WO2013018456A1

WO2013018456A1 - Multilayer substrate manufacturing method

Info

Publication number: WO2013018456A1
Application number: PCT/JP2012/065890
Authority: WO
Inventors: 季彦松村; 加納　丈嘉; 裕久外園; 威史濱
Original assignee: 富士フイルム株式会社
Priority date: 2011-07-29
Filing date: 2012-06-21
Publication date: 2013-02-07
Also published as: TW201309146A; JP2013051391A

Abstract

The purpose of the present invention is to provide a method capable of manufacturing a multilayer substrate in which a layer to be plated remains even after desmear treatment, which maintains the smoothness of the surface of said layer to be plated, and in which a metal layer formed on the layer to be plated has excellent adhesion. This multilayer substrate manufacturing method involves (A) a step for forming, on the surface on the conducting layer side of a substrate, a layer to be plated having functional groups that change from hydrophobic to hydrophilic with heat, acid or radiation, (B) a step for forming via holes that pass through the layer to be plated and reach the conducting layer, (C) a step for desmear treatment using a desmear treatment liquid, (D) a step for heating, supplying acid, or irradiating to change the functional groups from hydrophobic to hydrophilic, (E) a step for supplying the layer to be plated with a plating catalyst or precursor thereof, and (F) a step for performing plating treatment on the layer to be plated to which said plating catalyst or precursor thereof has been supplied.

Description

Multilayer substrate manufacturing method

The present invention relates to a method for manufacturing a multilayer substrate.

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

In the metal wiring substrate 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, there is a problem that the high frequency characteristics when used as a metal wiring are deteriorated due to the unevenness of the obtained metal pattern at the substrate interface. In addition, in order to obtain a metal pattern with excellent adhesion between the metal layer and the substrate, it is necessary to treat the substrate surface with a strong acid such as chromic acid in order to make the substrate surface uneven. There was also a problem that a complicated process was required.

As a means for solving this problem, a layer to be plated having high adhesion to the substrate was formed on the substrate, and a metal layer was formed on the layer to be plated by plating the layer to be plated. A method of etching a metal layer is known (Patent Document 1). According to this method, the adhesion between the substrate and the metal layer can be improved without roughening the surface of the substrate. This plated layer includes a hydrophilic carboxylic acid group that exhibits excellent affinity for a plating catalyst and its precursor.

JP 2010-248464 A

On the other hand, normally, when manufacturing a multilayer substrate having a plurality of conductive layers, a via hole forming process for ensuring conduction between conductive layers and a desmear process for removing a resin residue at the bottom of the formed via hole are performed. To be implemented.
The present inventors tried to produce a multilayer substrate using the layer to be plated described in Patent Document 1. Specifically, a layer to be plated described in Patent Document 1 was formed on a substrate having a conductive layer, and a via hole was formed in the layer to be plated. Then, when a desmear process using a known desmear process liquid was performed, most of the layer to be plated was decomposed and eluted during the desmear process. Therefore, after that, even if a plating process is performed to try to form a metal layer on the layer to be plated, there is a problem that the metal layer is not formed or the adhesion is not sufficient even if the metal layer is formed.

In view of the above situation, the present invention provides a multilayer in which the plated layer remains even if the desmear treatment is performed, the smoothness of the surface is maintained, and the adhesion of the metal layer formed on the plated layer is excellent. It is an object of the present invention to provide a method for producing a multilayer substrate capable of producing a substrate.

As a result of intensive studies on the above problems, the present inventors have found that the resistance of the plating layer to the desmear treatment liquid is reduced due to the influence of hydrophilic groups such as carboxylic acid groups contained in the plating layer. It was. Based on this knowledge, by introducing a functional group capable of converting hydrophilicity / hydrophobicity into the layer to be plated, the layer to be plated is given resistance to desmear treatment and has an affinity for the plating catalyst. As a result, the present invention has been completed.
That is, the present inventors have found that the above problems can be solved by the following configuration.

(1) On a conductive layer side of a substrate with a conductive layer having a substrate and a conductive layer formed on the surface thereof, a substrate containing a compound having a functional group that changes from hydrophobic to hydrophilic by heat, acid or radiation. forming a plating layer (a),
After the step (A), a step (B) of forming a via hole so as to penetrate the plated layer and reach the conductive layer, and a step (C) of performing a desmear treatment using a desmear treatment liquid after the step (B),
After the step (C), heating, supplying acid or irradiation with radiation to convert the functional group from hydrophobic to hydrophilic (D),
A step (E) of applying a plating catalyst or a precursor thereof to the layer to be plated after the step (D);
Performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal layer on the layer to be plated in contact with the conductive layer through the via hole. The manufacturing method of the multilayer substrate which has.

(2) The method for producing a multilayer substrate according to (1), wherein the functional group is a functional group that generates a carboxylic acid group, a sulfonic acid group, or a sulfinic acid group by heating, acid supply, or irradiation with radiation.
(3) The method for producing a multilayer substrate 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) The multilayer according to (3), wherein the functional group has a group represented by the general formula (1), a group represented by the general formula (2), or a group represented by the general formula (4). A method for manufacturing a substrate.

(5) The method for producing a multilayer substrate according to (3) or (4), wherein the functional group has a group represented by the general formula (1) or a group represented by the general formula (2).
(6) The compound includes a polymer having a functional group and a crosslinkable group,
The multilayer substrate according to any one of (1) to (5), further including a step (G) after the step (A) and before the step (E), for performing a curing treatment on the layer to be plated. Production method.
(7) The method for producing a multilayer substrate according to (6), wherein the crosslinkable group is at least one group selected from the group consisting of an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group, an epoxy group, and an oxetanyl group.

(8) The method for producing a multilayer substrate according to (6) or (7), wherein the layer to be plated further contains a crosslinking agent having a reactive functional group that reacts with the crosslinkable group.
(9) Before the step (A), the step (H) of forming an insulating layer on the surface on the conductive layer side of the substrate with the conductive layer is performed, and in the step (A), a layer to be plated is formed on the insulating layer. The method for producing a multilayer substrate according to any one of (1) to (8), wherein in the step (B), a via hole is formed so as to penetrate the insulating layer and the layer to be plated and reach the conductive layer.
(10) The method for producing a multilayer substrate according to any one of (1) to (9), further comprising a step (I) of forming the patterned metal layer by etching the metal layer into a pattern.
(11) A multilayer substrate produced by the production method according to any one of (1) to (10).
(12) A semiconductor package substrate including the multilayer substrate according to (11).

(13) On the conductive layer side of the substrate with the conductive layer having the substrate and the conductive layer formed on the surface thereof, there is a functional group and a crosslinkable group that change from hydrophobic to hydrophilic by heat, acid or radiation. A lower layer formed by a cross-linking reaction of a polymer and a polymer having a functional group that changes from hydrophobic to hydrophilic by heat, acid or radiation disposed on the lower layer, and having no cross-linkable group A step (J) of forming a layer to be plated including an upper layer to be formed;
After the step (J), a step (B) of forming a via hole so as to penetrate the plated layer and reach the conductive layer; and a step (C) of performing a desmear treatment using a desmear treatment liquid after the step (B);
After the step (C), heating, supplying acid or irradiation with radiation to convert the functional group from hydrophobic to hydrophilic (D),
A step (K) of removing the upper layer after the step (D);
A step (E) of applying a plating catalyst or a precursor thereof to the layer to be plated after the step (K);
Performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal layer on the layer to be plated in contact with the conductive layer through the via hole. The manufacturing method of the multilayer substrate which has.

According to the present invention, a multi-layer substrate is manufactured in which a layer to be plated remains even if desmearing is performed, the smoothness of the surface is maintained, and the adhesion of a metal layer formed on the layer to be plated is excellent. A method for manufacturing a multilayer substrate that can be provided is provided.

(A) to (E) are schematic cross-sectional views sequentially showing respective manufacturing steps in the first embodiment of the method for manufacturing a multilayer substrate of the present invention. (A) to (F) are schematic cross-sectional views sequentially showing respective manufacturing steps in the second embodiment of the method for manufacturing a multilayer substrate of the present invention. (A) to (F) are schematic cross-sectional views sequentially showing respective manufacturing steps in the third embodiment of the method for manufacturing a multilayer substrate of the present invention. (A) to (G) are schematic cross-sectional views sequentially showing respective manufacturing steps in the fourth embodiment of the method for manufacturing a multilayer substrate of the present invention.

Below, the suitable embodiment of the manufacturing method of the multilayer board | substrate of this invention is demonstrated.
First, the features of the present invention compared with the prior art will be described in detail.
In the present invention, a functional group that changes from hydrophobic to hydrophilic by heat, acid or radiation is introduced into the layer to be plated (hereinafter also referred to as a polar conversion group as appropriate), and the polarity of the functional group after desmear treatment This method is characterized in that a process for converting is provided.
As described above, the conventionally well-known plating layer has no resistance to the desmear treatment liquid, and most of the layer is decomposed and removed when the desmear treatment is performed. In addition, if a more hydrophobic layer to be plated is formed in order to increase resistance to desmear treatment, 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, when performing desmear treatment, first, the polarity of the polarity conversion group in the layer to be plated is made hydrophobic, increasing the hydrophobicity of the layer to be plated, and having resistance to desmear treatment liquid. Give. In addition, after desmear treatment, the polarity of the polarity conversion group is converted from hydrophobic to hydrophilic by a predetermined treatment, the layer to be plated is made more hydrophilic, and the affinity for the subsequent plating catalyst solution or plating solution is increased. . As a result, a metal layer having excellent adhesion can be obtained.

<First Embodiment>
The first embodiment of the method for producing a multilayer substrate according to the present invention includes a step (A) of forming a layer to be plated on a substrate with a conductive layer, and a via hole penetrating the layer to be plated and reaching the conductive layer. A step (B) for performing, a step (C) for performing a desmear treatment, a step (D) for performing a predetermined treatment to convert a functional group in the layer to be plated from hydrophobic to hydrophilic, and a layer to be plated. A step (E) of applying a plating catalyst or a precursor thereof and a step (F) of performing a plating treatment.
Hereinafter, with reference to the drawings, detailed in materials and procedures used in the respective steps. First, the step (A) will be described in detail.

<Step (A): Plated layer forming step>
In the step (A), a functional group (polarity conversion) that changes from hydrophobic to hydrophilic by heat, acid or radiation on the conductive layer side of the substrate with a conductive layer having a substrate and a conductive layer formed on the surface thereof. This is a step of forming a layer to be plated containing a compound having a group. 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. 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.
More specifically, in this step, as shown in FIG. 1A, a substrate 14 with a conductive layer having a substrate 10 and a conductive layer 12 is prepared, and as shown in FIG. A plated layer 16 is formed on the surface on the side where 12 is present.
First, members / materials used in this step (substrate with conductive layer, compound having a polar conversion group, etc.) will be described in detail, and then the procedure of this step will be described in detail.

[Substrate with conductive layer]
First, the board | substrate with a conductive layer used at this process is explained in full detail.
A board | substrate with a conductive layer has a board | substrate and the conductive layer formed on the surface, and is a member for supporting the to-be-plated layer and metal layer which are mentioned later.
Below, the board | substrate and conductive layer which are used are explained in full 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.

(Conductive layer)
The conductive layer is a portion provided on the surface of the substrate, and mainly functions as a wiring portion in the multilayer substrate. Although the material which comprises a conductive layer is not restrict | limited in particular, Usually, it is preferable to comprise from a metal. In other words, the conductive layer is preferably a metal layer.
When the conductive layer is a metal layer, the type of metal constituting the metal layer is not particularly limited, and examples thereof include copper, silver, tin, nickel, and gold.
The thickness of the conductive layer is not particularly limited, but is preferably about 4 to 50 μm from the viewpoint of application to a printed wiring board or the like.

The arrangement position of the conductive layer on the substrate is not particularly limited, and may be provided in a pattern as shown in FIG. 1A or may be provided on the entire surface of the substrate. When the conductive layer is a patterned metal layer, the metal layer may be formed by a known method (such as a subtractive method or a semi-additive method).

In FIG. 1A, the conductive layer 12 is disposed only on one side of the substrate 10, but the conductive layer 12 may be disposed on both sides of the substrate 10.

As specific examples of the substrate with a conductive layer, a double-sided or single-sided copper-clad laminate, a copper film of this copper-clad laminate, and the like are used. These may be flexible substrates or rigid substrates.
Note that the substrate with a conductive layer may further include an insulating layer or the like over the conductive layer. That is, you may use the wiring board provided with a board | substrate, a conductive layer, and an insulating layer in this order. The method for forming the insulating layer will be described in detail in the step (H) described later.

[Compound having a polar conversion group]
The plated layer formed in this step contains a compound having a polarity conversion group.
When the layer to be plated contains the compound, the hydrophilicity / hydrophobicity of the polarity conversion group changes from hydrophobic to hydrophilic by heating, supply of acid, or irradiation with radiation. As a result, the hydrophilicity / hydrophobicity of the layer to be plated also changes to the hydrophilic side. That is, it preferably changes from a hydrophobic plated layer to a hydrophilic plated layer. As will be described later, the step (D) performed after the desmear treatment: After the polarity conversion step, the plated layer exhibits more hydrophilicity, and therefore 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.
That is, the change in the hydrophilicity / hydrophobicity of the polarity converting group ensures both the resistance to desmearing of the layer to be plated and the adsorptivity to the plating catalyst or its precursor.

The compound may be a low molecular compound or a high molecular compound, but is preferably a high molecular compound (hereinafter also referred to as a polymer) from the viewpoint of film forming properties.
Below, the aspect of the polymer which has a polarity conversion group is explained in full detail.

(Polymer having polar conversion group)
The polymer has a polarity converting group in its side chain or terminal.
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, but in terms of better adhesion of the formed metal layer, a carboxylic acid group or a sulfonic acid group can be obtained by heating, supplying an acid, or irradiating with radiation. Or a functional group that generates a sulfinic acid group, and most preferably a functional group that generates a carboxylic acid 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, and 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, 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, the group represented by the general formula (1) (for example, tertiary carboxylic acid ester group) and the general formula (2) are more excellent in desmear resistance and more excellent in polarity conversion efficiency. Group (for example, arylalkyl ester group), group represented by general formula (3) (for example, alkoxyalkyl ester group), or group represented by general formula (4) (for example, secondary alkylsulfonic acid) An ester group) is preferred. Among these, a group represented by the general formula (1), a group represented by the general formula (2), or a group represented by the general formula (4) is preferable because the desmear resistance of the plated layer is more excellent. The group represented by the general formula (1) and the group represented by the general formula (2) are more preferable in that the adhesion to the metal layer is more excellent.
Below, each group is explained in full detail.

Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (1). * 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 carbon number of the alkyl group is preferably from 1 to 22 carbon atoms, more preferably from 1 to 8 carbon atoms, from the viewpoint of better adhesion of the metal layer. 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. In addition, the heterocyclic aryl group has 3 to 20 carbon atoms and 1 to 5 hetero atoms (for example, a pyridyl group, a furyl group, a quinolyl group condensed with a benzene ring, benzofuryl group, thioxanthone group, the group of carbazole group) preferably.

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 terms of better adhesion of the metal layer.
Further, the ring formed may form a ring via —O— group, —S— group, —CO— group, or —NR ₄ — group. R ₄ represents a hydrogen atom or an alkyl group (preferably having a carbon number of 8 or less. 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); sulfonamido 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 group Alkylamino groups such as groups (preferably having 1 to 8 carbon atoms); halogen atoms such as chlorine and bromine; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group (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 , R ₁ is an alkyl group having 1 to 8 carbon atoms in view of better adhesion to the metal layer and better polarity conversion efficiency. 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 Examples thereof include a heterocyclic aryl group having 3 to 20 carbon atoms having a group.
R ₂ and R ₃ may be bonded to form a 4- to 6-membered aliphatic hydrocarbon ring.

Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (2). * 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 type of alkyl group and the substituent which may be substituted on the aryl group is 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 preferred embodiments of R ₅ and R ₆ , R ₅ is an alkyl group having 1 to 8 carbon atoms, a carbocyclic aryl group having 6 to 19 carbon atoms, carbon A carbocyclic aryl group having 6 to 19 carbon atoms having an alkyl group having 1 to 6 carbon atoms, a carbocyclic aryl group having 6 to 19 carbon atoms having an alkoxy group having 1 to 6 carbon atoms, a complex having 3 to 20 carbon atoms A cyclic aryl group, or a heterocyclic aryl group having 3 to 20 carbon atoms having an alkyl group having 1 to 6 carbon atoms, wherein R ₆ is a carbocyclic aryl group having 6 to 19 carbon atoms, C6-C19 carbocyclic aryl group having 6 alkyl groups, C6-C19 carbocyclic aryl group having C1-C6 alkoxy groups, and C3-C20 heterocyclic aryl Group having 3 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms Include embodiments in which heterocyclic aryl groups.
R ₅ and R ₆ may be bonded to form a 4- to 6-membered aliphatic hydrocarbon ring.

Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (3). * 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 from the viewpoint of better temporal stability and desmear resistance. preferable.
In another preferred embodiment 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, An alkyl group having 1 to 8 carbon atoms having 7 alkoxycarbonyl groups, 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, 1 to 6 carbon atoms, An embodiment in which the alkyl group is an alkyl group having 1 to 8 carbon atoms having an alkoxy group, 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. Can be mentioned.
R ₇ and R ₈ may combine to form a 4- to 6-membered aliphatic hydrocarbon ring.

Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (4). * 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. The alkyl group preferably has 1 to 25 carbon atoms and more preferably 1 to 8 carbon atoms from the viewpoint that the effects of the present invention are 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 .

The polar conversion group may have a group other than the group represented by any one 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 divalent to tetravalent linking groups. 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 B
As the polarity converting group B, 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. in, wherein the hydrophilic changes from hydrophobic at high sensitivity.
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 polar conversion groups are shown below.

The type of polymer skeleton having a polar conversion 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, methacrylic resin, styrene Resin etc. are mentioned. Of these, acrylic resins and methacrylic resins are preferable in terms of availability of materials and film formability.

The weight average molecular weight of the polymer is not particularly limited, but is preferably from 5,000 to 500,000, more preferably from 10,000 to 300,000, from the viewpoint of film formability of the layer to be plated.
In addition, it is preferable that this polymer does not have a cyano group substantially, and it is more preferable that a cyano group is not contained. If the polymer contains a cyano group, the cyano group may be oxidized and converted to a hydrophilic group such as a carboxylic acid during the desmear process described later. In this case, the resistance to the desmear treatment liquid may be weakened. In addition, having substantially no cyano group means that the content of the cyano group in the polymer is 0.1% by mass or less.

(Preferred embodiment of polymer having polar conversion group: Part 1)
As a preferred embodiment of the polymer having a polar conversion group, it is preferable to have a unit represented by the following general formula (A) (also referred to as a polar conversion group unit). When a polymer has this unit, the adhesiveness of a metal layer improves more.

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 the general formula (A), L ₁ represents a single bond or a divalent organic group. Examples of the divalent organic group include 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, and a propylene group), a substituted or unsubstituted group. A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO ₂ —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like). 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 described above. Among these, a group represented by any one of the general formulas (1) to (4) is preferable from the viewpoint of better adhesion of the metal layer.

One preferred embodiment of the unit represented by the general formula (A) is a unit represented by the following general formula (A-1) in that the adhesion of the metal layer is more excellent.

In the general formula (A-1), the definition 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. Note that 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. However, in terms of better adhesion of the metal layer, In the polymer unit, 10 to 95 mol% is preferable, and 55 to 90 mol% is more preferable.

(Preferred embodiment of polymer having polar conversion group: Part 2)
As another preferred embodiment of the polymer having a polar converting group, a polymer having a polar converting group and a crosslinkable group can be mentioned. When the polymer has a crosslinkable group, it is possible to obtain a layer having a higher strength and a more hydrophobic layer by a crosslink reaction via the crosslinkable group, and as a result, the adhesion of the metal layer is improved.

The position in particular of the crosslinkable group contained in a polymer is not restrict | limited, For example, the terminal or side chain of a polymer is mentioned.
The type of the crosslinkable group is not particularly limited. For example, a conventionally known crosslinkable group (functional group having a structure used for the crosslinking reaction) as described in Shinji Yamashita “Crosslinking agent handbook” is used. Can do.
Among these conventionally known crosslinkable groups, a carboxylic acid group (—COOH), a hydroxyl group (—OH), an isocyanate group (—NCO), a silanol group (Si—OH) is used because the adhesion of the metal layer is more excellent. ), An alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group, a primary amino group (—NH ₂ ), a secondary amino group (—NHR _b (where R _b represents a substituent (preferably a hydrocarbon group)). )) Tertiary amino group (—NR _b R _c (wherein R _b and R _c each independently represents a substituent (preferably a hydrocarbon group))), epoxy group, oxetanyl group, ethylene Addition-polymerizable unsaturated groups (in particular, (meth) acrylamide groups are preferred from the viewpoint that the effects of the present invention are more excellent) are preferred. Among the crosslinkable groups, a carboxyl group, a hydroxyl group, an isocyanate group, an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group, a tertiary amino group, an epoxy group, or an oxetanyl group in that the desmear resistance of the plated layer is more excellent. Are more preferable, and an epoxy group, an oxetanyl group, and an alkoxysilyl group are particularly preferable.

The alkoxysilyl group means a group in which an alkoxy group is bonded to a silicon atom (—Si—OR _d (R _d : alkyl group). The acetoxysilyl group means a group in which an acetoxy group is bonded to a silicon atom. The chlorosilyl group means a group in which a chlorine atom is bonded to a silicon atom.

Preferred examples of the polymer having a polar conversion group and a crosslinkable group include a polymer having a unit represented by the general formula (B) (also referred to as a crosslinkable group unit). When a polymer has this unit, the adhesiveness of a metal layer improves more.

In the general formula (B), R ₁₂ 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 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 carboxylic acid group, a hydroxyl group, an isocyanate group, a silanol group, an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group, a primary amino group, a secondary amino group, a tertiary amino group, an epoxy. Represents a group, an oxetanyl group, or a group represented by the following general formula (C). Especially, an epoxy group, an oxetanyl group, and an alkoxysilyl group are more preferable at the point which is excellent in desmear tolerance and the adhesiveness of the metal layer obtained is more excellent.

In formula (C), R ₁₃ to R ₁₅ each independently 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 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. Among them, in terms of the effect of the present invention is more excellent, an alkyl group, an aryl group are more preferable.

One preferred embodiment of the unit represented by the general formula (B) is a unit represented by the following general formula (B-1) in that the adhesion of the metal layer is more excellent.

In the general formula (B-1), the definition 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 having 1 to 8 carbon atoms which may be bonded via a —O—, —COO— or —CONH— bond. When Z is a carboxyl group, both L _{5 and} L ₆ may be a single bond.

The content of the unit represented by the general formula (B) in the polymer (or the unit represented by the general formula (B-1)) is not particularly limited. However, in terms of better adhesion of the metal layer, In the polymer unit, 5 to 90 mol% is preferable, and 10 to 45 mol% is more preferable.

In addition, the polymer which has a unit represented by the unit represented by general formula (A) and a general formula (B) as a polymer aspect at the point which the adhesiveness of a metal layer improves more is mentioned. Among these, the polymer having the unit represented by the general formula (A-1) and the unit represented by the general formula (B-1) is most preferable as an embodiment of the polymer.
In this embodiment, in the unit represented by the general formula (A-1), L ₂ is a single bond or a phenylene group, L ₃ is a single bond, and Y is any one of the general formulas (1) to (4). R ₁₁ is a hydrogen atom, and in the unit represented by the general formula (B-1), L ₅ is an amide group, an ester group, or a phenyl group, and L ₆ is a carbon number An aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms via a —O—, —COO—, or —CONH— bond, and Z is a hydroxyl group, an isocyanate group, It is preferably an alkoxysilyl group, a tertiary amino group, an epoxy group, or an oxetanyl group, and R ₁₂ is preferably a hydrogen atom or a methyl group.

(Method of synthesizing a polymer having a polarity conversion group)
The method for synthesizing the polymer having a polarity converting group is not particularly limited, and a known method (for example, radical polymerization, cationic polymerization, etc.) can be used. More specifically, the polymer can be obtained by polymerizing a monomer having a polarity converting group.
Examples of the monomer used include the following monomers.

The method for synthesizing a polymer having a polar conversion group and a crosslinkable group is not particularly limited, and examples thereof include a method of copolymerizing a monomer having a public polarity conversion group and a monomer having a crosslinkable group. 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 by referring to a method described in JP-A-2009-007540.

A preferred embodiment of the polymer having a polar conversion group and a crosslinkable group includes a polymer synthesized by copolymerizing the monomer having the polar conversion 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.

[Procedure of step (A)]
A method for forming a plated layer containing a compound having a polarity conversion group on the conductive layer side of the substrate with the conductive layer 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 containing a compound having a polarity conversion group onto a substrate with a conductive layer, and applying the compound (for example, polymer) directly to the conductive layer For example, a method of laminating on the attached substrate can be 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 composition for forming a plating layer used in the coating method contains the compound having the polarity converting group.
The content of the compound in the composition for forming a layer to be plated is not particularly limited, but is preferably 2 to 50% by mass and more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

To be plated layer forming composition, if desired, it may contain a solvent.
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.
From the viewpoint of ease of handling, a solvent having a boiling point of 50 ° C. to 150 ° C. is preferable. Incidentally, the these solvents may be used singly, it may be used as a mixture.

The composition for forming a layer to be plated includes a crosslinking agent described later, a photoacid generator described later, a surfactant, a plasticizer, a polymerization inhibitor, a polymerization initiator for proceeding with curing, a curing accelerator, a rubber component (for example, CTBN), a flame retardant (for example, a phosphorus flame retardant), a diluent, a thixotropic agent, a pigment, an antifoaming agent, a leveling agent, a coupling agent, 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 method for applying the composition for forming a layer to be plated on the substrate with the conductive layer 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.) Can be used.
From the viewpoint of handleability and production efficiency, the composition for forming a layer to be plated is applied on a substrate with a conductive layer, and if necessary, a drying treatment is performed to remove the solvent contained therein to form a layer to be plated. Embodiments are preferred.

The thickness of the layer to be plated is not particularly limited, but is preferably 0.02 to 5.0 μm, more preferably 0.05 to 2.0 μm, from the viewpoint of better adhesion of the metal layer.
The content of the compound having a polarity converting group in the layer to be plated is not particularly limited, but is preferably 10 to 100% by mass with respect to the total amount of the layer to be plated, from the viewpoint of better adhesion of the metal layer. and more preferably 50 to 100 mass%.

(Preferred embodiment of the layer to be plated)
When the said layer to be plated contains the polymer which has a polar conversion group and a crosslinkable group, it is preferable to perform a hardening process with respect to this layer (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 (curing reaction). In the case of this mode, the curing of the layer proceeds through the crosslinkable group, the film strength of the layer to be plated itself is increased, the hydrophobicity is also increased, and the resistance to desmear treatment is improved. As a result, the adhesion of the metal layer is more excellent.
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 (E) mentioned later. More specifically, between step (A) and step (B), between step (B) and step (C), between step (C) and step (D), or step (D). it is between the step (E). By carrying out before the step (E), the resistance of the plating layer to the plating catalyst solution used in the step (E) and the plating solution used in the step (F) can be increased.
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 optimum method is appropriately selected depending on the kind of the crosslinkable group in the polymer, and 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, a self-condensation reaction can be advanced by applying heat to form a crosslinked structure in the layer to be plated.

The method using a crosslinking agent is to form a crosslinked structure in the layer to be plated by reacting the crosslinking group in the polymer with the reactive functional group of the crosslinking agent having a reactive functional group that reacts with the crosslinking group. It is a method to do.

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 2 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, carboxyl group) Boronic 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, halogenated) in that the desmear resistance of the plated layer is more excellent (Benzyl group), (hydroxyl group, isocyanate group), (oxetanyl group, epoxy group), (alkoxysilyl group, alkoxysilyl group) are more preferred combinations.

The amount of the crosslinking agent used is usually preferably 0.01 to 50 equivalents, more preferably 0.1 to 5 equivalents, still more preferably 0.8 to 2 equivalents, relative to the number of moles of the crosslinkable group.
When the usage-amount of a crosslinking agent is in the said range, desmear tolerance and the tolerance of the to-be-plated layer with respect to a plating solution can be made compatible.

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

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 viewpoint of suppressing the decomposition of the polarity converting group and productivity. The treatment time is preferably 2 to 60 minutes, more preferably 5 to 30 minutes.
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.

<Step (B): the via hole formation process>
The step (B) is a step of forming a via hole so as to penetrate the plated layer and reach the conductive layer after the step (A). The via hole formed in this step is provided for conducting a metal layer (described later) formed on the layer to be plated and a conductive layer.
More specifically, in this step, as shown in FIG. 1C, a via hole 18 that penetrates the plated layer 16 and reaches the vicinity of the surface of the conductive layer 12 is formed. When this step is performed, smear is usually deposited on the bottom of the via hole 18.
Hereinafter, detailed procedures of the present step.

The method for forming the via hole is not particularly limited, and a known method is employed. Of these, laser processing or drilling is preferable because it is easy to control the size of the diameter of the via hole to be formed and to perform alignment.
The type of laser used for laser processing is not particularly limited as long as the layer to be plated can be removed and a via hole having a desired diameter can be formed. Among these, an excimer laser, a carbon dioxide laser (CO ₂ laser), a UV-YAG laser, and the like are used from the viewpoint of excellent workability, that is, efficient ablation and excellent productivity. Of these, a carbon dioxide laser and a UV-YAG laser are preferable from the viewpoint of cost merit.

The drilling method is not particularly limited as long as the layer to be plated can be removed and a via hole having a desired diameter can be formed. Among them, the spin drill method is generally used from the viewpoint of productivity and small diameter via processability.

¡The diameter of the via hole formed in this process is appropriately selected according to the purpose of use. In particular, the top diameter (φ) is preferably 10 to 150 μm and the bottom diameter (φ) is preferably 10 to 150 μm from the viewpoint of downsizing the substrate and increasing the density of wiring, and the top diameter (φ) is preferably More preferably, it is 10 to 60 μm and the bottom diameter (φ) is 10 to 60 μm.

<Step (C): desmear process>
A process (C) is a process of performing a desmear process using a desmear process liquid after a process (B).
When the layer to be plated is partially removed by laser processing, drilling, etc., the melt or decomposition product when the compound melts or decomposes adheres to the side or bottom of the via hole, and exists at the bottom of the via hole. In order not to directly affect the conductive layer, a layer to be plated may remain at the bottom of the via hole by adjusting laser processing or the like. In this step, such a residue is removed.
In this step, the polarity conversion group in the layer to be plated is hydrophobic. Therefore, the plated layer itself is more hydrophobic. Therefore, the resistance of the plating layer to the desmear treatment liquid is excellent, and even when the desmear treatment is performed, the decomposition and removal of the plating layer is suppressed.
Below, the desmear process liquid used at this process is explained in full detail, and the procedure of this process is explained in full detail after that.

Examples of the desmear treatment liquid include known treatment liquids, and examples include treatment liquids (in particular, aqueous solutions) containing permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, or nitric acid. An aqueous solution containing a permanganate is preferred from the standpoint of process simplicity and smear removal. Note that the desmear treatment liquid mainly contains water as a solvent. You may use an organic solvent together as needed.
The pH of the desmear treatment liquid is not particularly limited, but is preferably alkaline from the viewpoint of better smear removability, and more preferably pH 13 or higher.

Examples of desmear treatment solutions include the MDK series commercially available from Muromachi Technos Co., Ltd., the Enplate series available from Meltex Co., Ltd., Atotech Co., Ltd., and Rohm and Haas Co., Ltd. A commercially available product can be used.

A known method can be used as the desmear treatment method performed in this step, for example, a method in which a desmear treatment solution and a substrate with a conductive layer having a plated layer having a via hole obtained in step (B) are brought into contact with each other. Can be mentioned. The method for bringing the desmear treatment liquid into contact with the layer to be plated is not particularly limited. The method for applying the desmear treatment liquid onto the layer to be plated or the substrate with the conductive layer having the layer to be plated is immersed in the desmear treatment liquid. The method etc. are mentioned.
Although the contact time is not particularly limited, it is preferably 3 to 80 minutes, more preferably 5 to 40 minutes, from the viewpoint of smear removability and plating layer resistance. The temperature of the desmear treatment liquid is preferably 40 to 90 ° C., and more preferably 60 to 80, from the viewpoint of smear removability and the resistance of the plated layer.

In addition, you may perform the swelling process of a to-be-plated layer before making a desmear process liquid and a board | substrate with a conductive layer contact as needed. For example, a method of bringing an organic solvent-based swelling liquid (liquid temperature: 60 ° C.) into contact with the layer to be plated for 5 minutes may be mentioned.
Moreover, you may perform the neutralization process using a weakly acidic solution etc., after making a desmear process liquid and a board | substrate with a conductive layer contact as needed. For example, a method in which a sulfuric acid-based neutralizing solution (liquid temperature: 40 ° C.) and a substrate are brought into contact with each other for 5 minutes can be used. In particular, when heating or radiation irradiation is performed in the polarity conversion step described later, in order to further suppress adverse effects such as decomposition of the layer to be plated due to residues in the layer (for example, sodium hydroxide, permanganic acid, etc.) a, it is preferable to perform the neutralization process.

The surface roughness Ra of the layer to be plated after the desmear treatment is preferably 0.1 μm or less, and more preferably 0.05 μm or less, because high-frequency characteristics are excellent when a metal layer is used as a wiring. Although a minimum in particular is not restrict | limited, 0 micrometer is preferable.
The surface roughness Ra is measured using a known measuring device (for example, AFM) based on JIS B0601 (2001).

<Process (D): Polarity conversion process>
Step (D) 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 (C). 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 100 to 250 ° C., more preferably 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 2 hours, and more preferably 5 minutes to 1 hour 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. Among them, hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, and trifluoroacetic acid are preferable in terms of more excellent polarity conversion efficiency, and sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid are preferable in terms of easier handling. Most preferred.
The acid content in the acidic solution is preferably about 5 to 50% by mass, 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.

Note that the acidic solution may contain a reducing agent (for example, hydroxylamine sulfate, etc.) as necessary. In particular, when neutralization treatment is not performed in the desmear treatment step, adverse effects such as decomposition of the layer to be plated due to residues in the layer such as permanganic acid can be further suppressed by including a reducing agent in the acidic solution.

The method of 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 with a conductive layer having a layer to be plated in the acidic solution. It is done.
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.
The liquid temperature of the acidic solution at the time of contact is not particularly limited, but is preferably 30 to 95 ° C., more preferably 40 to 90 ° C. from the viewpoint of productivity and good polarity conversion efficiency of the 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. Examples thereof include onium salt compounds such as iodonium salts and sulfonium salts.
The content of the photoacid generator in the layer to be plated is preferably about 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and preferably 0.1% to the total solid content of the layer to be plated. More preferably, it is ˜5% by mass.
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. Moreover, the method of apply | coating the solution containing a photo-acid generator on a to-be-plated layer, and supplying a photo-acid generator to a to-be-plated layer is mentioned.

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.

In addition, after the acid treatment, the plated layer may be washed with water or the like as necessary.

(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 (D).
In addition, when the polar conversion group has a group represented by the general formula (1), a group represented by the general formula (2), and a group represented by the general formula (3), the polarity is changed by heating or supplying an acid. Conversion is preferably performed, and when the polarity conversion group has a group represented by the general formula (4), it is preferable to perform polarity conversion by heating.

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 hydrophobic to hydrophilic. That is, it preferably changes from a hydrophobic plated layer to a hydrophilic 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 the desmear treatment liquid. 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 (E): Catalyst application step>
A process (E) is a process of providing a plating catalyst or its precursor to the to-be-plated layer obtained at the process (D).
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 that the adhesiveness of a metal layer is more excellent.
Hereinafter, mainly 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.

The 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 (E))
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. The method of apply | coating a plating catalyst liquid on a to-be-plated layer, the method of immersing the board | substrate with a conductive layer in which the to-be-plated layer was formed in the plating catalyst liquid, etc. are mentioned.
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., more preferably about 30 to 50 ° C.

<Step (F): plating process>
In the step (F), a plating process is performed on the layer to be plated to which the plating catalyst or its precursor has been applied in the above step (E), and a metal layer (plating) that comes into contact with the conductive layer through the via hole to conduct. Layer) on the layer to be plated. More specifically, by performing this step, as shown in FIG. 1D, a metal layer 20 is provided on the layer 16 to be plated so as to fill the via hole 18, and the conductive layer 12 and the metal are formed. multilayer substrate 22 having a layer 20 is obtained. The metal layer 20 is in contact with and electrically connected to the metal layer 20 through the via hole 18.

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.
The electroless plating in this step is performed, for example, by washing a substrate with a conductive layer provided with an electroless plating catalyst with water to remove excess electroless plating catalyst (metal) from the layer to be plated, and then using the electroless plating bath. Immerse. As the electroless plating bath used, a known electroless plating bath can be used. The electroless plating bath is preferably an alkaline electroless plating bath (preferably having a pH of about 9 to 14) from the viewpoint of availability.
In addition, when a substrate with a conductive layer to which an electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated on the layer to be plated, the substrate with a conductive layer Is washed with water to remove excess precursor (metal salt, etc.) and then immersed in an electroless plating bath. In this case, reduction of the 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 to 30% by 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. 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 water-soluble solvent, and from this point, 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.
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.
When applied to general electric wiring, the thickness of the metal layer is preferably 0.5 μm or more, more preferably 1 to 30 μm from the viewpoint of conductivity.

<Process (I): 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. 1E, in this step, the patterned metal layer 24 is formed on the plated layer 16 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.

Simultaneously with the removal of the metal layer, the layer to be plated is formed by a known means (for example, at least one resin etching process selected from the dry etching process and the wet etching process described in JP2009-10336A). You may remove together.

The multilayer substrate obtained by the above manufacturing method can be applied to various uses such as a printed wiring board, FPC, COF, TAB, motherboard, and package interposer substrate. The multilayer substrate may be included in a semiconductor package substrate. Note that in this specification, a multilayer substrate means a substrate having a total of two or more conductive layers or metal layers.
Moreover, you may provide an insulating layer further on a metal layer (or 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.
Note that the above-described plated layer and conductive layer may be further provided on the metal layer (or the patterned metal layer) and used as the above-described substrate with a conductive layer.

<Second Embodiment>
The second embodiment of the method for producing a multilayer substrate according to the present invention includes a step (H) of forming an insulating layer on the surface of the substrate with a conductive layer, and a step (A ′) of forming a layer to be plated on the insulating layer. And a step (B ′) of forming a via hole so as to penetrate the plated layer and the insulating layer and reach the conductive layer, a step (C) of performing a desmear treatment, and a predetermined treatment, A step (D) for converting the polar conversion group from hydrophobic to hydrophilic, a step (E) for imparting a plating catalyst or a precursor thereof to the layer to be plated, and a step (F) for performing a plating treatment.
The main difference between the second embodiment and the first embodiment described above is the point of step (H). In the following, this embodiment will be described in detail with reference mainly to FIG. 2 while mainly detailing the procedure (H). In FIG. 2, the same components as those of the multilayer substrate shown in FIG.

<Step (H): Insulating layer forming step>
Step (H) is a step of forming an insulating layer on the surface on the conductive layer side of the substrate with the conductive layer. By performing this step, the insulation between the conductive layer on the substrate and the metal layer formed on the layer to be plated is further ensured.
More specifically, in this step, as shown in FIG. 2A, a substrate 14 with a conductive layer having a substrate 10 and a conductive layer 12 is prepared, and as shown in FIG. An insulating layer 26 is formed on the surface on the side where 12 is present.
First, members / materials (such as an insulating layer) used in this step will be described in detail, and then the procedure of this step will be described in detail.

[Insulation 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.

The thickness of the insulating layer is appropriately selected according to the purpose of use of the multilayer substrate, but is preferably 10 to 150 μm, more preferably 20 to 40 μm, from the viewpoint of ensuring the insulation between the conductive layer and the metal layer.

[Procedure of Step (H)]
The method for forming the insulating layer is not particularly limited. For example, an insulating resin composition containing an insulating resin is applied on a substrate with a conductive layer, and heat treatment or exposure treatment is performed as necessary to form an insulating layer (coating method) or insulating Examples thereof include a method of laminating an insulating layer containing a resin on a 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 which is 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.
The concentration of the solid content in the insulating resin composition is preferably 2 to 50% by mass from the viewpoint of handleability.

After step (H), 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 process, the layer 16 to be plated is formed on the insulating layer 26 as shown in FIG.

After the step (A ′), a step (B ′) of forming a via hole so as to penetrate the plated layer and the insulating layer and reach the conductive layer is performed. The procedure of the process is the same as the process (B) described above. By performing this step, as shown in FIG. 2D, a via hole 18 that penetrates the plated layer 16 and the insulating layer 26 and reaches the vicinity of the surface of the conductive layer 12 is formed.

Next, after performing the above-described step (C) to remove smear in the via hole, the above-described step (D) is performed to convert the hydrophilicity / hydrophobicity of the layer to be plated.
Next, the process (E) mentioned above is implemented and a plating catalyst or its precursor is provided to a to-be-plated layer.

Further, by performing the subsequent step (F), a metal layer that comes into contact with the conductive layer through the via hole to be conductive is formed on the layer to be plated. More specifically, by carrying out this step, as shown in FIG. 2E, a metal layer 20 is provided on the plated layer 16 so as to fill the via hole 18, and the conductive layer 12 and the metal are formed. A multilayer substrate 22 having a layer 20 is obtained. The metal layer 20 is in contact with and electrically connected to the metal layer 20 through the via hole 18.

Thereafter, if necessary, step (I) is performed to obtain a patterned metal layer. More specifically, as shown in FIG. 2F, in this step, the patterned metal layer 24 is formed on the plated layer 16 by removing unnecessary portions of the metal layer 20.

<Third Embodiment>
In a third embodiment of the method for producing a multilayer substrate of the present invention, a lower layer formed by a crosslinking reaction of a polymer having a polar conversion group and a crosslinkable group is disposed on the substrate with a conductive layer, and the lower layer. A step (J) of forming a layer to be plated having an upper layer formed of a polymer having no crosslinkable group and having a polarity converting group, and a via hole is formed so as to penetrate the layer to be plated and reach the conductive layer Step (B) to perform, step (C) to perform desmear treatment, step (D) to convert the polar conversion group in the layer to be plated from hydrophobic to hydrophilic by performing predetermined treatment, and removing the upper layer A step (K), a step (E) of applying a plating catalyst or a precursor thereof to the lower layer, and a step (F) of performing a plating treatment.
The main difference between the third embodiment and the first embodiment described above is the point of step (J) and step (K). In the following, this embodiment will be described in detail with reference to FIG. 3 while mainly describing the steps (J) and (K) in detail. In FIG. 3, the same components as those of the multilayer substrate shown in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted.

<Process (J): Layered layer formation process>
Step (J) is a step of forming a plated layer including at least two layers of a lower layer and an upper layer on a substrate with a conductive layer. The lower layer is formed by a crosslinking reaction of a polymer having a polarity converting group and a crosslinkable group. The upper layer is formed of a polymer having no crosslinkable group and having a polarity converting group, and is removed in the step (K) described later. By making the layer to be plated into such a laminated structure, the upper layer is used as a protective layer for desmearing treatment during desmearing treatment, removed after desmearing treatment, and plating treatment is applied to the lower layer that is not damaged by peeling or dissolution As a result, improvement in adhesion of the metal layer, plating depositability, and via shape accuracy is achieved.
First, members / materials (two-layered layer to be plated, etc.) used in this step will be described in detail, and then the procedure of this step will be described in detail.

[Two-layer of the plated layer]
The lower layer of the two-layer type plated layer is formed by a crosslinking reaction of polymer X having a polarity converting group and a crosslinkable group. The aspect of the polymer X used is as described above, and the preferred aspect is also the same.

The upper layer of the two-layered layer to be plated is formed from polymer Y having no crosslinkable group and having a polarity converting group. Since the polymer Y does not have a crosslinkable group, the crosslinking reaction does not proceed in the upper layer and can be removed in the step (K) described later.
The polymer Y does not have a crosslinkable group, and the mode thereof is not particularly limited as long as it has a polar conversion group. However, the above general formula (A It is preferable that it is the homopolymer of the unit represented by this.
The weight average molecular weight of the polymer Y is not particularly limited, but is preferably from 5,000 to 500,000, more preferably from 10,000 to 300,000 from the viewpoint of the film formability of the layer to be plated.

The layer thickness ratio between the lower layer and the upper layer is not particularly limited, but the layer thickness ratio (upper layer thickness / The layer thickness of the lower layer is preferably from 0.1 to 10, and more preferably from 0.25 to 5.

[Procedure of step (J)]
The method for forming the two-layered layer to be plated is not particularly limited. For example, a composition for forming a layer to be plated containing polymer X is applied on a substrate with a conductive layer, and a curing process (step (G)) is performed. Then, after forming the lower layer, a method of forming an upper layer by applying a composition for forming a layer to be plated containing the polymer Y on the lower layer is exemplified. Also, there is a method in which the polymer X is directly laminated on the substrate with the conductive layer, the curing process (step (G)) is performed to form the lower layer, and then the polymer Y is directly laminated on the lower layer to form the upper layer. Can be mentioned.
The aspect of the composition for forming a layer to be plated is as described above.

<Step (K): Layer removal forming step>
A process (K) is a process of removing the upper layer in a to-be-plated layer after a process (D). By carrying out this step, the lower layer that is not affected by the desmear treatment is exposed, and the metal layer is formed thereon, thereby improving the adhesion and plating deposition of the metal layer.
The method for removing the upper layer is not particularly limited, and examples thereof include a method in which a solution in which the upper layer is dissolved is brought into contact with the upper layer to remove the upper layer, and a method in which the upper layer is mechanically shaved. Especially, the method of using a solvent is preferable from the point that the removal of an upper layer is easier.

As the solution to be used, a solution in which the polymer forming the upper layer dissolves is appropriately selected. Examples thereof include an aqueous alkali solution such as a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution, and sodium bicarbonate.

The method for contacting the solution with the upper layer is not particularly limited, and examples thereof include a method of applying the solution on the upper layer, a method of immersing a substrate having the upper layer in the solution, and the like.
The contact time between the solution and the upper layer is not particularly limited, but is preferably 30 seconds to 120 minutes, and more preferably 1 to 30 minutes, from the viewpoint of the removability and productivity of the upper layer.

Hereinafter, the third aspect will be described with reference to the drawings.
In the third aspect, first, the above-described step (J) is performed to form a laminated layer 16 to be plated having a lower layer 16a and an upper layer 16b on the conductive layer-equipped substrate 14, and then FIG. As shown in C), a step (B) of forming a via hole so as to penetrate the plated layer 16 and reach the conductive layer 12 is performed. The procedure of the process is the same as the process (B) described above.

Next, after performing the above-described step (C) to remove smear in the via hole, the above-described step (D) is performed to convert the hydrophilicity / hydrophobicity of the layer to be plated.
Next, a process (K) is implemented and the upper layer 16b is removed as shown in FIG.3 (D).
Next, the process (E) mentioned above is implemented and a plating catalyst or its precursor is provided to a to-be-plated layer.

Further, by performing the subsequent step (F), a metal layer that comes into contact with the conductive layer through the via hole to be conductive is formed on the layer to be plated. More specifically, by performing this step, as shown in FIG. 3E, a metal layer 20 is provided on the lower layer 16a so as to fill the via hole 18, and the conductive layer 12 and the metal layer 20 are provided. Is obtained. The metal layer 20 is in contact with and electrically connected to the metal layer 20 through the via hole 18.

Thereafter, if necessary, step (I) is performed to obtain a patterned metal layer. More specifically, as shown in FIG. 3F, in this step, the patterned metal layer 24 is formed by removing unnecessary portions of the metal layer 20.

<Fourth embodiment>
Fourth embodiment of the method for manufacturing a multilayer substrate of the present invention, the conductive layer with the substrate on the surface of the step (H) to form an insulating layer, a layer to be plated with the lower layer and upper layer on the insulating layer formed Step (J), forming a via hole so as to penetrate the layer to be plated and reaching the conductive layer, step (C) for performing a desmear treatment, and performing a predetermined treatment, A step (D) for converting the polar conversion group from hydrophobic to hydrophilic, a step (K) for removing the upper layer, a step (E) for applying a plating catalyst or its precursor to the layer to be plated, and plating. And a step (F) of performing processing.
The main difference between the fourth embodiment and the third embodiment described above is the step (H). The procedure of the step (H) is as described above.

Below, the 4th aspect is demonstrated with reference to drawings.
As shown in FIG. 4, in the present embodiment, as shown in FIG. 4 (A), prepared conductive layer-attached substrate 14 having a substrate 10 and the conductive layer 12, as shown in FIG. 4 (B) The insulating layer 26 is formed on the surface on the side where the conductive layer 12 is present.
Then, after performing the process (J) mentioned above and forming the multilayer-type to-be-plated layer 16 which has the lower layer 16a and the upper layer 16b on the board | substrate 14 with a conductive layer as shown in FIG.4 (C), As shown in FIG. 4D, a step (B) of forming a via hole so as to penetrate the plated layer 16 and the insulating layer 26 and reach the conductive layer 12 is performed. The procedure of the process is the same as the process (B) described above.

Next, after performing the above-described step (C) to remove smear in the via hole, the above-described step (D) is performed to convert the hydrophilicity / hydrophobicity of the layer to be plated.
Next, a process (K) is implemented and the upper layer 16b is removed as shown in FIG.4 (E).
Next, the process (E) mentioned above is implemented and a plating catalyst or its precursor is provided to a to-be-plated layer.

Further, by performing the subsequent step (F), a metal layer that comes into contact with the conductive layer through the via hole to be conductive is formed on the layer to be plated. More specifically, by performing this step, as shown in FIG. 4F, a metal layer 20 is provided on the lower layer 16a so as to fill the via hole 18, and the conductive layer 12 and the metal layer 20 are provided. Is obtained. The metal layer 20 is in contact with and electrically connected to the metal layer 20 through the via hole 18.

Thereafter, if necessary, step (I) is performed to obtain a patterned metal layer. More specifically, as shown in FIG. 4G, in this step, the patterned metal layer 24 is formed by removing unnecessary portions of the metal layer 20.

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. 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 (14.2 g) was added, and the temperature was raised to 60 ° C. A mixed solution of cyclomer A (manufactured by Daicel Chemical Industries) (2.75 g), t-butyl acrylate (17.4 g), V-601 (0.277 g), and PEGMEA (33.2 g) was added for 4 hours. It was dripped over. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (68g) 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 = 105,000 (Mw / Mn = 3.8) 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 (8.4 g) was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream. Thereto, N, N-dimethylacetamide (19.5 g) of monomer A (7.3 g) obtained above, t-butyl acrylate (20.54 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (0.335 g). ) The solution 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 (130 g) was added to the reaction solution, and the reaction solution was cooled to room temperature. 4-Hydroxy TEMPO (manufactured by Tokyo Chemical Industry) (0.04 g) and DBU (16.63 g) were added to the above reaction solution, and reacted at room temperature for 12 hours. Then, 70 mass% methanesulfonic acid aqueous solution (16.5g) was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain 15 g of polymer C (weight average molecular weight 65,000). 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)
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 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 = 121,000 (Mw / Mn = 4.0) in terms of polystyrene.

(Synthesis Example 5: Polymer E)
A 500 mL three-necked flask was purged with nitrogen, toluene (7.8 g) was added, and the temperature was raised to 65 ° C. A mixture of glycidyl methacrylate (1.16 g), 1-ethylcyclopentyl acrylate (10.0 g), V-601 (0.125 g), and toluene (18.3 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 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 = 50,000 (Mw / Mn = 2.6) in polystyrene conversion.

(Synthesis Example 6: Polymer F)
4-Methoxy-α-methylbenzyl alcohol (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 mixture 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 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 = 76,000 (Mw / Mn = 4.2) in terms of polystyrene.

(Synthesis Example 7: Polymer G)
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 (6.3 g) was added, and the temperature was raised to 60 ° C. In it, a mixed solution of glycidyl methacrylate (1.02 g), t-butyl acrylate (6.0 g), monomer D (1.92 g), V-65 (0.11 g), and PEGMEA (14.6 g). It was dripped over 2 hours. Reaction was performed after completion | finish of dripping for 2 hours, and the 30 wt% solution (29.9g) of the polymer G was obtained. The unit ratio in the polymer was crosslinkable group unit: t-butyl acrylate unit: monomer D unit = 12: 78: 10 (mol ratio). Moreover, the weight average molecular weight was Mw = 66,000 (Mw / Mn = 2.8) in polystyrene conversion.

(Synthesis Example 8: Polymer H)
A 500 mL three-necked flask was charged with acrylic acid (6.08 g), 10-camphorsulfonic acid (3 mg), and hexane (100 mL). The internal temperature of the reaction solution was adjusted to 30 ° C. or lower, and octadecyl 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 carried out using the product name KYOWARD 1000 (manufactured by Kyowa Chemical Industry Co., Ltd.) and the product name KYOWARD 200 (manufactured by Kyowa Chemical Industry Co., Ltd.). )

A 500 mL three-necked flask was purged with nitrogen, PEGMEA (6.3 g) was added, and the temperature was raised to 70 ° C. Into this, a mixture of glycidyl methacrylate (0.53 g), monomer E (10.0 g), V-601 (0.11 g), and PEGMEA (11.6 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was performed for 3 hours, reprecipitation was performed with acetonitrile, the solid matter was taken out, and polymer H (7 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 = 50,000 (Mw / Mn = 2.7) in polystyrene conversion.

(Synthesis Example 9: Polymer I)
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 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 22 g of monomer F.

A 500 mL three-necked flask was purged with nitrogen, PEGMEA (6.3 g) was added, and the temperature was raised to 60 ° C. In it, a mixed solution of glycidyl methacrylate (1.02 g), t-butyl acrylate (6.0 g), monomer F (1.98 g), V-65 (0.11 g), and PEGMEA (14.6 g) was added. It was dripped over 4 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (30g) of the polymer I was obtained. The unit ratio in the polymer was crosslinkable group unit: t-butyl acrylate unit: monomer F unit = 12: 78: 10 (mol ratio). Moreover, the weight average molecular weight was Mw = 76,000 (Mw / Mn = 3.1) in polystyrene conversion.

(Synthesis Example 10: Polymer J)
A 500 mL three-necked flask was purged with nitrogen and charged with PEGMEA (30 g), t-butyl acrylate (12.8 g), and V-601 (0.35 g), heated to 60 ° C., reacted for 5 hours, A 30 wt% solution of polymer J (43 g) was obtained. The weight average molecular weight was Mw = 80,000 (Mw / Mn = 2.1) in terms of polystyrene.

(Synthesis Example 11: Polymer K)
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 K 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 12: Polymer L)
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 mixture 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 L 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 13: Polymer M)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (30.3 g) was added, and the temperature was raised to 70 ° C. A mixed solution of dimethylaminoethyl metallate (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. did. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (86.7g) of the polymer M 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 14: Polymer N)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (14.1 g) was added, and the temperature was raised to 60 ° C. A mixed solution of OXE-30 (manufactured by Osaka Organic Chemical Industry) (2.78 g), t-butyl acrylate (17.4 g), V-601 (0.277 g), and PEGMEA (33 g) was added for 4 hours. It was dripped over. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (67.2g) of the polymer N 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 15: Polymer O)
A 500 mL three-necked flask was purged with nitrogen, PEGMEA (23.7 g) was added, and the temperature was raised to 60 ° C. Into this, a mixture of glycidyl methacrylate (17.7 g), t-butyl acrylate (16.3 g), V-601 (0.46 g), and PEGMEA (55.2 g) was added dropwise over 4 hours. Reaction was performed after completion | finish of dripping for 3 hours, and the 30 wt% solution (113g) of the polymer O was obtained. In addition, each unit ratio in a polymer was crosslinkable group unit: polar conversion group unit = 50: 50 (mol ratio). Moreover, the weight average molecular weight was Mw = 91,000 (Mw / Mn = 4.1) in terms of polystyrene.

(Synthesis Example 16: Polymer P)
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 mixture 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 P 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 17: Polymer Q)
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 mixture 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 the dropwise addition, the reaction was performed for 3 hours, reprecipitation was performed with acetonitrile, the solid matter was taken out, and polymer Q (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 18: Polymer R)
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 mixture 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 R 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 19: Comparative polymer 1)
N, N-dimethylacetamide (13.8 g) was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream. Thereto, N, N-dimethylacetamide solution (32.2 g) of monomer A (11.53 g), acrylic acid (8.21 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (0.276 g) was added for 4 hours. It was dripped over. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, N, N-dimethylacetamide (154 g) was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry) (0.06 g) and DBU (58 g) were added to the above reaction solution, and the reaction was carried out at room temperature for 12 hours. Then, 70 mass% methanesulfonic acid aqueous solution (55g) was added to the reaction solution. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain comparative polymer 1 (15 g). In addition, each unit ratio in a polymer was crosslinkable group unit: acrylic acid unit = 24: 76 (mol ratio). Moreover, the weight average molecular weight was Mw = 52,000 (Mw / Mn = 2.2) in terms of polystyrene.
The comparative polymer 1 does not contain a polarity converting group.

(Synthesis Example 20: Comparative polymer 2)
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 mixture 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 2 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 2 does not contain a polarity converting group.

(Synthesis Example 21: Comparative polymer 3)
N, N-dimethylacetamide (9.4 g) was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream. There, 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry) (5.8 g), acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) (3.8 g), acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (9.0 g) ), A solution of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 g) in N, N-dimethylacetamide (9.4 g) was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, N, N-dimethylacetamide (56 g) was added, and the reaction solution was cooled to room temperature. To the above reaction solution, Karenz MO (I 7.6 g), U-600 (manufactured by Nitto Kasei) (0.2 g), TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.08 g) was added and heated to 45 ° C. And allowed to react for 6 hours. Thereafter, methanol (1.6 g) was added and reacted for 1.5 hours to complete the reaction. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain comparative polymer 3 (14 g). In addition, each unit ratio in a polymer was crosslinkable group unit: acrylonitrile unit: acrylic acid unit = 20: 30: 50 (mol ratio). Moreover, the weight average molecular weight was Mw = 4.2 (Mw / Mn = 2.2) in terms of polystyrene.
The comparative polymer 3 is a polymer used in Patent Document 1 and does not contain a polarity converting group.

(Synthesis Example 22: Comparative polymer 4)
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 of 2-hydroxyethyl acrylate (commercial product, 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 solution of dimethylacetamide (35 g) was added dropwise over 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Ditertiary butyl hydroquinone (0.29 g), dibutyltin dilaurate (0.29 g), Karenz AOI (manufactured by Showa Denko KK) (18.56 g), N, N-dimethylacetamide (19 g) And reacted at 55 ° C. for 4 hours. Thereafter, methanol (3.6 g) 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 4 (weight average molecular weight 62,000) (32 g). In addition, each unit ratio in a polymer was crosslinkable group 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 4 does not contain a polarity converting group.

The structural formulas of the various polymers synthesized in Synthesis Examples 1 to 22 are summarized below. In addition, the numerical value written together with the repeating unit in the polymer shown below shows superposition | polymerization molar ratio.

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

(Formation of 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 for forming a layer to be plated.
The prepared composition for forming a layer to be plated is applied onto the insulating layer by spin coating so that the thickness of the layer to be plated becomes 1 μm, dried and cured at 150 ° C. for 20 minutes, and the layer to be plated is formed. 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))
A via hole having a top diameter of 60 μm and a bottom diameter of 50 μm is formed on the substrate with the layer to be plated obtained in the step (A) by a CO ₂ laser to reach the copper film surface through the layer to be plated and the insulating layer. did.

(Process (C))
Subsequently, desmear treatment was performed on the surface on which the via hole was formed.
Specifically, the following conditioner aqueous solution was prepared, and the substrate obtained in the step (B) was immersed in the aqueous solution at 60 ° C. for 10 minutes while stirring the aqueous solution. Swelling treatment was performed. Next, the substrate was taken out from the conditioner aqueous solution and treated with warm water at 50 ° C. for 3 minutes. Next, the desmear treatment was performed by immersing the hot-water treated substrate in the desmear solution at 80 ° C. for 30 minutes while stirring the desmear solution (alkaline permanganese aqueous solution: pH = 13.5).
Thereafter, the desmeared substrate was immersed in hot water at 50 ° C. for 3 minutes.
The liquid composition of the used conditioner liquid and desmear liquid is shown below.

(Conditioner aqueous solution)
・ Distilled water 49g
・ Swelling Dip Securigand P (Atotech Japan Co., Ltd.) 51g
・ Sodium hydroxide (Wako Pure Chemical) 0.3g
(Desmear liquid)
・ 42g distilled water
・ Concentrate Compact CP (Atotech Japan Co., Ltd.) 62g
・ Sodium hydroxide (Wako Pure Chemical) 4g
As a result of measuring the surface roughness Ra of the plated layer after the desmear treatment using AFM (S-image, manufactured by SII Nano Technology Co., Ltd.) based on JIS B0601 (2001), Ra = 0.05 μm Met.

(Process (D))
The substrate obtained in step (C), hydroxylamine 1.5 wt% and the acid treatment solution comprising an aqueous solution containing sulfuric acid 40 wt% (liquid temperature: 90 ° C.) sulfate in, were immersed while applying stirring for 30 min, a hydrophilic The treatment was performed. 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

(Process (E))
The substrate obtained in the step (D) was immersed in a 5 wt% aqueous solution (liquid temperature: 50 ° C.) of Sulcup ACL-009 (manufactured by Uemura Kogyo Co., Ltd.) for 5 minutes, and washed twice with 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.

(Process (F))
(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 on both the plated layer and the bottom of the via hole.

(Electrolytic plating)
Electroplating was performed on the obtained substrate with an electroless copper plating layer as follows. As the electroplating solution, use a mixed solution of water 1283g, copper sulfate pentahydrate 135g, 98% concentrated sulfuric acid 342g, 36% concentrated hydrochloric acid 0.25g, ET-901M (Rohm and Haas) 39.6g, and attach the holder The substrate and the copper plate were connected to a power source and subjected to electrolytic copper plating at 3 A / dm ^{2 for} 45 minutes to obtain a substrate (multilayer substrate) having a metal layer of about 18 μm. The thickness of the obtained electrolytic copper plating layer was 18 μm on the layer to be plated and 58 μm on the bottom of the via hole.

[Evaluation: Resistance to desmear]
After the said process (C), the remaining-film rate of the to-be-plated layer before and behind a desmear process was measured, and the desmear tolerance was evaluated on the following references | standards. The results are shown in Table 1. Practically, “A” and “B” are preferable.
The film thickness of the “A” plated layer hardly changed. (Residual film ratio 95% or more)
Most of the “B” plated layer remained. (Residual film ratio 50% or more and less than 95%)
A portion of the “C” plated layer remained. (Residual film ratio 25% or more and less than 50%)
The “D” layer to be plated was almost lost. (Residual film rate less than 25%)
In addition, as a measuring method of a to-be-plated layer residual film rate, the board | substrate which has a to-be-plated layer before and behind a desmear process was cut | disconnected perpendicularly | vertically with respect to the substrate plane, the cross section was observed by SEM, and the thickness of the to-be-plated 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 desmear treatment {(thickness of the plated layer after the desmear treatment / thickness of the plated layer before the desmear treatment) × 100} was measured.

[Evaluation: Adhesion evaluation]
The adhesion evaluation was performed in the same manner as in Example 1 except for the above step (B), thereby obtaining a substrate with a metal layer having no via structure corresponding to Example 1. Thereafter, the substrate with the metal layer was subjected to heat treatment at 180 ° C. 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 tester (RTM-100, manufactured by A & D Co., Ltd.), the peeled metal layer end was held and the 90 ° peel strength was measured (tensile speed: 10 mm / min). The results are shown in Table 1. Practically, “A” and “B” are preferable.
The evaluation criteria are as follows.
“A”: The peel strength is 0.60 kN / m or more.
“B”: The peel strength is 0.30 kN / m or more and less than 0.60 kN / m.
“C”: The peel strength is 0.10 kN / m or more and less than 0.30 kN / m.
“D”: No plating was deposited, and no metal layer was obtained.

<Example 2>
A multilayer substrate was produced 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 that the step (D1) was performed instead of the above step (D). 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 (D1)]
Using a UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD) on the substrate having the layer to be plated after desmear treatment, an irradiation power of 10 mW / cm ² ( Exposure was performed for 100 seconds using a UV integrated light meter UIT150 manufactured by USHIO INC. (Measurement of irradiation power with a light receiving sensor UVDS254). When the IR spectrum of the plated layer after exposure 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 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

<Example 3>
A multilayer substrate was manufactured according to the same procedure as in Example 1 except that the 30 wt% solution of polymer B prepared above was used instead of the 30 wt% solution of polymer A. Various measurement results are summarized in Table 1.

<Example 4>
Using the polymer C in place of the polymer A, except for changing the formation of the plated layer in the following steps, following the same procedure as in Example 1 to produce a multilayer substrate. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
Polymer C (1g), MFG (9g), mixed and stirred Irgacure 2959 (0.05 g), was prepared to be plated layer forming composition.
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), an irradiation power of 10 mW / cm ² (ultraviolet integrated light meter UIT150 manufactured by Ushio Electric Co., Ltd.) -Irradiation power was measured with a light receiving sensor UVDS254) and cured for 500 seconds to form a layer to be plated.

<Example 5>
A multilayer substrate was manufactured according to the same procedure as in Example 1 except that the 30 wt% solution of polymer D prepared above was used instead of the 30 wt% solution of polymer A. Various measurement results are summarized in Table 1.

<Example 6>
The same procedure as in Example 1 was performed except that the 30 wt% solution of polymer E prepared above was used instead of the 30 wt% solution of polymer A, and the following step (D2) was performed instead of the above step (D). A multilayer substrate was manufactured according to the procedure. Various measurement results are summarized in Table 1.

[Step (D2)]
The substrate having the layer to be plated after the desmear treatment was immersed in a neutralizing solution at 40 ° C. for 5 minutes, washed with distilled water at a liquid temperature of 50 ° C. for 5 minutes, and then baked at 180 ° C. for 1 hour. The liquid composition of the neutralization liquid is shown below.
(Neutralizing solution)
・ Distilled water 216.25g
・ Concentrated sulfuric acid 8.75g
・ Reduction Solution Securigant P-500 (Atotech Japan Co., Ltd.) 25g

When the IR spectrum of the plated layer after 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 1337 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 heat baking was measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model DM500), it is 39 degrees, and the contact angle of a to-be-plated layer falls. It was confirmed that

<Example 7>
A multilayer substrate was manufactured according to the same procedure as in Example 1 except that the 30 wt% solution of polymer F prepared above was used instead of the 30 wt% solution of polymer A. Various measurement results are summarized in Table 1.

<Example 8>
Using the polymer G instead of the polymer A, by changing the formation of the plated layer in the following procedure, except that further steps were performed (D3) in place of the step (D), the same procedure as in Example 1 According to the above, a multilayer substrate was manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
A 30 wt% solution of polymer G (3 g) 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. .

[Step (D3)]
The board | substrate which has a to-be-plated layer after a desmear process was heat-baked for 30 minutes at 150 degreeC.
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 (tertiary ester group) at 1367 cm ⁻¹ 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).
Moreover, the contact angle of the to-be-plated layer after heat baking was 50 °, and it was confirmed that the to-be-plated layer 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 9>
Using Polymer H instead of Polymer A, to change the formation of the plated layer in the following procedure, except that further steps were performed (D4) in place of the step (D), the same procedure as in Example 1 According to the above, a multilayer substrate was manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
Polymer H (1 g), THF (9 g), and trimethylhexamethylenediamine (15 mg) were mixed and stirred to prepare a composition for forming a plating 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 (D4)]
A substrate having a plated layer formed after the desmear treatment was immersed for 5 minutes in neutralizing solution of 40 ° C., and 30 minutes heat-baked at 0.99 ° C. After washing 5 minutes at 50 ° C. distilled water.
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 heat baking was measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model: DM500), it was 62 degrees, and the contact angle of a to-be-plated layer fell It was confirmed that

<Example 10>
Using the polymer I in place of the polymer A, by changing the formation of the plated layer in the following procedure, except that further steps were performed (D5) in place of the step (D), the same procedure as in Example 1 According to the above, a multilayer substrate was manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
A 30 wt% solution of polymer I (3 g) 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 (D5)]
A substrate having a layer to be plated after desmear treatment is applied to a 10 mW / cm ² irradiation power (USHIO) using a 150 UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD). after exposure 100 seconds at Denki Co. accumulated UV actinometer UIT150- irradiation power measured by the light receiving sensor UVDS254), was heated for 5 minutes at 90 ° C..
When the IR spectrum of the plated layer after the 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. 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 light irradiation was 52 °, and it was confirmed that the layer to be plated was hydrophilized.
From the above, it was confirmed that a sulfonic acid group and a carboxylic acid group were generated by light treatment, and the plated layer was made hydrophilic.

<Example 11>
Instead of 30 wt% solution of the polymer A, except for using 30 wt% solution of polymer J was prepared in the above, according to the procedure as in Example 2, was prepared a multi-layer substrate. Various measurement results are summarized in Table 1.

<Example 12>
A multilayer substrate according to the same procedure as in Example 1 except that the 30 wt% solution of polymer K prepared above was used instead of the 30 wt% solution of polymer A, and the formation of the layer to be plated was changed to the following procedure. Manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
A 30 wt% solution of polymer K (4 g), THF (6 g), and tetramethoxysilane (0.16 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 becomes 1 μm, and dried and cured at 150 ° C. for 30 minutes to form a layer to be plated. did.

<Example 13>
A multilayer substrate according to the same procedure as in Example 1 except that the 30 wt% solution of polymer L prepared above was used instead of the 30 wt% solution of polymer A, and the formation of the layer to be plated was changed to the following procedure. Manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
30 wt% solution of polymer L (4g), THF (6g), stirred and mixed tolylene-2,4-diisocyanate (0.20 g), was prepared to be plated layer forming composition.
The prepared composition for forming a layer to be plated is applied onto the insulating layer by spin coating so that the thickness of the layer to be plated becomes 1 μm, and dried and cured at 150 ° C. for 30 minutes. Formed.

<Example 14>
A multilayer substrate according to the same procedure as in Example 1 except that the 30 wt% solution of polymer M prepared above was used instead of the 30 wt% solution of polymer A, and the formation of the layer to be plated was changed to the following procedure. Manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
30 wt% solution of the polymer M (4g), THF (6 g), 1,4-bis (chloromethyl) benzene (0.10 g) were mixed and stirred to prepare a layer to be plated forming composition.
The prepared composition for forming a layer to be plated is applied onto the insulating layer by spin coating so that the thickness of the layer to be plated becomes 1 μm, and dried and cured at 150 ° C. for 30 minutes. Formed.

<Example 15>
A multilayer substrate according to the same procedure as in Example 1 except that the 30 wt% solution of polymer N prepared above was used instead of the 30 wt% solution of polymer A, and the formation of the layer to be plated was changed to the following procedure. Manufactured. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
30 wt% solution of the polymer N (4g), THF (6g), stirred and mixed bisphenol A diglycidyl ether (0.20 g), was prepared to be plated layer forming composition.
The prepared composition for forming a layer to be plated is applied onto the insulating layer by spin coating so that the thickness of the layer to be plated becomes 1 μm, and dried and cured at 150 ° C. for 30 minutes. Formed.

<Example 16>
A multilayer substrate was produced according to the same procedure as in Example 1 except that the 30 wt% solution of polymer O prepared above was used instead of the 30 wt% solution of polymer A. Various measurement results are summarized in Table 1.

<Example 17>
A multilayer substrate was manufactured according to the same procedure as in Example 8 except that the 30 wt% solution of polymer P prepared above was used instead of the 30 wt% solution of polymer G. Various measurement results are summarized in Table 1.

<Example 18>
A multilayer substrate was produced according to the same procedure as in Example 9 except that the polymer Q was used instead of the polymer H, and the formation of the plated layer was changed to the following procedure. Various measurement results are summarized in Table 1.

[Formation of layer to be plated]
Polymer Q (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. .

<Example 19>
A multilayer substrate was manufactured according to the same procedure as in Example 10 except that the 30 wt% solution of polymer R prepared above was used instead of the 30 wt% solution of polymer I. Various measurement results are summarized in Table 1.

<Comparative Example 1>
A multilayer substrate was manufactured according to the same procedure as in Example 1 except that the step (D) was not performed. Various measurement results are summarized in Table 1.

<Comparative Example 2>
And performing step (D) after the step (A), followed in the same manner as in Example 1 step (B), step (C), and carrying out step (E), step (F), producing a multi-layer board did. Various measurement results are summarized in Table 1.

<Comparative Example 3>
A multilayer substrate was produced according to the same procedure as in Example 1, except that Comparative Polymer 1 (0.9 g) was used instead of the 30 wt% solution of Polymer A.
In Comparative Example 3, the step (D) was not performed because the layer to be plated had disappeared when the step (C) was performed. Various measurement results are summarized in Table 1.

<Comparative example 4>
According to the same procedure as in Example 1, except that the comparative polymer 2 (0.9 g) was used instead of the 30 wt% solution of the polymer A and the above step (D6) was performed instead of the above step (D), the multilayer A substrate was manufactured. Various measurement results are summarized in Table 1.

[Step (D6)]
The substrate having the layer to be plated after the desmear treatment was hydrophilized by immersing the substrate at 90 ° C. for 30 minutes with stirring using an acid treatment aqueous solution composed of a 40 wt% sulfuric acid aqueous solution. Thereafter, the substrate was taken out and further immersed in hot water at 50 ° C. for 3 minutes.
When the IR spectrum of the plated layer before and after acid treatment was measured using an ATR-infrared spectrophotometer, no change was observed in the IR spectrum, and no peak derived from a carboxylic acid group was confirmed.
Moreover, the contact angle of the to-be-plated layer after an acid treatment is 90 degrees, and it was confirmed that the polarity of the to-be-plated layer has not changed.

<Comparative Example 5>
A multilayer substrate was manufactured 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.
In Comparative Example 5, the step (D) was not performed because the layer to be plated had disappeared when the step (C) was performed. Various measurement results are summarized in Table 1.

<Comparative Example 6>
A multilayer substrate was produced according to the same procedure as in Example 1 except that Comparative Polymer 4 (0.9 g) was used instead of the 30 wt% solution of Polymer A.
In Comparative Example 6, the step (D) was not performed because the plated layer disappeared when the step (C) was performed. Various measurement results are summarized in Table 1.

In Table 1 above, “-” in the processing method column of step (D) means not implemented.

As shown in Table 1, according to the method for manufacturing a multilayer substrate of the present invention, the smoothness of the surface of the layer to be plated is maintained even if the desmear treatment is performed (excellent resistance to desmear treatment) and on the layer to be plated. A multilayer substrate having excellent adhesion of the metal layer formed on the substrate can be produced. Further, it was confirmed that the desired effect can be obtained in any of the heating (thermal baking), the acid supply, and the radiation emission as the step (D) (polarity conversion step).
As shown in Table 1, in the example in which the desmear resistance indicates “A”, the surface roughness is more flat (less than 0.10 μm) compared to the example in which the desmear resistance indicates “B”. Nevertheless, it was confirmed that the same degree of adhesion was exhibited.

In particular, as can be seen from a comparison between Example 9 and other examples, the functional group that changes from hydrophobic to hydrophilic by heat, acid, or radiation is a group represented by the general formula (1): When the group represented by (2) or the group represented by the general formula (4) was used, it was confirmed that the resistance to desmear treatment was more excellent.
As can be seen from the comparison between Example 9 and Example 18, in the group represented by the general formula (3), the shorter the length of the alkyl group represented by R ₈ , the better the adhesion. It was confirmed that there was an improvement.

Further, as can be seen from the comparison between Example 11 and other examples, when the compound having a functional group that changes from hydrophobic to hydrophilic by heat, acid or radiation has a crosslinkable group, It was confirmed that the properties were more excellent.
Further, as shown in Examples 1 to 3, Examples 4 to 8, Example 10, Example 12, Example 15, Example 17, and Example 19, as a crosslinkable group, an epoxy group, an oxetanyl group, or When an alkoxysilane group was used, it was confirmed that the desmear treatment resistance was more excellent.

As can be seen from the comparison between Example 16 and Example 1, it was confirmed that the adhesiveness of the metal layer was more excellent when there were many units having a polar conversion group.

On the other hand, in Comparative Example 1 in which the step (D) was not performed, although the desmear treatment resistance was excellent, plating did not precipitate and a metal layer was not obtained. This is presumably because the plating layer was hydrophobic and the plating catalyst solution or the plating solution did not easily penetrate, and the plating did not precipitate.
Moreover, in the comparative example 2 which implemented the process (D) (polarity conversion process) before the process (C) (desmear process process), the desmear process tolerance is inferior and the adhesiveness of the obtained metal layer is also inferior. It was. This is because the functional group was converted from hydrophobic to hydrophilic before the desmear treatment, so that the layer to be plated itself became hydrophilic and the resistance to the desmear treatment liquid was lost.

Moreover, in Comparative Examples 3, 5 and 6 using Comparative Polymers 1, 3 and 4 having no polarity converting group, the desmear treatment resistance was inferior, and the adhesion of the obtained metal layer was also inferior. In particular, Comparative Polymer 3 used in Comparative Example 5 is a polymer disclosed in Patent Document 1, and it was confirmed that the desired effect could not be obtained with this polymer.
Furthermore, also in the comparative example 4 using the comparative polymer 2 which does not have a polarity conversion group, it was inferior to the adhesiveness of the obtained metal layer.

<Example 20>
The multilayer substrate 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 metal layer 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 a comb-type wiring (compliant with JPCA-BU01-2007) as defined in JPCA-ET01 is closely attached to the laminate obtained by laminating the dry resist film, and the resist is adhered to 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 layer.
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 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.

(Synthesis Example 23: Polymer X)
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 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 X was obtained. Moreover, the weight average molecular weight was Mw = 74,000 (Mw / Mn = 4.2) in terms of polystyrene.

(Synthesis Example 24: Polymer Y)
A 500 mL three-necked flask was purged with nitrogen, toluene (7.8 g) was added, and the temperature was raised to 65 ° C. Into this, a mixed liquid of 1-ethylcyclopentyl acrylate (10.0 g), V-601 (0.125 g), and toluene (18.3 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 Y was obtained. Moreover, the weight average molecular weight was Mw = 121,000 (Mw / Mn = 4.1) in terms of polystyrene.

<Example 21>
(Process (H))
An epoxy insulating film GX-13 (film thickness: 40 μm) manufactured by Ajinomoto Fine Techno Co., Ltd. is applied to the copper film side of a substrate having a copper film having a thickness of 18 μm on one side and a pressure of 0.2 MPa by a vacuum laminator at 100 to 110 ° C. The insulating layer was formed on the substrate by bonding under the above conditions.

(Process (J))
A 30 wt% solution (3 g) of polymer D obtained above and propylene glycol monomethyl ether (hereinafter abbreviated as MFG) (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 is 1.5 μm, dried and cured at 150 ° C. for 20 minutes, and the lower layer of the layer to be plated is formed. Formed.
Next, polymer X (3 g) and MFG (7 g) are mixed and stirred to prepare a composition for forming a layer to be plated, and the composition is applied on the lower layer and dried at 150 ° C. for 20 minutes. (2.0 μm) was formed.
When the contact angle with respect to the water of the obtained layer to be plated was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., model: DM500), it was 91 ° and was hydrophobic.

Next, step (B) and step (C) performed in Example 1 were performed.

(Process (D))
The substrate having the layer to be plated after the desmear treatment was immersed in a neutralizing solution at 40 ° C. for 5 minutes, washed with distilled water at a liquid temperature of 50 ° C. for 5 minutes, and then baked at 180 ° C. for 1 hour. The liquid composition of the neutralization liquid is shown below.
(Neutralizing solution)
・ Distilled water 216.25g
・ Concentrated sulfuric acid 8.75g
・ Reduction Solution Securigant P-500 (Atotech Japan Co., Ltd.) 25g

When the IR spectrum of the plated layer after 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 1337 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 is 41 degrees, and the contact angle of a to-be-plated layer falls. It was confirmed that

(Process (K))
After the heat baking, the obtained substrate was immersed in a 4 mass% NaOH aqueous solution heated to 60 ° C. to remove the upper layer.

(Process (E))
The obtained substrate was immersed in the cleaner liquid (liquid temperature: 50 ° C.) described below for 5 minutes, and then immersed in pure water for 1 minute after the immersion was performed twice.
Thereafter, the substrate subjected to the above treatment is immersed in the following plating catalyst solution (liquid temperature: 26 ° C.) for 5 minutes to give a plating catalyst precursor, and then immersed in pure water for 1 minute. Was performed twice.
Subsequently, the substrate subjected to the above treatment is immersed in the reducer solution (liquid temperature: 30 ° C.) described below for 3 minutes to perform a reduction treatment, and then immersed twice in pure water for 2 minutes. It was.
Further, the substrate subjected to the above treatment was immersed in an accelerator liquid (liquid temperature: 26 ° C.) described below for 1 minute for activation treatment.

(Cleaner solution)
-ACL009 (manufactured by Uemura Kogyo Co., Ltd.): 5 Vol%
・ Pure water: 95Vol%

(Plating catalyst solution)
・ NaOH: 0.035 g / L
・ MAT2-B (Uemura Kogyo Co., Ltd.): 40.4g / L
・ MAT2-A (manufactured by Uemura Kogyo Co., Ltd.): 200 g / L
・ Pure water: Approximately 760 g / L

(Reducer solution)
・ MAB4-A (manufactured by Uemura Kogyo Co., Ltd.): 2Vol%
・ MAB4-B (manufactured by Uemura Kogyo Co., Ltd.): 20Vol%
・ Pure water: 78 Vol%

(Accelerator liquid)
・ MEL3-A (manufactured by Uemura Kogyo Co., Ltd.): 5Vol%
・ Pure water: 95Vol%

(Process (F))
As described above, electroless plating is performed for 60 minutes using an electroless plating bath (temperature: 30 ° C.) having the following composition using a sulcup PEA manufactured by Uemura Kogyo Co., Ltd. A laminate having an electroless plating layer was obtained. The thickness of the obtained electroless plating layer was 1 μm.

The preparation order of the electroless plating solution and the raw materials are as follows.
Distilled water: 76.9 Vol%
PEA-A: 10 Vol%
PEA-B 2X: 5 Vol%
PEA-C: 1.4 Vol%
PEA-D: 1.2 Vol%
PEA-E: 5 Vol%
Formalin solution: 0.5 Vol%
* The formalin used here is a Wako Pure Chemical formaldehyde solution (special grade).

As described above, electrolytic plating was performed on the substrate on which the electroless plating layer was formed.
Specifically, the surface of the electroless plating layer in the substrate was degreased for 3 minutes with the following degreasing liquid (liquid temperature: 45 ° C.), and then the laminate was washed with water.
Next, the acid active liquid described below was prepared, the substrate was immersed for 1 minute while stirring the acid active liquid (liquid temperature: room temperature), and then the laminate was taken out and washed with water.
Furthermore, the electrolytic plating solution described below was prepared, and the laminated body with holes was immersed while stirring the electrolytic plating solution (liquid temperature: room temperature), and electrolytic copper plating treatment was performed at 1.6 A / dm ^{2 for} 75 minutes. A multilayer substrate having a metal layer of about 20 μm was obtained.

(Degreasing liquid)
Melplate PC-316 (Meltex Co., Ltd.): 10Vol%
・ Pure water: 90Vol%

(Acid active solution)
・ 98% sulfuric acid: 10Vol%
・ Pure water: 90Vol%

(Electrolytic plating solution (solvent: water))
CuSO ₄ · 5H ₂ O: 160 g / L
98% sulfuric acid: 150 g / L
・ NaCl: 70 mg / L
・ Inplate DI2 leveler (manufactured by Atotech): 12ml / L
・ Brightener inplate (manufactured by Atotech): 0.6 ml / L

[Evaluation: Adhesion evaluation]
The adhesion of the metal layer was evaluated according to the same procedure and evaluation criteria as those described above. The results are shown in Table 2.

[Via shape evaluation]
From the cross-sectional SEM of the obtained wiring board, 100 arbitrarily selected vias were observed, and their deposition defects were observed. With respect to the top diameter of 60 μm, when the plated layer protrudes (overhangs) in the via inside / outside direction and the via hole diameter is 100%, a failure is defined as 2% or more.
When observing 100 holes, “A” indicates that the number of holes identified as a failure is 1 or less, “B” indicates that the number is 2 or more, and 3 or less indicates “B”. Evaluated as “C”. The results are summarized in Table 2. In practice, it is desirable not to be “C”.

<Example 22>
A multilayer substrate was produced according to the same procedure as in Example 21 except that the contact time with the desmear liquid in step (C) was changed from 30 minutes to 20 minutes.

<Example 23>
A multilayer substrate was produced according to the same procedure as in Example 21 except that the contact time with the desmear liquid in step (C) was changed from 30 minutes to 40 minutes.

<Example 24>
A multilayer substrate was produced according to the same procedure as in Example 21, except that polymer E was used instead of polymer D and polymer Y was used instead of polymer X.

<Example 25>
A multilayer substrate was produced according to the same procedure as in Example 24 except that the contact time with the desmear liquid in the step (C) was changed from 30 minutes to 20 minutes.

<Example 26>
A multilayer substrate was produced according to the same procedure as in Example 24 except that the contact time with the desmear liquid in step (C) was changed from 30 minutes to 40 minutes.

As shown in Table 2, according to the manufacturing method of the multilayer substrate of the present invention in which the laminated plating layer forming step is performed, the smoothness of the surface of the plating layer is maintained even when the desmearing treatment is performed (desmearing treatment). It is possible to produce a multilayer substrate having excellent resistance) and excellent adhesion of the metal layer formed on the layer to be plated. Furthermore, in this aspect, it was confirmed that the shape of the via formed was also excellent.

<Example 27>
A multilayer substrate was manufactured according to the same procedure as in Example 21 except that the electroplating time was changed from 75 minutes to 30 minutes.
Using this multilayer substrate, a multilayer wiring substrate having L / S = 20 μm / 20 μm was obtained according to the procedure of Example 20.

<Example 28>
A multilayer wiring board was obtained according to the same procedure as in Example 27 except that the multilayer board obtained in Example 24 was used.

10: Substrate 12: Conductive layer 14: Substrate with

conductive layer

16, 16a, 16b: Plated layer 18: Via hole 20: Metal layer 22: Multilayer substrate 24: Patterned metal layer 26: Insulating layer

Claims

On the conductive layer side of a substrate with a conductive layer having a substrate and a conductive layer formed on the surface thereof, a layer to be plated containing a compound having a functional group that changes from hydrophobic to hydrophilic by heat, acid or radiation. Forming (A),
After the step (A), a step (B) of forming a via hole so as to penetrate the plated layer and reach the conductive layer, and a step of performing a desmear treatment using a desmear treatment liquid after the step (B) ( C) and
After the step (C), heating, supplying an acid or irradiating with radiation to convert the functional group from hydrophobic to hydrophilic (D);
A step (E) of applying a plating catalyst or a precursor thereof to the layer to be plated after the step (D);
A step of performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal layer on the layer to be plated in contact with the conductive layer through the via hole. And a method for producing a multilayer substrate.
The method for producing a multilayer substrate according to claim 1, wherein the functional group is a functional group that generates a carboxylic acid group, a sulfonic acid group, or a sulfinic acid group by heating, supply of an acid, or irradiation of radiation.
3. The method for producing a multilayer substrate according to claim 1, wherein the functional group has a group represented by any one of the following 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.
The functional group has a group represented by the general formula (1), a group represented by the general formula (2), or a group represented by the general formula (4). A method for producing a multilayer substrate.
The method for producing a multilayer substrate according to claim 3 or 4, wherein the functional group has a group represented by the general formula (1) or a group represented by the general formula (2).
The compound includes a polymer having the functional group and a crosslinkable group,
The multilayer substrate according to any one of claims 1 to 5, further comprising a step (G) of performing a curing process on the layer to be plated after the step (A) and before the step (E). Manufacturing method.
The method for producing a multilayer substrate according to claim 6, wherein the crosslinkable group is at least one group selected from the group consisting of an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group, an epoxy group, and an oxetanyl group.
The method for producing a multilayer substrate according to claim 6 or 7, wherein the plated layer further contains a crosslinking agent having a reactive functional group that reacts with the crosslinking group.
Before the step (A), the step (H) of forming an insulating layer on the surface of the substrate with the conductive layer on the conductive layer side is performed, and in the step (A), a layer to be plated is formed on the insulating layer. Then, in the step (B), the via hole is formed so as to penetrate the insulating layer and the layer to be plated and reach the conductive layer.
10. The method for manufacturing a multilayer substrate according to claim 1, further comprising a step (I) of forming the patterned metal layer by etching the metal layer into a pattern.
A multilayer substrate produced by the production method according to any one of claims 1 to 10.
A semiconductor package substrate comprising the multilayer substrate according to claim 11.
Crosslinking of a polymer having a functional group and a crosslinkable group that changes from hydrophobic to hydrophilic by heat, acid or radiation on the conductive layer side of a substrate with a conductive layer having a substrate and a conductive layer formed on the surface of the substrate A lower layer formed by a reaction, and an upper layer formed from a polymer that is disposed on the lower layer and has a functional group that changes from hydrophobic to hydrophilic by heat, acid, or radiation and does not have a crosslinkable group. A step (J) of forming a plated layer including:
After the step (J), a step (B) of forming a via hole so as to penetrate the plating layer and reach the conductive layer, and a step of performing a desmear treatment using a desmear treatment liquid after the step (B) ( C) and
After the step (C), heating, supplying an acid or irradiating with radiation to convert the functional group from hydrophobic to hydrophilic (D);
A step (K) of removing the upper layer after the step (D);
A step (E) of applying a plating catalyst or a precursor thereof to the layer to be plated after the step (K);
A step of performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal layer on the layer to be plated in contact with the conductive layer through the via hole. And a method for producing a multilayer substrate.