned.

In general formula (B-1), the definitions of R ₁₂ and Z are as described above.
L ₅ represents a single bond, an amide group, an ester group, or a phenyl group. L ₆ represents a single bond or an aliphatic hydrocarbon group which may be interposed via a —O—, —COO— or —CONH— bond. When Z is a carboxyl group, L ₅ and L ₆ may both be single bonds.

  The method for synthesizing the polymer having a polar conversion group and a crosslinkable group is not particularly limited, and a known method (for example, radical polymerization, cationic polymerization, etc.) can be used. For example, a method of copolymerizing a monomer having a polarity converting group and a monomer having a crosslinkable group can be mentioned. Examples of the monomer having a crosslinkable group used include the following monomers.

Examples of the monomer having a crosslinkable group used include the following monomers.

  Further, when an ethylene addition polymerizable unsaturated group is used as the crosslinkable group, for example, a polymer can be synthesized with reference to a method described in JP 2009-007540 A.

  A preferred embodiment of the polymer having a polar converting group and a crosslinkable group includes a polymer synthesized by copolymerizing the monomer having the polar converting group and the monomer having the crosslinkable group. Specific examples are shown below, but are not limited to these polymers. In addition, the numerical value written together by the repeating unit in the polymer shown below shows mol% of each unit.

  Although content of the said 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.

(solvent)
The composition for forming a layer to be plated may contain a solvent, if necessary.
Examples of solvents that can be used include alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether; acids such as acetic acid; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; formamide and dimethyl Amide solvents such as acetamide and N-methylpyrrolidone; Nitrile solvents such as acetonitrile and propionitrile; Ester solvents such as methyl acetate, ethyl acetate and propylene glycol monomethyl ether acetate; Carbonates such as dimethyl carbonate and diethyl carbonate A solvent is mentioned.
A solvent having a boiling point of 50 ° C. to 150 ° C. is preferred for ease of handling. In addition, these solvents may be used alone or in combination.

(Crosslinking agent)
The composition for forming a layer to be plated may contain a cross-linking agent having a reactive functional group that reacts with the cross-linkable group described above, if necessary. By including the cross-linking agent, a chemical bond is formed with the cross-linkable group in the above-described polymer, and the resistance of the plated layer to the alkaline aqueous solution is further improved.

As the crosslinking agent to be used, those conventionally known as described in Shinji Yamashita “Crosslinking agent handbook” can be used.
More specifically, the crosslinking agent usually has two or more reactive functional groups that react with the crosslinkable group, and preferably has 2 to 6 reactive functional groups.
Examples of the reactive functional group include a hydroxyl group, an isocyanate group, a carboxylic acid group, an epoxy group, a carboxylic anhydride group, a primary amino group, a secondary amino group, an alkoxysilyl group, and a benzyl halide group.

  As a preferable combination of the crosslinkable group in the polymer and the reactive functional group in the crosslinking agent, for example, (crosslinkable group, reactive functional group) = (carboxyl group, primary or secondary amino group), (carboxyl group) , Aziridine group), (carboxyl group, isocyanate group), (carboxyl group, epoxy group), (carboxyl group, halogenated benzyl group), (primary or secondary amino group, isocyanate group), (primary, secondary, or Tertiary amino group, halogenated benzyl group), (primary amino group, aldehydes), (isocyanate group, primary or secondary amino group), (isocyanate group, isocyanate group), (isocyanate group, hydroxyl group), (isocyanate group) , Epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl group), (hydroxyl group, cal group) Acid anhydride group), (hydroxyl group, epoxy group), (hydroxyl group, alkoxysilyl group), (epoxy group, primary or secondary amino group), (epoxy group, carboxylic acid anhydride group), (epoxy group, hydroxyl group) ), (Epoxy group, epoxy group), (oxetanyl group, epoxy group), (alkoxysilyl group, alkoxysilyl group) and the like. Among these, (crosslinkable group, reactive functional group) = (epoxy group, amino group), (epoxy group, epoxy group), (tertiary amino group) in terms of suppressing the occurrence of uneven plating and contamination of the plating solution. Group, halogenated benzyl group), (hydroxyl group, isocyanate group), (oxetanyl group, epoxy group), and (alkoxysilyl group, alkoxysilyl group) are more preferable combinations.

  Examples of the crosslinking agent used include the following crosslinking agents.

  As a usage-amount of the crosslinking agent in the composition for to-be-plated layer forming, 0.01-50 equivalent is normally preferable with respect to the number-of-moles of a crosslinkable group, 0.01-10 equivalent is more preferable, and 0.0. 5 to 3 equivalents are more preferable. When the usage-amount of a crosslinking agent is in the said range, it will become easy to osmose | permeate the plating catalyst liquid mentioned later and a plating solution.

(Photoacid generator)
The composition for forming a layer to be plated may contain a photoacid generator, if necessary. When a photoacid generator is contained in the composition for forming a layer to be plated, an acid can be supplied into the layer to be plated by light irradiation in the step (C) described later.

  As the photoacid generator to be used, known compounds (for example, a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, etc.) can be used. Examples thereof include onium salt compounds such as iodonium salts and sulfonium salts.

  Although content in particular of the photo-acid generator in the composition for to-be-plated layer forming is not restrict | limited, About 0.001-40 mass% is preferable with respect to the total solid of a composition, 0.01-20 mass% Is more preferable, and 0.1-5 mass% is further more preferable. If it is in the said range, in the process (C) mentioned later, the polarity conversion of a functional group will progress more efficiently.

(Other optional ingredients)
In addition to the components described above, the composition for forming a layer to be plated includes a surfactant, a plasticizer, a polymerization inhibitor, a polymerization initiator for proceeding with curing, a curing accelerator, and a rubber component (for example, CTBN). ), Flame retardants (for example, phosphorus flame retardants), diluents, thixotropic agents, pigments, antifoaming agents, leveling agents, coupling agents and the like.
In addition, the composition for forming a layer to be plated has a polymerizable group and a catalyst adsorbing group described in JP2009-7540A or JP2010-248464A as long as the effects of the present invention are not impaired. It may contain a polymer.

<The 1st embodiment of the manufacturing method of a layered product>
The first embodiment of the laminate manufacturing method of the present invention includes a step (A) of forming a layer to be plated on the surface of the substrate, a step (B) of bringing the layer to be plated into contact with an alkaline aqueous solution, Performing a treatment to convert a functional group in the layer to be plated from hydrophobic to hydrophilic (C), applying a plating catalyst or a precursor thereof to the layer to be plated (D), and performing a plating treatment And a step (E).
Hereinafter, materials used in each step and the procedure thereof will be described in detail with reference to the drawings. First, the step (A) will be described in detail.

<Step (A): Plated layer forming step>
A process (A) is a process of forming a to-be-plated layer on the surface of a board | substrate using the said composition for to-be-plated layer forming. By performing this step, a layer to be plated to which a plating catalyst or the like to be described later is applied is formed.
More specifically, in this step, a substrate 10 is prepared as shown in FIG. 1A, and a layer 12 to be plated is formed on the surface of the substrate 10 as shown in FIG.

As will be described later, the layer to be plated formed in this step changes the hydrophilicity / hydrophobicity of the polarity conversion group from hydrophobic to hydrophilic by heating, supply of acid, or irradiation of radiation. The hydrophilicity / hydrophobicity of is also changed to more hydrophilic. That is, it preferably changes from a hydrophobic plated layer to a hydrophilic plated layer. As will be described later, since the layer to be plated exhibits hydrophilicity after contact with an alkaline aqueous solution, it efficiently adsorbs a plating catalyst or a precursor thereof described later. That is, the layer to be plated functions as a good receiving layer for the plating catalyst (or its precursor). As a result, excellent adhesion with the metal layer formed on the surface of the layer to be plated can be obtained.
In the following, first, materials (such as a substrate) used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(substrate)
The substrate is a member for supporting each layer described below, and any conventionally known substrate (for example, a resin substrate, a ceramic substrate, a glass substrate, a metal substrate, etc., preferably an insulating substrate) is used. be able to. More specifically, metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene) , Polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide, epoxy resin, and the like), and plastic films on which the above metal is laminated or vapor-deposited.

Moreover, the board | substrate may have metal wiring in the inside or one side or both surfaces. The metal wiring may be formed in a pattern with respect to the surface of the substrate or may be formed on the entire surface. Typically, those formed by a subtractive method using an etching process and those formed by a semi-additive method using electrolytic plating may be used, and those formed by any method may be used.
Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, and gallium.

(Procedure of step (A))
The method for forming the layer to be plated on the substrate is not particularly limited, and a known method can be adopted. For example, a method for forming a layer to be plated (coating method) by applying a composition for forming a layer to be plated on the substrate, and a film of the layer to be plated formed from the composition for forming a layer to be plated directly on the substrate The method of laminating etc. is mentioned. Especially, the coating method is preferable from the point that the film thickness control of a to-be-plated layer is easy.
Hereinafter, the aspect of the coating method will be described in detail.

The method for applying the composition for forming a layer to be plated on the substrate is not particularly limited, and a known method (for example, spin coating, dip coating, double roll coater, slit coater, air knife coater, wire bar coater, etc.) should be used. Can do.
From the viewpoint of handleability and production efficiency, an embodiment in which the composition for forming a layer to be plated is applied on a substrate, and if necessary, is subjected to a drying treatment to remove the contained solvent to form a layer to be plated. .

Although the thickness of a to-be-plated layer is not restrict | limited in particular, 0.02-5.0 micrometers is preferable from the point which the adhesiveness of a metal layer is more excellent, and 0.05-2.0 micrometers is more preferable.
The content of the polymer in the layer to be plated is not particularly limited, but is preferably 10 to 100% by mass, and 50 to 100% by mass with respect to the total amount of the layer to be plated, because the adhesion of the metal layer is more excellent. It is more preferable that

(Preferred embodiment of the layer to be plated)
As a process aspect of a to-be-plated layer, it is preferable to perform a hardening process with respect to the to-be-plated layer mentioned above (process (G)). In other words, the layer to be plated is preferably a layer obtained by curing a polymer having a polarity converting group and a crosslinkable group by a crosslinking reaction. In the case of this mode, the curing of the layer proceeds via the crosslinkable group, the film strength of the layer to be plated itself is increased, the hydrophobicity is also increased, and the resistance to the aqueous alkali solution is improved.
Hereinafter, the aspect of the step (G) will be described in detail.

It is preferable to implement a hardening process (process (G)) after this process (A), and before the process (D) mentioned later. More specifically, it is between step (A) and step (B), between step (B) and step (C), or between step (C) and step (D). By carrying out before the step (D), it is possible to increase the resistance of the plating layer to the plating catalyst solution used in the step (D) and the plating solution used in the step (E).
In addition, it is preferable to implement a process (G) between a process (A) and a process (B) at the point which can suppress the elution and decomposition | disassembly of the to-be-plated layer in another process.

  As the method for crosslinking the polymer in the step (G), an optimal method is appropriately selected depending on the type of the crosslinkable group in the polymer. Examples thereof include a method of reacting crosslinkable groups with each other and a method of using a crosslinking agent. .

  The method of reacting crosslinkable groups is a method of forming a crosslinked structure in the layer to be plated through an addition reaction or a condensation reaction between the crosslinkable groups. For example, when the crosslinkable group is -NCO, the self-condensation reaction can be advanced by applying heat to form a crosslinked structure in the layer to be plated.

  A method using a crosslinking agent is a method in which a crosslinkable group in a polymer is reacted with a reactive functional group of a crosslinker having a reactive functional group that reacts with the above-described crosslinkable group. It is a method of forming.

The type of curing treatment varies depending on the type of polymer used and the crosslinking agent, and an optimum treatment method is appropriately selected. Usually, heat treatment or exposure treatment is carried out.
When performing the heat treatment, the heating temperature is preferably from 50 to 200 ° C, more preferably from 80 to 150 ° C, from the viewpoints of suppression of decomposition of the polarity conversion group, productivity, and the like. As processing time, 2 to 60 minutes are preferable and 5 to 30 minutes are more preferable.
When performing the exposure process, the type of light to be irradiated is not particularly limited, but ultraviolet light or visible light is preferably used. The irradiation energy is preferably from 100 to 10,000 mJ, more preferably from 500 to 5000 mJ, from the viewpoint of productivity.

<Process (B): Alkaline aqueous solution contact process>
A process (B) is a process of making a to-be-plated layer and alkaline aqueous solution contact after the said process (A). By carrying out this step, the organic adsorbate on the layer to be plated is removed, and as a result, the uniformity of plating is improved. Moreover, the penetration of the plating catalyst described later is promoted by increasing the wettability of the layer to be plated.
Below, the material (alkali aqueous solution etc.) used at this process is explained in full detail first, and the procedure of the post process is explained in full detail.

(Alkaline aqueous solution)
The type of the aqueous alkali solution used in the step (B) is not particularly limited as long as the pH is alkaline.
The pH of the alkaline aqueous solution is preferably 10 to 14, and more preferably 12 to 14 in terms of suppressing the occurrence of uneven plating and contamination of the plating solution.

  As the solvent used for the alkaline aqueous solution, water is usually used. If necessary, organic solvents (alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, hydroxyacetic acid and aminocarboxylic acid, ketones such as acetone and methyl ethyl ketone) Solvents, amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propyronitrile, carbonate solvents such as dimethyl carbonate and diethyl carbonate, glycol solvents, etc.) may be used in combination. .

The type of the alkaline aqueous solution is not particularly limited, and examples thereof include a lithium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a lithium carbonate aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a lithium hydrogen carbonate aqueous solution, and a sodium hydrogen carbonate aqueous solution. Examples include aqueous solutions, potassium hydrogen carbonate aqueous solutions, calcium hydroxide aqueous solutions, strontium hydroxide aqueous solutions, barium hydroxide aqueous solutions, calcium carbonate aqueous solutions, strontium carbonate aqueous solutions, and barium carbonate aqueous solutions.
The content of the alkali component (inorganic base) is preferably adjusted to a range where the pH is in the above range.

  A surfactant may be added to the alkaline aqueous solution. The type of the surfactant used is not particularly limited, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

  More specifically, examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N- Examples include acylamino acid type surfactants, alkyl or alkenyl phosphate esters and salts thereof.

  Nonionic surfactants include, for example, polyoxyalkylene alkyls or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, Examples include alkylamine oxide.

  Examples of the cationic surfactant include alkyl cationic surfactants, amide type quaternary cationic surfactants, ester type quaternary cationic surfactants, and the like. Examples of amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants.

(Procedure of step (B))
The contact method of a to-be-plated layer and aqueous alkali solution is not restrict | limited, A well-known method is used. For example, a method of applying an alkaline aqueous solution on the layer to be plated (spray coating, spin coating, printing method, etc.), a method of immersing a substrate having a layer to be plated in an alkaline aqueous solution (dip immersion), etc. Dip dipping and spray coating are preferred because of their simplicity and ease of adjusting the processing time.

Although the liquid temperature of the aqueous alkali solution at the time of contact is not particularly limited, the range of 30 ° C. to 90 ° C. is preferable and the range of 50 ° C. to 70 ° C. is more preferable in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. preferable.
The contact time between the layer to be plated and the aqueous alkali solution is preferably in the range of 5 seconds to 30 minutes, more preferably in the range of 30 seconds to 25 minutes, in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. A range of ˜20 minutes is more preferred.
Moreover, it is preferable to wash | clean the alkaline aqueous solution adhering to the to-be-plated layer with a pure water after a contact with alkaline aqueous solution at the point which can suppress generation | occurrence | production of plating unevenness and plating solution contamination.

<Process (C): Polarity conversion process>
Step (C) is a step of converting the polarity conversion group from hydrophobic to hydrophilic by performing heating, acid supply, or irradiation with radiation after the step (B). More specifically, by performing the treatment, the contact angle with the water of the layer to be plated after the treatment is lower than the contact angle with the water of the layer to be plated before the treatment. That is, the treatment changes the hydrophilicity / hydrophobicity of the layer to be plated so that the contact angle with water decreases.
By carrying out this step, the layer to be plated is converted from hydrophobic to hydrophilic, and the affinity for the plating catalyst or its precursor is improved. Moreover, the permeability | transmittance of the plating catalyst liquid used at the catalyst provision process mentioned later and the plating liquid used at a plating process improves, As a result, the adhesiveness of a metal layer improves.
The treatment performed in this step is appropriately performed appropriately depending on the type of polarity conversion group in the layer to be plated. Below, each procedure is explained in full detail.
In addition, you may implement the following polarity conversion processes in a pattern form as needed. That is, the pattern of the hydrophilic region and the hydrophobic region may be formed on the surface of the layer to be plated by performing imagewise heating, acid supply, or irradiation with radiation.

(Heat treatment)
The conditions for the heat treatment are not particularly limited, but the heating temperature is preferably from 100 to 250 ° C, more preferably from 150 to 200 ° C, from the viewpoint of the heat resistance of the layer to be plated and the good polarity conversion efficiency of the polarity conversion group. The heating time is preferably 1 minute to 1 hour, more preferably 5 minutes to 30 minutes from the viewpoint of productivity and good polarity conversion efficiency of the polarity conversion group.
In addition, as an apparatus used in the case of heat processing, a well-known apparatus (For example, a ventilation dryer, oven, an infrared dryer, a heating drum etc.) can be used.

(Acid supply treatment)
The method for supplying the acid is not particularly limited. For example, the method in which the layer to be plated is brought into contact with an acidic solution, the photoacid generator is contained in the layer to be plated, and the photoacid generator is heated or exposed to light. The method of generating an acid is mentioned.

In the case of using an acidic solution, the pH of the acidic solution is not particularly limited, but is preferably 3 or less, more preferably 1 or less, from the viewpoint of good polarity conversion efficiency of the polarity conversion group.
The kind of the acidic component in the acidic solution is not particularly limited, and known acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, paratoluenesulfonic acid, methanesulfonic acid, and trifluoroacetic acid can be used.
The content of the acid in the acidic solution is preferably about 5 to 50% by mass and more preferably 10 to 40% by mass from the viewpoint of good polarity conversion efficiency of the polar conversion group.
In addition, the type of the solvent in the acidic solution is not particularly limited, and for example, water or an organic solvent is used.

The method for bringing the acidic solution into contact with the layer to be plated is not particularly limited, and examples thereof include a method of applying the acidic solution on the layer to be plated and a method of immersing a substrate having the layer to be plated in the acidic solution.
The contact time between the acidic solution and the layer to be plated is not particularly limited, but is preferably 1 minute to 1 hour and more preferably 5 minutes to 30 minutes from the viewpoint of productivity and good polarity conversion efficiency of the polarity conversion group.
Although the liquid temperature of the acidic solution at the time of a contact is not restrict | limited in particular, 30-95 degreeC is preferable and 40-90 degreeC is more preferable from the point of productivity and the favorable polarity conversion efficiency of a polarity conversion group.

When using a photoacid generator, the photoacid generator used is a known compound (for example, a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, etc.). Can be used.
About 0.001-40 mass% is preferable with respect to the total solid of a to-be-plated layer, and, as for content of the photo-acid generator in a to-be-plated layer, 0.01-20 mass% is more preferable, 0.1 -5 mass% is further more preferable.
The method for supplying the photoacid generator into the layer to be plated is not particularly limited, and examples thereof include a method of forming the layer to be plated by adding the photoacid generator to the above-described composition for forming a layer to be plated.

In addition, although the method in particular of generating an acid from the photo-acid generator in a to-be-plated layer is not restrict | limited, Usually, it is performed by heat processing or exposure processing.
As the conditions for the heat treatment, the above-mentioned conditions are preferably exemplified. Moreover, the conditions for the exposure process include conditions for a radiation irradiation process described later.

(Radiation irradiation treatment)
The type of radiation used is not particularly limited, and radiation in the optimum wavelength range is used according to the type of polarity conversion group. Especially, it is preferable to use ultraviolet light or visible light from the point which performs the polarity conversion of a polarity conversion group more efficiently.
The irradiation time varies depending on the reactivity of the polar conversion group and the type of the light source, but is preferably 10 seconds to 5 hours from the viewpoint of productivity. The exposure energy is preferably about 10 to 8000 mJ, more preferably 100 to 3000 mJ.

  In addition, the said heating, supply of an acid, and a radiation irradiation process may implement 2 or more processes by a process (C).

It is preferable that the hydrophilicity / hydrophobicity of the polarity conversion group in the layer to be plated is changed by performing the above-described treatment, and as a result, the hydrophilicity / hydrophobicity of the layer to be plated is changed from hydrophilic to hydrophobic. That is, it preferably changes from a hydrophilic plated layer to a hydrophobic plated layer.
Usually, the to-be-plated layer before polarity conversion shows hydrophobicity, and the water contact angle is preferably 70 ° or more, more preferably 80 ° or more from the viewpoint of better resistance to an aqueous alkali solution. The upper limit is not particularly limited, but is usually 120 ° or less.
On the other hand, the layer to be plated after polarity conversion usually exhibits hydrophilicity, and the water contact angle is preferably less than 70 °, more preferably 50 ° or less, from the viewpoint of better affinity for the plating catalyst and the like.
When the converted polarity conversion group is a carboxylic acid group, a sulfonic acid group, or a sulfinic acid group, the layer to be plated after the polarity conversion contains these acid groups when an alkaline plating solution is used. By being salted to form a salt, the hydrophilicity is further increased and the penetration of the plating solution can be further promoted.

In the present specification, a layer to be plated having a water contact angle of 70 ° or more is referred to as a hydrophobic layer and a layer to be plated that is less than 70 ° is referred to as a hydrophilic layer.
As a method for measuring the water contact angle, a tangential method using two points of contact between the top of the dropped water and the substrate is used.

<Step (D): catalyst application step>
A process (D) is a process of providing a plating catalyst or its precursor to the to-be-plated layer obtained at the process (C).
In this step, a plating catalyst or a precursor thereof is applied to a layer to be plated that exhibits hydrophilicity (hydrophilic layer to be plated). In particular, when the polar conversion group converted to hydrophilicity is a carboxylic acid group, a sulfonic acid group, or a sulfinic acid group, the plating catalyst or precursor thereof to which these groups are attached is efficiently attached (adsorbed).
First, materials (plating catalyst or its precursor etc.) used at this process are explained in full detail, and the procedure of this process is explained in full detail after that.

(Plating catalyst or its precursor)
The plating catalyst or its precursor functions as a catalyst or electrode for plating treatment in the plating step described later. Therefore, the type of plating catalyst or precursor used is appropriately determined depending on the type of plating treatment.
In addition, it is preferable that the plating catalyst used or its precursor is an electroless plating catalyst or its precursor from the point which improves the uniformity of plating.
Hereinafter, electroless plating or a precursor thereof will be described in detail.

As the electroless plating catalyst, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal having a catalytic ability for autocatalytic reduction reaction (which tends to be more ionized than Ni). And those known as metals capable of low electroless plating). More specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, etc. are mentioned. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
As the electroless plating catalyst, metal colloid (metal particles) may be used. Generally, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent.

  Any electroless plating catalyst precursor can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the metals mentioned as the electroless plating catalyst are mainly used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is an electroless plating catalyst precursor may be used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating solution, by separately changing to a zero-valent metal by a reduction reaction. The electroless plating catalyst precursor may be immersed in an electroless plating solution and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating solution.

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. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. In view of the number of types of groups and catalytic ability, Ag ions and Pd ions are preferred.

  In this step, zero-valent metals other than those described above can also be used as a catalyst used for direct electroplating without electroless plating.

The plating catalyst or a precursor thereof is preferably used in the form of a solution in which these are dispersed or dissolved in a solvent (hereinafter also referred to as a plating catalyst solution as appropriate). That is, the plating catalyst solution contains a plating catalyst or a precursor thereof.
The plating catalyst solution usually contains a solvent, and an organic solvent and / or water is used as the type of solvent. Usually, water is used as the main component. When the plating catalyst liquid contains an organic solvent, the permeability of the plating catalyst liquid to the layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the layer to be plated.

  The organic solvent used in the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the plating layer. Specifically, 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, and the like can be used.

(Procedure of step (D))
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 containing a plating catalyst or a precursor thereof (a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing a dissociated metal ion in which a metal salt is dissolved in an appropriate solvent) is prepared. And a method of applying a plating catalyst solution on the layer to be plated, or a method of immersing a substrate on which the layer to be plated is formed in the plating catalyst solution.
The contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 10 minutes, and more preferably about 3 minutes to 5 minutes.
The temperature of the plating catalyst solution at the time of contact is preferably about 20 to 60 ° C, and more preferably about 30 to 50 ° C.

<Process (E): Plating process>
The step (E) is a step of forming a metal layer (plating layer) on the layer to be plated by performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied in the step (D). is there. More specifically, by performing this step, as shown in FIG. 1C, the metal layer 14 is provided on the layer 12 to be plated, and the laminate 16 is obtained.

Examples of the plating treatment performed in this step include electroless plating and electrolytic plating. In the above step, the plating treatment can be selected depending on the function of the plating catalyst applied to the layer to be plated or its precursor.
Especially, it is preferable to perform electroless plating from the point of the adhesive improvement of the metal layer formed. Further, in order to obtain a metal layer having a desired layer thickness, it is a more preferable aspect that electrolytic plating is further performed after electroless plating.
Hereinafter, the plating suitably performed in this process will be described.

(Electroless plating)
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
In the electroless plating in this step, for example, the substrate to which the electroless plating catalyst has been applied is washed with water to remove excess electroless plating catalyst (metal) from the layer to be plated, and then immersed in an electroless plating bath. Do. 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 the electroless plating bath, the substrate is washed with water to remove excess precursor (metal salt, etc.), and then in the electroless plating bath. Soak in. 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, known reducing agents (for example, boron-based reducing agents such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphorous acid, etc.) can be used.
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, for example, in addition to a solvent (for example, water), 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, rhodium are known, and from the viewpoint of conductivity, copper and gold are among others. Particularly preferred. Moreover, the optimal reducing agent and additive are selected according to the said metal.

The thickness of the metal layer obtained 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, but from the viewpoint of conductivity, it is 0. .1 μm or more is preferable, and 0.2 to 2 μm is more preferable.
However, when performing electroplating to be described later using a metal layer formed by electroless plating as a conductive layer, it is preferable that a layer 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.
Moreover, after the above-mentioned electroless plating, the formed metal layer may be used as an electrode, and electrolytic plating may be further performed. Thereby, a new metal layer having an arbitrary thickness can be easily formed on the electroless plating layer having excellent adhesion to the substrate. As described above, by performing electroplating after electroless plating, the metal layer can be formed in a thickness according to the purpose, which is suitable for applying the metal layer 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.

Further, the thickness of the metal layer obtained by electrolytic plating can be controlled by adjusting the concentration of metal contained in the plating bath, the current density, or the like.
In addition, when applying to general electrical wiring etc., the layer thickness of the metal layer is preferably 0.5 μm or more, more preferably 1 to 30 μm from the viewpoint of conductivity.

<Process (H): Pattern formation process>
A pattern formation process is a process provided as needed, and is a process of etching the metal layer obtained by the plating process in pattern shape, and forming a pattern-shaped metal layer. In this step, a metal layer having a desired pattern can be generated by removing unnecessary portions of the metal layer formed on the entire substrate surface by etching.
More specifically, as shown in FIG. 1D, in this step, the patterned metal layer 18 is formed on the plated layer 12 by removing unnecessary portions of the metal layer.

  Any method can be used to form this pattern. Specifically, a generally known subtractive method (a patterned mask is provided on a metal layer, and an unformed region of the mask is etched). After that, the mask is removed to form a patterned metal layer), a semi-additive method (a plating process is performed so that a patterned mask is provided on the metal layer, and a metal layer is formed in a non-mask formation region) , Removing the mask, etching, and forming a patterned metal layer).

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

In the semi-additive method, a resist layer is provided on the formed metal layer, the same pattern as the non-metal layer pattern portion is formed by pattern exposure and development, and the resist pattern is removed by electrolytic plating using the resist pattern as a mask. This is a method of forming a patterned metal layer by performing quick etching later and removing the metal layer in a pattern.
The resist, the etching solution, etc. can use the same material as the subtractive method. Moreover, the above-described method can be used as the electrolytic plating method.

  Note that the layer to be plated may be removed together with a known means (for example, dry etching) simultaneously with the removal of the metal layer.

The laminate (surface metal layer material) obtained by the above production method has a metal layer as the outermost layer and can be used for various applications. For example, the present invention can be applied to various uses such as FPC, COF, TAB, motherboard, and package interposer substrate. Especially, it is preferable to use as wiring boards, such as a printed wiring board.
Moreover, you may provide an insulating layer further on a patterned metal layer as needed. A known material can be used for the insulating layer, and examples thereof include a known interlayer insulating film and a solder resist.
In addition, the laminated body (metal pattern material) which has a pattern-like metal layer may be used as a board | substrate mentioned above, and may laminate | stack a to-be-plated layer and a metal layer further.

<Second Embodiment of Laminate Production Method>
The second embodiment of the laminate manufacturing method of the present invention includes a step (F) of forming an insulating layer on a substrate, a step (A ′) of forming a layer to be plated on the insulating layer, and a layer to be plated. A step (B) of contacting the aqueous solution with an alkaline aqueous solution, a step (C) for performing a predetermined treatment to convert the polarity conversion group in the layer to be plated from hydrophobic to hydrophilic, and a plating catalyst or its A step (D) of applying a precursor and a step (E) of performing a plating treatment are provided.
The main difference between the second embodiment and the first embodiment described above is the point of step (F). In the following, this embodiment will be discussed with reference to FIG. 2 while mainly detailing the procedure (F). In FIG. 2, the same components as those shown in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted.

<Step (F): Insulating layer forming step>
Step (F) is a step of forming an insulating layer on the surface of the substrate. By performing this step, insulation is further ensured.
More specifically, in this step, the substrate 10 is prepared as shown in FIG. 2A, and the insulating layer 20 is formed on the surface as shown in FIG.
First, materials (insulating layer etc.) used in this step will be described in detail, and then the procedure of this step will be described in detail.

(Insulating layer)
The material which comprises an insulating layer is not restrict | limited in particular, For example, well-known insulating resins, such as a thermosetting resin or a thermoplastic resin, are mentioned.
More specifically, examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, and isocyanate resins. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.

  Although the thickness of an insulating layer is suitably selected according to the intended purpose of a laminated body, 10-150 micrometers is preferable and 30-50 micrometers is more preferable from the point of insulation ensuring.

[Procedure of Step (F)]
The method for forming the insulating layer is not particularly limited. For example, an insulating resin composition containing an insulating resin is applied onto a substrate, and heat treatment or exposure treatment is performed as necessary to form an insulating layer (coating method) or an insulating resin is contained. And a method of laminating an insulating layer on the substrate.

Note that a solvent may be included in the insulating resin composition. From the viewpoint of ease of drying and workability, a solvent having a boiling point not too high is preferable, and a solvent having a boiling point of about 40 to 150 ° C. is preferably selected. Specifically, cyclohexanone, methyl ethyl ketone, or the like can be used.
In addition, the density | concentration of solid content in an insulating resin composition has a preferable handling point of 2-50 mass%.

  After the step (F), a step (A ′) of forming a layer to be plated on the obtained insulating layer is performed. The procedure of the process is the same as the process (A) described above. By performing this step, the layer 12 to be plated is formed on the insulating layer 20 as shown in FIG.

Next, after performing the step (B) described above to remove the organic adsorbate on the layer to be plated, the step (C) described above is performed to convert the hydrophilicity / hydrophobicity of the layer to be plated.
Next, the above-described step (D) is performed to give a plating catalyst or a precursor thereof to the layer to be plated.

  Furthermore, a metal layer is formed on a to-be-plated layer by implementing a subsequent process (E). More specifically, by carrying out this step, as shown in FIG. 2D, a metal layer 14 is provided on the layer 12 to be plated, and a laminate 16 is obtained.

  Then, a process (H) is implemented as needed and a patterned metal layer is obtained. More specifically, as shown in FIG. 2E, in this step, the patterned metal layer 18 is formed on the plated layer 12 by removing unnecessary portions of the metal layer 14.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
First, the synthesis method of the polymer used in the examples will be described in detail.

(Synthesis Example 1: Polymer A)
A 500 mL three-necked flask was purged with nitrogen, propylene glycol monomethyl ether acetate (hereinafter referred to as PEGMEA) (27.6 g) was added, and the temperature was raised to 60 ° C. Into that, a mixed solution of glycidyl methacrylate (5.19 g), t-butyl acrylate (34.3 g), V-601 (1.05 g), and propylene glycol monomethyl ether acetate (64.5 g) was added over 4 hours. It was dripped. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (131.6g) of the polymer A was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 108,000 (Mw / Mn = 4.0) in terms of polystyrene.

(Synthesis Example 2: Polymer B)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (14.1 g) was added, the temperature was raised to 60 ° C., and OXE-30 (manufactured by Osaka Organic Chemical Industry) (2.78 g), t-butyl was contained therein. A mixture of acrylate (17.4 g), V-601 (0.277 g), and PEGMEA (33 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (67.2g) of the polymer B was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 10: 90 (mol ratio). Moreover, the weight average molecular weight was Mw = 92,000 (Mw / Mn = 3.5) in terms of polystyrene.

(Synthesis Example 3: Polymer C)
T-butyl methyl ether (600 g), water (330 g), and 2-butylaminoethanol (200 g) were placed in a 2 L three-necked flask and cooled in an ice bath. The internal temperature of the reaction solution was adjusted to 20 ° C. or lower, and 2-bromoisobutyric acid bromide (98 g) was added dropwise thereto. Thereafter, the internal temperature of the reaction solution was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, distilled water (300 mL) was added to stop the reaction. Thereafter, the t-butyl methyl ether layer was washed four times with distilled water (300 mL), dried over magnesium sulfate, and the t-butyl methyl ether layer was distilled off to obtain a raw material A (91 g).
Next, raw material A (91 g), dimethylaminopyridine (4.2 g), and acetone (300 mL) were placed in a 1 L three-necked flask, and methacrylic anhydride (53 g) was further added dropwise. Then, it was made to react under heating-refluxing for 4 hours. After completion of the reaction, ethyl acetate (1 L) and distilled water (300 mL) were added to the reaction solution. Thereafter, the ethyl acetate layer was washed twice with distilled water (300 mL), dried over magnesium sulfate, ethyl acetate was distilled off, and monomer A (50 g) was further purified by column chromatography.

  N, N-dimethylacetamide (16.2 g) was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream. Thereto, N, N-dimethylacetamide (38 g) solution of monomer A (10.43 g) obtained above, t-butyl acrylate (12.67 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (0.24 g). Was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was further stirred for 3 hours. Thereafter, N, N-dimethylacetamide (154 g) was added to the reaction solution, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) (0.05g) and DBU (50g) were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 49 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 15 g of polymer C (weight average molecular weight 650,000) was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio).

(Synthesis Example 4: Polymer D)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (17 g) was added, and the temperature was raised to 60 ° C. Into this, a mixed solution of acrylic acid (1.73 g), t-butyl acrylate (22.56 g), V-601 (0.46 g), and PEGMEA (39.7 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (81.6g) of the polymer D was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 15,000 (Mw / Mn = 3.5) in terms of polystyrene.

(Synthesis Example 5: Polymer E)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (17.7 g) was added, and the temperature was raised to 60 ° C. Into this, a mixed solution of hydroxylethyl acrylate (2.79 g), t-butyl acrylate (22.56 g), V-601 (0.69 g), and PEGMEA (41.4 g) was added dropwise over 2 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (84.5g) of the polymer E was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 175,000 (Mw / Mn = 3.7) in terms of polystyrene.

(Synthesis Example 6: Polymer F)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (33.3 g) was added, and the temperature was raised to 70 ° C. In it, a mixed solution of 3- (trimethoxysilyl) propyl methacrylate (5.96 g), t-butyl acrylate (22.56 g), V-601 (0.69 g), and PEGMEA (33.3 g) was added. It was dripped over 2 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (95g) of the polymer F was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 92,000 (Mw / Mn = 5.2) in terms of polystyrene.

(Synthesis Example 7: Polymer G)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (30.3 g) was added, and the temperature was raised to 70 ° C. Into this, a mixed solution of dimethylaminoethyl acrylate (3.44 g), t-butyl acrylate (22.56 g), V-601 (0.69 g), and PEGMEA (30.3 g) was added dropwise over 2 hours. . Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (86.7g) of the polymer G was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 130,000 (Mw / Mn = 3.9) in polystyrene conversion.

(Synthesis Example 8: Polymer H)
2-phenyl-2-propanol (Wako Pure Chemical Industries, Ltd.) (25 g), triethylamine (30 g), and tetrahydrofuran (150 mL) were placed in a 500 mL three-necked flask and cooled in an ice bath. The inner temperature of the reaction solution was adjusted to 10 ° C. or lower, and acryloyl chloride (25 g) was added dropwise thereto. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 5 hours. After completion of the reaction, 300 mL of ethyl acetate and 100 mL of distilled water were added. Thereafter, the ethyl acetate layer was washed with 100 mL of saturated aqueous sodium bicarbonate, then with 100 mL of saturated brine, and dried over magnesium sulfate. Then, ethyl acetate was distilled off and purified by column chromatography to obtain monomer B (10 g).

  A 500 mL three-necked flask was purged with nitrogen, PEGMEA (7.7 g) was added, and the temperature was raised to 65 ° C. Into this, a mixture of glycidyl methacrylate (1.0 g), monomer B (10.0 g), V-601 (0.11 g), and PEGMEA (18.1 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 4 hours, and the 30 wt% solution (37g) of the polymer H was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 121,000 (Mw / Mn = 4.0) in terms of polystyrene.

(Synthesis Example 9: Polymer I)
4-Methoxy-α-methylbenzyl alcohol (manufactured by ALDRICH) (25 g), triethylamine (26 g), and tetrahydrofuran (150 mL) were placed in a 500 mL three-necked flask and cooled in an ice bath. The inner temperature of the reaction solution was adjusted to 10 ° C. or lower, and acryloyl chloride (22.3 g) was added dropwise thereto. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 5 hours. After completion of the reaction, 300 mL of ethyl acetate and 100 mL of distilled water were added. Thereafter, the ethyl acetate layer was washed with 100 mL of saturated aqueous sodium bicarbonate, then with 100 mL of saturated brine, and dried over magnesium sulfate. Thereafter, ethyl acetate was distilled off, and the residue was purified by column chromatography to obtain monomer C (20 g).

  A 500 mL three-necked flask was purged with nitrogen, toluene (7.7 g) was added, and the temperature was raised to 65 ° C. Into this, a mixed solution of glycidyl methacrylate (0.94 g), monomer-C (10.0 g), V-601 (0.19 g), and toluene (17.7 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 4 hours, and the 30 wt% solution (36.7g) of the polymer I was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 76,000 (Mw / Mn = 4.2) in terms of polystyrene.

(Synthesis Example 10: Polymer J)
A 500 mL three-necked flask was charged with acrylic acid (17.99 g), 10-camphorsulfonic acid (6 mg), and hexane (100 mL). The internal temperature of the reaction solution was adjusted to 30 ° C. or lower, and isobutyl vinyl ether (25 g) was added dropwise thereto. Then, it was made to react at room temperature (25 degreeC) for 3 hours. After completion of the reaction, adsorption treatment was performed using trade name Kyoward 1000 (manufactured by Kyowa Chemical Industry Co., Ltd.) and trade name Kyoword 200 (manufactured by Kyowa Chemical Industry Co., Ltd.), and hexane was distilled off under reduced pressure to give monomer G (42 g )

  A 500 mL three-necked flask was purged with nitrogen, PEGMEA (4.6 g) was added, and the temperature was raised to 70 ° C. Into this, a mixed liquid of glycidyl methacrylate (1.02 g), monomer G (9.1 g), V-601 (0.208 g), and PEGMEA (11.5 g) was added dropwise over 2 hours. After completion of dropping, the reaction was carried out for 3 hours, reprecipitation was performed with acetonitrile, the solid was taken out, and polymer J (6 g) was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 62,000 (Mw / Mn = 2.9) in polystyrene conversion.

(Synthesis Example 11: Polymer K)
Cyclohexanol (15 g), pyridine (12.5 g), and acetonitrile (100 mL) were placed in a 500 mL three-necked flask and cooled in an ice bath. The inner temperature of the reaction solution was adjusted to 10 ° C. or lower, and p-styrenesulfonyl chloride (20 g) dissolved in acetonitrile (50 mL) was added dropwise thereto. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 5 hours. After completion of the reaction, 300 mL of ethyl acetate and 100 mL of distilled water were added. Thereafter, the ethyl acetate layer was washed with 100 mL of saturated aqueous sodium bicarbonate, then with 100 mL of saturated brine, and dried over magnesium sulfate. Then, ethyl acetate was distilled off and purified by column chromatography to obtain monomer D (20 g).

  A 500 mL three-necked flask was purged with nitrogen, PEGMEA (10.7 g) was added, and the temperature was raised to 55 ° C. Into this, a mixed solution of glycidyl methacrylate (0.85 g), monomer D (14.4 g), V-65 (0.11 g), and PEGMEA (24.9 g) was added dropwise over 2 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (50.8g) of the polymer K was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: monomer D unit = 10: 90 (mol ratio). Moreover, the weight average molecular weight was Mw = 86,000 (Mw / Mn = 3.8) in terms of polystyrene.

(Synthesis Example 12: Polymer L)
N-hydroxyphthalimide (15 g), pyridine (8.7 g), and acetonitrile (100 mL) were placed in a 500 mL three-necked flask and cooled in an ice bath. The inner temperature of the reaction solution was adjusted to 10 ° C. or lower, and p-styrenesulfonyl chloride (20 g) dissolved in acetonitrile (50 mL) was added dropwise thereto. Thereafter, the internal temperature of the reaction solution was raised to room temperature (25 ° C.) and reacted for 5 hours. After completion of the reaction, 300 mL of ethyl acetate and 100 mL of distilled water were added to the reaction solution. Thereafter, the ethyl acetate layer was washed with 100 mL of saturated aqueous sodium bicarbonate, then with 100 mL of saturated brine, and dried over magnesium sulfate. Then, ethyl acetate was distilled off and the residue was purified by column chromatography to obtain monomer F (22 g).

  A 500 mL three-necked flask was purged with nitrogen, PEGMEA (6.5 g) was added, and the temperature was raised to 60 ° C. Into this, a mixed solution of glycidyl methacrylate (0.43 g), monomer F (8.89 g), V-65 (0.055 g), and PEGMEA (15.2 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (30g) of the polymer L was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: monomer F unit = 10: 90 (mol ratio). Moreover, the weight average molecular weight was Mw = 72,000 (Mw / Mn = 3.0) in polystyrene conversion.

(Synthesis Example 13: Comparative polymer 1)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (10 g) was added, and the temperature was raised to 60 ° C. Into this, a mixed solution of glycidyl methacrylate (1.71 g), isobutyl methacrylate (12.51 g), V-601 (0.184 g), and PEGMEA (23.2 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 4 hours, and the 30 wt% solution (47.6g) of the comparison polymer 1 was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: isobutyl methacrylate unit = 12: 88 (mol ratio). Moreover, the weight average molecular weight was Mw = 88,000 (Mw / Mn = 3.5) in terms of polystyrene.
The comparative polymer 1 does not contain a polarity converting group.

(Synthesis Example 14: Comparative polymer 2)
N, N-dimethylacetamide (35 g) was placed in a 1000 ml three-necked flask and heated to 75 ° C. under a nitrogen stream. There, N, N-dimethylacetamide of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry) (6.60 g), t-butyl acrylate (29.1 g), V-601 (manufactured by Wako Pure Chemical Industries) (0.65 g) A 35 g solution was added dropwise over 2.5 hours. After completion of dropping, the reaction solution was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Ditertiary butyl hydroquinone (0.29 g), dibutyltin dilaurate (0.29 g), Karenz AOI (manufactured by Showa Denko KK) (18.56 g), N, N-dimethylacetamide (19 g) Was added and reacted at 55 ° C. for 4 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane = 1: 1, and the solid matter was taken out to obtain comparative polymer 2 (32 g). The unit ratio in the polymer was acrylonitrileoxy unit: polar conversion group unit = 20: 80 (mol ratio). Moreover, the weight average molecular weight was Mw = 7.2 (Mw / Mn = 2.4) in terms of polystyrene.
The comparative polymer 2 does not contain a specific crosslinkable group.

(Synthesis Example 15: Comparative Polymer 3)
N, N-dimethylacetamide (35 g) was placed in a 1000 ml three-necked flask and heated to 75 ° C. under a nitrogen stream. There, N, N-dimethylacetamide of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry) (6.60 g), 2-cyanoethyl acrylate (28.4 g), V-601 (manufactured by Wako Pure Chemical Industries) (0.65 g) A 35 g solution was added dropwise over 2.5 hours. After completion of dropping, the reaction solution was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Ditertiary butyl hydroquinone (0.29 g), dibutyltin dilaurate (0.29 g), Karenz AOI (manufactured by Showa Denko KK) (18.56 g), N, N-dimethylacetamide (19 g) Was added and reacted at 55 ° C. for 4 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane = 1: 1, and the solid matter was taken out to obtain comparative polymer 3 (32 g). The unit ratio in the polymer was acrylonitrileoxy unit: cyano group unit = 20: 80 (mol ratio). Moreover, the weight average molecular weight was Mw = 6.2 (Mw / Mn = 2.3) in terms of polystyrene.
The comparative polymer 3 does not contain a polarity converting group or a specific crosslinkable group.

(Synthesis Example 16: Comparative polymer 4)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (30 g), t-butyl acrylate (12.8 g), and V-601 (0.35 g) were added, heated to 60 ° C., reacted for 5 hours, A 30 wt% solution (43 g) of Comparative Polymer 4 was obtained. The weight average molecular weight was Mw = 80,000 (Mw / Mn = 2.1) in terms of polystyrene.
The comparative polymer 4 does not contain a specific crosslinkable group.

  Structural formulas of the various polymers synthesized in Synthesis Examples 1 to 16 are summarized below.

<Example 1>
(Process (A))
An epoxy insulating film GX-13 (film thickness: 40 μm) manufactured by Ajinomoto Fine Techno Co., Ltd. was bonded to a substrate having a copper film with a thickness of 18 μm on one side at a pressure of 0.2 MPa with a vacuum laminator at 100 to 110 ° C. An insulating layer was formed on the substrate.

(Preparation of composition for forming plated layer)
A 30 wt% solution (3 g) of polymer A obtained above and propylene glycol monomethyl ether (hereinafter abbreviated as MFG) (7 g) were mixed and stirred to prepare a composition X for forming a layer to be plated.

(Formation of plated layer)
The prepared composition for plating layer X was applied on the insulating layer by spin coating so that the thickness of the layer to be plated was 1 μm, dried and cured at 150 ° C. for 30 minutes, and then the layer to be plated Formed.
When the contact angle with respect to the water of the obtained to-be-plated layer was measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model: DM500), it was 89 degrees and was hydrophobic.

(Process (B))
Sodium hydroxide was added to a cleaner conditioner 902 (manufactured by Atotech Japan) (degreasing agent) to prepare a sodium hydroxide concentration of 4% by mass. The substrate with the layer to be plated obtained in the step (A) was immersed in the prepared liquid (pH: 13.6) at 60 ° C. for 10 minutes, and then washed twice with pure water.
In addition, when the remaining-film rate of the to-be-plated layer before and behind alkali treatment was measured after the said process (B), it was confirmed that the film thickness has hardly changed. The alkali resistance was evaluated according to the following criteria. The results are shown in Table 1.
“◎” The film thickness of the layer to be plated was hardly changed. (Residual film ratio 95% or more)
“◯” Most of the plated layer remained. (Residual film ratio 50% or more and less than 95%)
“△” A part of the plated layer remained. (Residual film ratio 25% or more and less than 50%)
The “x” plated layer almost disappeared. (Residual film rate less than 25%)
In addition, as a method for measuring the plating layer residual film ratio, a substrate having a plating layer before and after the alkali treatment (before and after the step (B)) was cut perpendicularly to the substrate plane, and the cross section was observed by SEM, The thickness of the plating layer was measured. Using an average value obtained by measuring three points per sample, the remaining film ratio (%) from the film thickness before and after the alkali treatment {(thickness of the plated layer after the alkali treatment / thickness of the plated layer before the alkali treatment) × 100} was measured.
Moreover, when the contact angle with respect to the water of a to-be-plated layer is measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model: DM500) after the said process (B), a contact angle changes before and behind alkali treatment. It wasn't.

(Process (C))
The substrate obtained in the step (B) was immersed in an acid treatment aqueous solution (liquid temperature: 90 ° C.) composed of an aqueous solution containing 40 wt% sulfuric acid for 30 minutes with stirring to perform a hydrophilic treatment. Thereafter, the substrate was taken out from the acid-treated aqueous solution and immersed in hot water at 50 ° C. for 3 minutes.

When the IR spectrum of the plated layer after acid treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the polar conversion group (tertiary ester group) at 1367 cm ⁻¹ disappeared. A new peak derived from a carboxylic acid group was confirmed at 1710 cm ⁻¹ . That is, it was confirmed that the polar conversion group was converted to a hydrophilic group (carboxylic acid group). Moreover, when the contact angle with respect to the water of the to-be-plated layer after an acid treatment was measured using the contact angle measuring apparatus (Kyowa Interface Science company make, model: DM500), it was 39 degrees, and the contact angle of the to-be-plated layer fell. It was confirmed that
From the above, it was confirmed that a carboxyl group was generated by acid treatment, and the plated layer was made hydrophilic.

(Step (D))
(C) The board | substrate obtained at the process was immersed for 5 minutes in 5 wt% aqueous solution (liquid temperature: 50 degreeC) of Sulcup ACL-009 (made by Uemura Kogyo Co., Ltd.), and it wash | cleaned twice with the pure water after immersion. Thereafter, the substrate subjected to the above treatment was immersed in an activator Neogant 834 (manufactured by Atotech Japan Co., Ltd.) which is a Pd catalyst application solution for 5 minutes at room temperature, and then washed twice with pure water after immersion.

(Step (E))
(Electroless plating)
Next, the substrate subjected to the above treatment was immersed in a reducer Neogant WA (manufactured by Atotech Japan), which is a Pd reducing agent, at 36 ° C. for 5 minutes and washed twice with pure water. In addition, the palladium particle (electroless-plating catalyst) with an average particle diameter of 1 nm was provided to the to-be-plated layer by performing the said process.
Thereafter, the substrate was printed with Print Gantt PV (manufactured by Atotech Japan) (pH: 12.8, containing metal ions: copper ions, nickel ions, reducing agent: formaldehyde, amount of reducing agent: 0.45. A metal layer (plating layer) was prepared on the layer to be plated by immersing in mass% (relative to the total amount of liquid) at room temperature for 30 minutes. The thickness of the obtained metal layer (electroless copper plating layer) was 0.5 μm.

(Electrolytic plating)
Electroplating was performed on the obtained substrate with an electroless copper plating layer as follows. As an electrolytic plating solution, a mixed solution of 1283 g of water, 135 g of copper sulfate pentahydrate, 342 g of 98% concentrated sulfuric acid, 0.25 g of 36% concentrated hydrochloric acid, and 39.6 g of ET-901M (Rohm and Haas) is attached to the holder. The substrate and the copper plate were connected to a power source, and electrolytic copper plating was performed at 3 A / dm ^{2 for} 45 minutes to obtain a substrate having a metal layer of about 20 μm.

[Evaluation: Surface condition evaluation]
100 laminates after the electroless plating were prepared, and a cross section cut perpendicular to the substrate plane was observed with an SEM, and the thickness of the metal layer (plating layer) was measured. The difference between the maximum value and the minimum value of the plating layer thickness was regarded as the variation of the plating layer thickness, and the case where the plating layer thickness variation was 100 nm or more was judged as defective. A defect rate (%) {(number of sheets determined to be defective / 100) × 100} was calculated and evaluated according to the following criteria. The results are shown in Table 1. Practically, “◎” and “◯” are preferable.
“◎”: A defect rate of 0% or more and less than 5% “◯”: A defect rate of 5% or more and less than 10% “Δ”: A defect rate of 10% or more and less than 20% “X”: Defect "XX" with a rate of 20% or more: No plating was deposited

[Evaluation: Evaluation of plating bath contamination]
In the electroless plating, the presence or absence of copper powder precipitated in the electroless plating solution was evaluated. The results are shown in Table 1. Practically, “◯” is preferable.
“◯”: No copper powder was deposited in the electroless plating solution even when 100 sheets were plated.
“Δ”: Copper powder was deposited in the electroless plating solution during plating of 50 to 99 sheets.
"X": Copper powder deposited in the electroless plating solution during plating of 1 to 49 sheets.

[Evaluation: Adhesion evaluation]
The board | substrate with a metal layer after the electrolytic copper plating process was heat-processed at 180 degreeC for 1 hour. Thereafter, a gap of 5 mm was made in the obtained metal layer, a cut of 130 mm was made in parallel, and the end was cut with a cutter and started up by 10 mm. Using a tensile testing machine (RTM-100, manufactured by A & D Co., Ltd.), the peeled end of the metal layer was grasped and the 90 ° peel strength was measured (tensile speed: 10 mm / min). The results are shown in Table 1. Practically, “◯” and “Δ” are preferable.
The evaluation criteria are as follows.
“◯”: Peel strength is 0.60 kN / m or more “Δ”: Peel strength is 0.30 kN / m or more and less than 0.60 kN / m “X”: Peel strength is 0.10 kN / m or more 0 “XX” which is less than 30 kN / m: Plating was not deposited, and a metal layer was not obtained.

<Example 2>
A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of polymer B was used instead of the 30 wt% solution of polymer A. The evaluation results are summarized in Table 1.

<Example 3>
A laminate was produced according to the same procedure as in Example 1 except that the polymer C was used instead of the polymer A, and the formation of the plated layer was changed to the following procedure. The evaluation results are summarized in Table 1.

[Formation of layer to be plated]
Polymer C (1 g), MFG (9 g), and Irgacure 2959 (0.05 g) were mixed and stirred to prepare a composition for forming a layer to be plated.
The prepared composition for forming a layer to be plated was applied on the insulating layer by a spin coating method so that the thickness of the layer to be plated was 1 μm, and dried at 150 ° C. for 20 minutes. Then, using a UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD), irradiation power of 10 mW / cm ² (Ushio Electric Co., Ltd. UV integrated light meter UIT150) -Irradiation power measurement with a light receiving sensor UVDS254) and exposure and curing for 500 seconds to form a plated layer.

<Example 4>
Instead of the composition X for forming a layer to be plated, a 30 wt% solution of polymer D (4 g), 1,4-butylene glycol diglycidyl ether (0.12 g) as a crosslinking agent, and MFG (6 g) were mixed and stirred. A laminate was produced according to the same procedure as in Example 1, except that the obtained composition for forming a layer to be plated was used. The evaluation results are summarized in Table 1.

<Example 5>
Instead of the composition X for forming a layer to be plated, a 30 wt% solution of polymer E (4 g), tolylene-2,4-diisocyanate (0.20 g) as a crosslinking agent, and MFG (6 g) were mixed and stirred. A laminate was produced according to the same procedure as in Example 1, except that the obtained composition for forming a layer to be plated was used. The evaluation results are summarized in Table 1.

<Example 6>
In place of the composition for forming a layer to be plated X, a layer to be plated formed by mixing and stirring a 30 wt% solution of polymer F (4 g), tetramethoxysilane (0.16 g) as a crosslinking agent, and MFG (6 g) A laminate was produced according to the same procedure as in Example 1 except that the composition for use was used. The evaluation results are summarized in Table 1.

<Example 7>
Instead of the composition X for forming the plating layer, a 30 wt% solution of polymer G (4 g), 1,4-bis (chloromethyl) benzene (0.10 g) as a crosslinking agent, and MFG (6 g) were mixed and stirred. A laminate was produced according to the same procedure as in Example 1, except that the composition for forming a layer to be plated obtained was used. The evaluation results are summarized in Table 1.

<Example 8>
A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of polymer H was used instead of the 30 wt% solution of polymer A. The evaluation results are summarized in Table 1.

<Example 9>
A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of polymer I was used instead of the 30 wt% solution of polymer A. The evaluation results are summarized in Table 1.

<Example 10>
The same as Example 1 except that the polymer J was used instead of the polymer A, the formation of the layer to be plated was changed to the following procedure, and the following step (C1) was performed instead of the above step (C). A laminate was produced according to the procedure. The evaluation results are summarized in Table 1.

[Formation of layer to be plated]
Polymer J (1 g), THF (9 g), and trimethylhexamethylenediamine (30 mg) were mixed and stirred to prepare a composition for forming a plated layer.
The prepared composition for forming a layer to be plated was applied onto the insulating layer by spin coating so that the thickness of the layer to be plated was 1 μm, and dried at 80 ° C. for 30 minutes to form a layer to be plated. .

[Step (C1)]
The substrate obtained in the step (B) was baked at 150 ° C. for 30 minutes.
When the IR spectrum of the plated layer after the heat treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the polar conversion group (acetal group) at 1141 cm ⁻¹ had disappeared. A peak derived from a carboxylic acid group was confirmed at 1710 cm ⁻¹ . That is, it was confirmed that the polar conversion group was converted to a hydrophilic group (carboxylic acid group). Moreover, when the contact angle with respect to the water of the to-be-plated layer after an acid treatment was measured using the contact angle measuring apparatus (Kyowa Interface Science company make, model: DM500), it was 40 degrees, and the contact angle of the to-be-plated layer fell. It was confirmed that
From the above, it was confirmed that carboxylic acid groups were generated by the heat treatment, and the plated layer was made hydrophilic.

<Example 11>
According to the same procedure as in Example 1, except that the polymer K was used instead of the polymer A, the formation of the layer to be plated was changed to the following procedure, and the following step (C2) was performed instead of the step (C). A laminate was produced. The evaluation results are summarized in Table 1.

[Formation of layer to be plated]
A 30 wt% solution (3 g) of polymer K and THF (7 g) were mixed and stirred to prepare a composition for forming a layer to be plated.
The prepared composition for forming a layer to be plated was applied onto the insulating layer by spin coating so that the thickness of the layer to be plated was 1 μm, and dried at 80 ° C. for 20 minutes to form a layer to be plated. .

(Process (C2))
The substrate obtained in the step (B) was heat baked at 150 ° C. for 30 minutes. When the IR spectrum of the layer to be plated after heat treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the 1367 cm ⁻¹ polar conversion group (tertiary ester group) had disappeared, new peak derived from a carboxylic acid group was observed at 1710 cm ^-1, further 1030 cm ^-1 and 1000 cm ^-1 absorption of a sulfonic acid group was observed. That is, it was confirmed that the polar conversion group was converted into a hydrophilic group (carboxylic acid group and sulfonic acid group). The contact angle of the layer to be plated after heat baking was 50 °, and it was confirmed that the layer to be plated was hydrophilized.
From the above, it was confirmed that sulfonic acid groups and carboxylic acid groups were generated by heat baking, and the plated layer was made hydrophilic.

<Example 12>
The same as in Example 1 except that the polymer L was used instead of the polymer A, the formation of the layer to be plated was changed to the following procedure, and the following step (C3) was performed instead of the above step (C). A multilayer substrate was manufactured according to the procedure. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
A 30 wt% solution (3 g) of polymer L and THF (7 g) were mixed and stirred to prepare a composition for forming a layer to be plated.
The prepared composition for forming a layer to be plated is applied on the insulating layer by spin coating so that the thickness of the layer to be plated is 1 μm, and dried at 80 ° C. for 20 minutes to form the layer to be plated. did.

[Step (C3)]
The substrate obtained in the step (B) was irradiated with 10 mW / cm ² (USHIO ELECTRIC CO., LTD.) Using a 150 UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD). After exposure for 100 seconds with a UV integrated light meter UIT150 (irradiation power measurement with UVDS254 manufactured by Co., Ltd.), heating was performed at 90 ° C. for 5 minutes.
When the IR spectrum of the layer to be plated after heat treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the 1367 cm ⁻¹ polar conversion group (tertiary ester group) had disappeared, new peak derived from a carboxylic acid group was observed at 1710 cm ^-1, further 1030 cm ^-1 and 1000 cm ^-1 absorption of a sulfonic acid group was observed. That is, it was confirmed that the polar conversion group was converted into a hydrophilic group (carboxylic acid group and sulfonic acid group). The contact angle of the layer to be plated after heat baking was 52 °, and it was confirmed that the layer to be plated was hydrophilized.
From the above, it was confirmed that sulfonic acid groups and carboxylic acid groups were generated by heat baking, and the plated layer was made hydrophilic.

<Example 13>
A multilayer substrate was manufactured according to the same procedure as in Example 1 except that the formation of the layer to be plated was changed to the following procedure and the following step (C4) was performed instead of the above step (C). Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
A 30 wt% solution of polymer A (3 g), THF (7 g), and triphenylsulfonium triflate 0.15 g were mixed and stirred to prepare a composition for forming a layer to be plated.
The prepared composition for forming a layer to be plated was applied on the insulating layer by spin coating so that the thickness of the layer to be plated was 1 μm, and dried at 100 ° C. for 20 minutes to form a layer to be plated. .

[Step (C4)]
Using a UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD), the irradiation power of 10 mW / cm ² (made by USHIO INC.) Exposure was carried out for 100 seconds using a UV integrated light meter UIT150-irradiation power measurement with a light receiving sensor UVDS254. When the IR spectrum of the layer to be plated after exposure and heat treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the polar conversion group (tertiary ester group) at 1367 cm ⁻¹ disappeared. In addition, a peak derived from a carboxylic acid group was newly confirmed at 1710 cm ⁻¹ . That is, it was confirmed that the polar conversion group was converted to a hydrophilic group (carboxylic acid group). Moreover, when the contact angle with respect to the water of the to-be-plated layer after an acid treatment was measured using the contact angle measuring device (Kyowa Interface Science company make, model: DM500), it was 48 degrees, and the contact angle of the to-be-plated layer fell. It was confirmed that

<Comparative Example 1>
A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of Comparative Polymer 1 was used instead of the 30 wt% solution of Polymer A. The evaluation results are summarized in Table 1.

<Comparative example 2>
A laminate was produced according to the same procedure as in Example 1 except that Comparative Polymer 2 (0.9 g) was used instead of the 30 wt% solution of Polymer A. The evaluation results are summarized in Table 1.

<Comparative Example 3>
A laminate was produced according to the same procedure as in Example 1, except that Comparative Polymer 3 (0.9 g) was used instead of the 30 wt% solution of Polymer A, and Step (C) was not performed. The evaluation results are summarized in Table 1.
In addition, when the contact angle with respect to the water of the to-be-plated layer after a (B) process was measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model: DM500), it is 38 degrees and is to be plated by alkali treatment. Since it was confirmed that the layer was hydrophilized, step (C) was not performed.

<Comparative example 4>
A laminate was produced according to the same procedure as in Example 13, except that a 30 wt% solution of Comparative Polymer 4 was used instead of the 30 wt% solution of Polymer A. The evaluation results are summarized in Table 1.

<Comparative Example 5>
A laminate was produced according to the same procedure as in Example 1 except that the step (C) was not performed. The evaluation results are summarized in Table 1.

From Table 1, it can be seen that the laminate produced using the composition for forming a layer to be plated according to the present invention has little plating unevenness and suppresses the contamination of the plating bath during plating. Moreover, the adhesiveness of the metal layer was also excellent.
Furthermore, from the value of the water contact angle, it was confirmed that the to-be-plated layer formed using the composition for forming to-be-plated layer of this invention has changed from hydrophobic to hydrophilic by the polarity conversion process.

  That is, in the present invention, a specific crosslinkable group having high resistance to an alkaline aqueous solution is introduced, and when contacting with the alkaline aqueous solution, the polarity of the polarity conversion group in the plating layer is set to be hydrophobic, Increases the hydrophobicity of the plating layer and imparts resistance to an aqueous alkaline solution. After contact with the alkaline aqueous solution, the polarity of the polarity conversion group is changed from hydrophobic to hydrophilic by a predetermined treatment, and the layer to be plated is made more hydrophilic, and the affinity for subsequent plating catalyst solution and plating solution is increased. Increase. As a result, a laminate having a metal layer with little plating unevenness can be obtained while suppressing contamination of the plating solution.

As can be seen from the results of Example 1, Example 2, Example 5, Example 6, Example 8, and Example 9, the crosslinkable group is an epoxy group, oxetanyl group, hydroxyl group or alkoxysilyl group, When the polarity converting group is a group represented by the general formula (1) or (2), it was confirmed that plating unevenness was further suppressed.
Moreover, when the polarity conversion group is a group represented by any one of the general formulas (1) to (3), the adhesion of the metal layer is more excellent than the comparison between Examples 11 and 12 and other examples. It was confirmed.

On the other hand, in Comparative Example 1 using Comparative Polymer 1 having no polarity conversion group, the plating layer itself did not precipitate.
In Comparative Example 2 using Comparative Polymer 2 (acryloyloxy group-containing polymer) having no predetermined crosslinkable group, plating unevenness and plating bath contamination were poor.
In Comparative Example 3 using Comparative Polymer 3 described in Patent Document 1, plating unevenness and plating bath contamination were poor.
In Comparative Example 4 using Comparative Polymer 4 having no crosslinkable group, plating unevenness and plating bath contamination were poor.
Even when the same polymer A as in Example 1 was used, in Comparative Example 5 where the step (C) (polarity conversion step) was not performed, plating did not precipitate.

<Example 14>
The laminate having the metal layer obtained in Example 1 was heat-treated at 180 ° C./1 hour, and then a dry resist film (manufactured by Hitachi Chemical Co., Ltd .; RY3315, film) was formed on the surface of the laminate. 15 μm thick) was laminated at 70 ° C. and 0.2 MPa with a vacuum laminator (manufactured by Meiki Seisakusho: MVLP-600). Next, a glass mask capable of forming comb wiring (JPCA-BU01-2007 compliant) defined in JPCA-ET01 is closely attached to the laminate obtained by laminating the dry resist film, and the resist is 70 mJ with an exposure machine having a central wavelength of 405 nm. Irradiated with light energy. Development was performed by spraying a 1% Na ₂ CO ₃ aqueous solution onto the layered product after the exposure with a spray pressure of 0.2 MPa. Thereafter, the laminate was washed with water and dried to form a resist pattern for the subtractive method on the metal film.
Etching was performed by immersing the laminate on which the resist pattern was formed in an FeCl ₃ / HCl aqueous solution (etching solution) at a temperature of 40 ° C., and the metal layer present in the region where the resist pattern was not formed was removed. Thereafter, the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the laminate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a comb-shaped wiring (pattern A metal film) was obtained. The obtained wiring was L / S = 20 μm / 75 μm.

Furthermore, a solder resist (PFR800; manufactured by Taiyo Ink Mfg. Co., Ltd.) is vacuum-laminated on a laminate having a patterned copper metal layer under conditions of 110 ° C. and 0.2 MPa, and an exposure machine having a center wavelength of 365 nm. The light energy of 420 mJ was irradiated.
Next, the laminate was subjected to a heat treatment at 80 ° C./10 minutes, and then developed by applying a NaHCO ₃ : 10% aqueous solution to the laminate surface at a spray pressure of 2 kg / m ² and dried. Thereafter, the laminate was irradiated again 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.

10: Substrate 12: Plated layer 14: Metal layer 16: Laminate 18: Patterned metal layer 20: Insulating layer

Claims (10)

  Functional groups that change from hydrophobic to hydrophilic by heat, acid or radiation, carboxyl group, hydroxyl group, isocyanate group, alkoxysilyl group, acetoxysilyl group, chlorosilyl group, primary amino group, secondary amino group, 3 Layer to be plated containing a polymer having at least one crosslinkable group selected from the group consisting of a primary amino group, an epoxy group, an oxetanyl group, a (meth) acrylamide group, an allyl group, a styryl group, a maleimide group, and a cinnamoyl group Forming composition.   The composition for forming a layer to be plated according to claim 1, wherein the functional group is a functional group that generates carboxylic acid, sulfonic acid, or sulfinic acid when heated, supplied with acid, or irradiated with radiation. The composition for to-be-plated layer forming of Claim 1 or 2 in which the said functional group has group represented by either of General formula (1)-(4).

(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represents an alkyl group that may have a substituent or an aryl group that may have a substituent. Two or all of R ₁ , R ₂ , and R ₃ may be bonded to form a ring, and an —O— group, —S— group, —CO— group, or —NR ₄ — group (R ₄ represents a hydrogen atom or an alkyl group, and * represents a bonding position.)

(In the general formula (2), R ₅ and R ₆ each independently represent a hydrogen atom, an optionally substituted alkyl group or an aryl group which may have a substituent,, R ₅ and (At least one of R ₆ represents an aryl group, and R ₅ and R ₆ may be bonded to form a ring. * Represents a bonding position.)

(In the general formula (3), R ₇ is .R ₈ representing an alkyl group which may have a hydrogen atom or a substituent, represents an alkyl group which may have a substituent. In addition, R ₇ and R ₈ may be bonded to form a ring. * Represents the bonding position.)

(In General Formula (4), R ₉ and R ₁₀ each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ₉ and R 10 ₁₀ may combine with each other to form a ring.   Furthermore, the composition for to-be-plated layer forming in any one of Claims 1-3 containing a crosslinking agent.   The laminated body which has a board | substrate and the to-be-plated layer formed using the composition for to-be-plated layer forming in any one of Claims 1-4 on the said board | substrate. Using the composition for forming a layer to be plated according to any one of claims 1 to 4, a step (A) of forming a layer to be plated on a substrate;
After the step (A), the step (B) for bringing the layer to be plated into contact with the alkaline aqueous solution;
(C) after the step (B), heating, supplying acid or irradiating with radiation to convert the functional group from hydrophobic to hydrophilic;
A step (D) of applying a plating catalyst or a precursor thereof to the layer to be plated after the step (C);
After the step (D), a plating process is performed on the plating layer to which the plating catalyst or its precursor is applied, and a metal layer is formed on the plating layer (E),
The manufacturing method of the laminated body which has a metal layer containing this.   The manufacturing method of the laminated body which has a metal layer of Claim 6 further provided with the process (H) which etches the said metal layer in a pattern shape, and forms a patterned metal layer.   The laminated body which has a metal layer obtained from the manufacturing method of Claim 6 or 7.   A wiring board comprising the laminate according to claim 8. A polymer comprising a unit represented by the general formula (D) and a unit represented by the general formula (A).

(In the general formula (D), R ₁₂ and R _{13 to} R ₁₅ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. L ₄ represents a single bond or a divalent organic group. R ₁₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
In general formula (A), R ₁₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. L ₁ represents a single bond or a divalent organic group. Y represents a functional group represented by any one of the general formulas (1) to (4).

(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represents an alkyl group that may have a substituent or an aryl group that may have a substituent. Two or all of R ₁ , R ₂ , and R ₃ may be bonded to form a ring, and an —O— group, —S— group, —CO— group, or —NR ₄ — group (R ₄ represents a hydrogen atom or an alkyl group, and * represents a bonding position.)

(In the general formula (2), R ₅ and R ₆ each independently represent a hydrogen atom, an optionally substituted alkyl group or an aryl group which may have a substituent,, R ₅ and (At least one of R ₆ represents an aryl group, and R ₅ and R ₆ may be bonded to form a ring. * Represents a bonding position.)

(In the general formula (3), R ₇ is .R ₈ representing an alkyl group which may have a hydrogen atom or a substituent, represents an alkyl group which may have a substituent. In addition, R ₇ and R ₈ may be bonded to form a ring. * Represents the bonding position.)

(In General Formula (4), R ₉ and R ₁₀ each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ₉ and R 10 ₁₀ may combine with each other to form a ring.