JP7208913B2 - Copper sulfate plating solution and copper sulfate plating method using the same - Google Patents

Description

The present invention relates to a copper sulfate plating solution containing a specific compound and a copper sulfate plating method using the same.

In recent years, electronic devices have become more compact, and printed wiring boards with fine and diverse wiring designs are in demand. An amine-containing compound that is usually used as a leveler is known as a component that suppresses plating (Patent Documents 1 to 5).

However, in order to uniformly form various wiring widths and fill vias, it is necessary to provide different suppression effects to each wiring width, peripheries and interiors of vias. For example, the periphery of the via exhibits a strong suppressive force, and if the suppressive effect is not exhibited inside the via, the plating preferentially deposits and fills the inside of the via. On the other hand, since the current concentrates in the wide portion and the isolated portion of the wiring, if the suppressing force is shown in the order of the wiring width and the density of the wiring, the plating will be uniform.

For this reason, it is extremely difficult for conventional amine-based levelers to distinguish between the above suppression points and to control the suppression force suitable for that point. Abnormalities in shape were caused, and conversely, filling of vias became insufficient even when wiring uniformity was achieved.

JP 2007-138265 A International publication WO2002/90623 pamphlet U.S. Pat. No. 7,374,652 JP-A-2003-13277 International publication WO2011/135716 pamphlet

An object of the present invention is to form wiring of various designs with a uniform thickness and to fill vias.

As a result of intensive research to solve the above problems, the present inventors have found that the above problems can be solved by using a specific compound that satisfies the formulas described below, and have completed the present invention.

で示される全原子数における窒素原子数の割合（Ｘ）と、相対分子量（Ｍｗ）が下記式（２）または（３）

を満たす化合物であることを特徴とする硫酸銅めっき液である。That is, the present invention is a copper sulfate plating solution containing a compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom,
The compound has the following formula (1) in the molecular formula excluding hydrogen atoms in the whole or repeating units

The ratio (X) of the number of nitrogen atoms in the total number of atoms represented by the relative molecular weight (Mw) is the following formula (2) or (3)

It is a copper sulfate plating solution characterized by being a compound that satisfies the following:

で示される全原子数における窒素原子数の割合（Ｘ）と、相対分子量（Ｍｗ）が下記式（２）または（３）

を満たすことを特徴とする化合物である。The present invention also provides a compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom,
The compound has the following formula (1) in the molecular formula excluding hydrogen atoms in the whole or repeating units

The ratio (X) of the number of nitrogen atoms in the total number of atoms represented by the relative molecular weight (Mw) is the following formula (2) or (3)

It is a compound characterized by satisfying

Further, the present invention is an additive for a copper sulfate plating solution containing the above compound.

Further, the present invention is a method for filling vias in an object to be plated, characterized in that the object to be plated having vias is treated with the copper sulfate plating solution.

Further, the present invention is a method for forming a circuit pattern on an object to be plated, characterized by treating the object to be plated having a circuit pattern with the copper sulfate plating solution.

According to the present invention, it is possible to form wirings of various designs with a uniform thickness, form circuit patterns, and fill vias.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram summarizing the results of Test Example 1 (in the figure, ◯ indicates an example, x indicates a comparative example, and the numbers on the upper right indicate the number of the example or the comparative example, respectively).

で示される全原子数における窒素原子数の割合（Ｘ：Ｎ率ともいう）と、相対分子量（Ｍｗ）が下記式（２）または（３）

を満たす化合物（以下、これを「本発明化合物」という）である。なお、Ｍｗの上限は特に限定されないが、例えば、５００,０００が好ましく、１００,０００がより好ましい。The compound contained in the copper sulfate plating solution of the present invention (hereinafter referred to as "the plating solution of the present invention") is a compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom, excluding hydrogen atoms in the whole or repeating units. In the molecular formula, the following formula (1)

The ratio of the number of nitrogen atoms in the total number of atoms represented by (X:N ratio) and the relative molecular weight (Mw) are expressed by the following formula (2) or (3)

(hereinafter referred to as "the compound of the present invention"). Although the upper limit of Mw is not particularly limited, for example, 500,000 is preferable, and 100,000 is more preferable.

The compound of the present invention is, for example, a compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom, and from among the molecular formulas excluding hydrogen atoms in the whole or repeating units, those satisfying the above requirements may be appropriately selected. Such compounds include, for example, a polymer of an amine compound and a carboxylic acid compound, a polymer of a vinyl compound or an allylamine compound with a vinyl compound or an allyl compound, a polymer of an amine compound and an epoxy compound, and Furthermore, adducts obtained by adding an alkyl group, an alkenyl group, an alkynyl group, or an aryl group are also included.

Among these compounds, a polymer of an amine compound and an epoxy compound is preferred. Such a polymer of an amine compound and an epoxy compound can be obtained, for example, by polymerizing an amine compound represented by the general formula (i) and an epoxy compound represented by the general formula (ii), and determining the relative molecular weight, for example, in the literature (Ash It can be obtained by controlling by a known method described in "Kendai Physics Koza 13 Macromolecules" written by Masao Sasa.

In formula (i), X represents a linear or cyclic alkyl, alkenyl, alkynyl, alkyl ether, or aromatic hydrocarbon, and said X is an amino group, a substituted amino group represented by —NR ₃ R ₄ , nitro group, hydroxy group, sulfo group and nitrile group, and R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, alkyl group having 1 to 9 carbon atoms, alkenyl, alkynyl or alkyl Ethers or aromatic hydrocarbons, each of which may have a nitro group, hydroxy group, sulfo group, nitrile group, or the like. Examples of the alkyl ethers include alkylene oxides and polyalkylene oxides. Examples of the aromatic hydrocarbon include phenyl and benzyl.

In formula (ii), Y represents a linear or cyclic alkyl, alkenyl, alkynyl, alkyl ether, aromatic hydrocarbon, glyceryl, or polyglyceryl, and Y represents a glycidyl group, a nitro group, a hydroxy group, a sulfo may have a group or a nitrile group. Examples of the alkyl ethers include alkylene oxides and polyalkylene oxides. Examples of the aromatic hydrocarbons include phenyl, bisphenol A, and the like.

As the polymer of the amine compound and the epoxy compound, for example, a polymer of the amine compound represented by the general formula (iii) and the epoxy compound represented by the general formula (iv) is more preferable.

式（iii）中、Ａは炭素数１～９のアルキル基、Ｂはヒドロキシル基あるいはＮＲ_７Ｒ_８で表されるアミノ基を示す。Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８はそれぞれ独立して水素、炭素数１～９のアルキル基、アルケニル、アルキニル、あるいはアルキルエーテル、あるいは芳香族炭化水素で、それぞれニトロ基、ヒドロキシ基、スルホ基、ニトリル基等を持っていても良い。前記アルキルエーテルおよび前記芳香族炭化水素としては、式（i）と同じものが挙げられる。

In formula (iii), A is an alkyl group having 1 to 9 carbon atoms, and B is a hydroxyl group or an amino group represented by NR ₇ R ₈ . R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, alkyl group having 1 to 9 carbon atoms, alkenyl, alkynyl or alkyl ether, or aromatic hydrocarbon, nitro group, hydroxy group, sulfo group, respectively. group, nitrile group, or the like. Examples of the alkyl ether and the aromatic hydrocarbon include the same as those of formula (i).

In the formula (iii), A is an alkyl group having 1 to 3 carbon atoms, B is a hydroxy group, R ₅ and R ₆ are an alkyl group having 1 to 3 carbon atoms and hydrogen, and furthermore, they each contain one or more hydroxy groups. or A is an alkyl group having 1 to 6 carbon atoms, B is NR ₇ R ₈ and R ₅ , R ₆ , R ₇ and R ₈ are alkyl groups having 1 to 3 carbon atoms. preferable.

式（iv）中、Ｚは炭素数１～１５の直鎖あるいは分岐アルキルあるいは環状アルキルで、前記Ｚはそれぞれグリシジル基あるいはヒドロキシル基を持っていても良く、ｍは１～９、好ましくは１～８、より好ましくは１～６の整数を示す。

In formula (iv), Z is a linear or branched alkyl or cyclic alkyl having 1 to 15 carbon atoms, each of said Z may have a glycidyl group or a hydroxyl group, m is 1 to 9, preferably 1 to 8, more preferably an integer from 1 to 6.

Among the formula (iv), Z is a linear alkyl having 2 to 6 carbon atoms and m is 1 to 9, or Z is a branched alkyl having 2 to 4 carbon atoms and m is 1 to 3, Preferably, these may have one or more glycidyl groups and/or hydroxy groups.

More specifically, the compounds of the present invention include the following (corresponding to the polymers obtained in Examples 1 to 8 in order from the top).

※これらの化合物におけるｎ、ｍ、ｏは任意の数であり、式（iv）のｍとは意味が異なる。

* n, m, and o in these compounds are arbitrary numbers and have different meanings from m in formula (iv).

Although the content of the compound of the present invention in the plating solution of the present invention is not particularly limited, it is, for example, 1 ppb or more, preferably 1 ppb to 100 ppm. The compound of the present invention functions as a leveler in the plating solution.

The plating solution of the present invention may contain sulfuric acid, copper, chlorine, etc., which are contained in conventionally known copper sulfate plating solutions. The content of sulfuric acid in the plating solution of the present invention is not particularly limited, but is, for example, 30 g/L or more, preferably 50 to 200 g/L.

The plating solution of the present invention preferably further contains a brightener. Although the type of brightener is not particularly limited, it contains, for example, one or more sulfur compounds such as sulfoalkylsulfonic acids or salts thereof and thiourea. The content of the brightener in the plating solution of the present invention is not particularly limited, but is preferably 0.1 mg/L or more, preferably 1 mg/L to 100 mg/L.

The plating solution of the present invention preferably further contains a carrier such as a surfactant. Although the type of surfactant is not particularly limited, examples thereof include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, alkyl or alkenyl, alkynyl, phenyl alcohol, glycerin, and alkylene oxide polymers of polyglycerin. The content of the carrier in the plating solution of the present invention is not particularly limited, but is preferably 1 mg/L or more, preferably 100 mg/L to 1000 mg/L.

The plating solution of the present invention may further contain metal salts other than copper such as iron sulfate, antioxidants such as catechol, and levelers other than the compounds of the present invention, as long as the effects of the present invention are not impaired.

Although the plating solution of the present invention may be prepared by mixing the above components, an additive for a copper sulfate plating solution containing the compound of the present invention is prepared and added to a separately prepared copper sulfate plating solution. You may The additives for the copper sulfate plating solution may contain brighteners, carriers, etc., if necessary.

The plating solution of the present invention can be used for copper sulfate plating according to a conventionally known method. Specifically, the object to be plated can be plated with copper sulfate by a method of treating the object to be plated with the plating solution of the present invention (hereinafter referred to as "the plating method of the present invention").

Objects to be plated that can be plated by the plating method of the present invention are not particularly limited, but for example, a printed wiring board in which a conductive layer such as metal is formed on a substrate made of resin, etc., and a circuit is patterned, a semiconductor substrate such as a silicon wafer, etc. is mentioned. Among these objects to be plated, those having vias and/or circuit patterns are preferred.

As described above, the plating method of the present invention is preferable for forming a circuit pattern on an object to be plated and for filling vias. Specifically, to fill the vias, plating may be performed at a current density equivalent to 1.5 A/dm ² for about 45 minutes at a solution temperature of about 25° C., although there is no particular limitation. Furthermore, during plating, it is preferable to agitate the solution by aeration, pump circulation, paddle agitation, or the like.

By the plating method of the present invention, it is possible to form wiring of various designs with a uniform thickness, form circuit patterns, and fill vias.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. In the following examples, relative molecular weights are values measured by gel permeation chromatography (GPC) using a TSKgel G3000PWXL-CP (manufactured by Tosoh Corporation) column using polyethylene glycol as a standard calibration sample. Further, the elemental analysis values are measured by the oxygen circulation combustion/TCD detection method for N, C, and H, the impulse heating/melting in inert gas-NDIR detection method for O, and the oxygen flask combustion/ion chromatography method for S. value.

Example 1
Preparation of compounds of the present invention (1):
The amine compound and the epoxy compound shown in Table 2 below are reacted as an aqueous solution of 10 wt% at the equivalent weight shown in Table 2 at 5°C for 0.5 hours and at 40°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. got Table 2 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer. The elemental analysis values are C: 50.8%, N: 2.7%, H: 9.0%, O: 33.3%, S: 2.9%, and S atoms are sulfate ions or hydrogen sulfate. Since it is derived from ions, the compositional formula excluding hydrogen atoms from which the hydrogen atoms were subtracted was C(4.23)N(0.193)O(1.74), and the N ratio could be calculated as 3.13. It was found that the N ratio calculated from this measured value has little error with the calculated value, and there is no problem in using the calculated value in practice.

Example 2
Preparation of compounds of the present invention (2):
The amine compound and epoxy compound shown in Table 3 below are reacted in an aqueous solution having an equivalent weight of 10 wt. Obtained. Table 3 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Example 3
Preparation of compounds of the present invention (3):
The amine compound and the epoxy compound shown in Table 4 below are reacted in an aqueous solution of 10 wt % equivalent weight shown in Table 4 at 5° C. for 0.5 hours and at 40° C. for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 4 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Example 4
Preparation of compounds of the invention (4):
The amine compound and the epoxy compound shown in Table 5 below are reacted in an aqueous solution of 10 wt % equivalent weight shown in Table 5 at 5° C. for 0.5 hours and at 40° C. for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 5 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Example 5
Preparation of compounds of the invention (5):
The amine compound and epoxy compound shown in Table 6 below are reacted in an aqueous solution having an equivalent weight of 10 wt. Obtained. Table 6 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer. The elemental analysis values are C: 45.3%, N: 2.7%, H: 7.4%, O: 36.6%, S: 2.5%, and S atoms are sulfate ions or hydrogen sulfate. Since it is derived from ions, the compositional formula excluding the subtracted hydrogen atoms was C(3.77)N(0.193)O(1.98), and the N ratio could be calculated as 3.25.

Example 6
Preparation of compounds of the invention (6):
The amine compound and epoxy compound shown in Table 7 below are reacted in an aqueous solution having an equivalent weight of 10 wt. Obtained. Table 7 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Example 7
Preparation of compounds of the invention (7):
The amine compound and the epoxy compound shown in Table 8 below are reacted in an aqueous solution of 10 wt% equivalent weight shown in Table 8 at 5°C for 0.5 hours and at 40°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 8 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 1
Preparation of Comparative Compound (1):
The amine compound and the epoxy compound shown in Table 9 below were reacted at 25° C. for 0.5 hour and at 97° C. for 3 hours as a 10 wt % aqueous solution at 1/2 equivalent weight shown in Table 9. After that, the remaining 1/2 equivalent of the amine compound and the epoxy compound was added and reacted at 105° C. for 30 minutes to obtain a polymer of the amine compound and the epoxy compound. Table 9 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 2
Preparation of Comparative Compound (2):
The amine compound and epoxy compound shown in Table 10 below are reacted in an aqueous solution of 10 wt % equivalent weight shown in Table 10 at 5° C. for 0.5 hours and at 98° C. for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 10 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 3
Preparation of Comparative Compound (3):
The amine compound and epoxy compound listed in Table 11 below were reacted at 25° C. for 0.5 hour and at 97° C. for 3 hours as a 10 wt % aqueous solution at 1/2 equivalents listed in Table 11. After that, the remaining 1/2 equivalent of the amine compound and the epoxy compound was added and reacted at 105° C. for 30 minutes to obtain a polymer of the amine compound and the epoxy compound. Table 11 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 4
Preparation of Comparative Compound (4):
The amine compound and the epoxy compound shown in Table 12 below are reacted in an aqueous solution of 10 wt% equivalent weight shown in Table 12 at 5°C for 0.5 hours and at 40°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 12 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 5
Preparation of Comparative Compound (5):
A polyallylamine compound (PAS-24) manufactured by Nittobo Medical Co., Ltd. described in Table 13 below was used. The N ratio and relative molecular weight (Mw) are also shown in Table 13.

Comparative example 6
Preparation of Comparative Compound (6):
The amine compound and the epoxy compound shown in Table 14 below are reacted as an aqueous solution of 10 wt% in equivalent weight shown in Table 14 at 5°C for 0.5 hours and at 40°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 14 also shows the N ratio and relative molecular weight (Mw) of the obtained polymer.

Comparative example 7
Preparation of Comparative Compound (7):
The amine compound and the epoxy compound shown in Table 15 below are reacted as an aqueous solution of 10 wt% in equivalent weight shown in Table 15 at 5°C for 0.5 hours and at 40°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. Obtained. Table 15 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 8
Preparation of Comparative Compound (8):
The amine compound and the epoxy compound shown in Table 16 below are reacted as an aqueous solution of 10 wt% equivalent weight shown in Table 16 at 5°C for 0.5 hours and at 25°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. got Table 16 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Comparative example 9
Preparation of Comparative Compound (9):
The amine compound and the epoxy compound shown in Table 17 below are reacted as an aqueous solution of 10 wt% in equivalent weight shown in Table 17 at 5°C for 0.5 hours and at 25°C for 3 hours to obtain a polymer of the amine compound and the epoxy compound. got Table 17 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Example 8
Preparation of compounds of the invention (8):
The amine compound and the epoxy compound shown in Table 18 below are reacted in the equivalent amounts shown in Table 18 as a 10 wt% aqueous solution at 5°C for 0.5 hours and at 40°C for 3 hours to polymerize the amine compound and the epoxy compound. got stuff Table 18 also shows the N ratio and relative molecular weight (Mw) of the resulting polymer.

Test example 1
Plating test:
5 to 30 mg/L of the compounds prepared in Examples 1 to 8 were added to copper sulfate plating solutions having compositions shown in Table 19, respectively, to prepare copper sulfate plating solutions of the present invention. In these copper sulfate plating solutions, 30/150, 15/150, 9/150 using a resin substrate having a blind via hole with an opening diameter of φ60 μm and a depth of 35 μm and a DFR with a thickness of 25 μm subjected to electroless copper plating. , 30/30, 15/15, and 9/9, and copper sulfate plating was performed under the following conditions. The substrate after plating was evaluated for filling property and maximum film thickness difference as follows. Those results are shown in Table 20. For comparison, copper sulfate plating solutions containing the compounds prepared in Comparative Examples 1 to 9 were prepared, and the same copper sulfate plating was performed and evaluated. Those results are shown in Table 21.

ＳＰＳ：ビス―（３－ナトリウムスルホプロピル）ジスルフィド
ＰＥＧ：ポリエチレングリコール（分子量４０００）
ＰＯ：グリセリンのポリプロピレングリコール付加物（分子量７００）<Copper sulfate plating solution composition>

SPS: bis-(3-sodium sulfopropyl) disulfide PEG: polyethylene glycol (molecular weight 4000)
PO: Polypropylene glycol adduct of glycerin (molecular weight 700)

<Copper sulfate plating conditions>
Current density: 1.65A/ ^dm2
Time: 45 minutes Bath volume: 500 mL
Stirring: Aeration 1.5 L/min

<Filling property evaluation criteria>
The amount of depression (μm) above the filled via hole was measured using a three-dimensional white light interference microscope. The amount of dent was designated as ○ within 5 μm, and × as 5 μm or more.

<Maximum film thickness difference evaluation criteria>
The circuit height of each wiring width was measured using a three-dimensional white light interference microscope. The maximum film thickness difference between the maximum height and the minimum height was defined as the maximum film thickness difference.

A summary of the above results is shown in FIG. From these results, it was shown that by including the compound of the present invention in the copper sulfate plating solution, wiring of various designs can be formed with a uniform thickness and vias can be filled. On the other hand, even if the compound contains at least a nitrogen atom, a hydrogen atom, and a carbon atom, if X and Mw do not fall within the scope of the compound of the present invention, it is not possible to form wiring of various designs with a uniform thickness, and it is impossible to fill vias. was also shown

INDUSTRIAL APPLICABILITY The present invention can be used to manufacture printed wiring boards and the like because it is possible to form wiring of various designs with a uniform thickness, form circuit patterns, and fill vias.

that's all

Claims (9)

A copper sulfate plating solution containing a compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom,
The compound has the following formula (1) in the molecular formula excluding hydrogen atoms in the whole or repeating units

The ratio (X) of the number of nitrogen atoms in the total number of atoms represented by the relative molecular weight (Mw) is the following formula (2) or (3)

is a compound that satisfies
The compound is a polymer of an amine compound and an epoxy compound,
A polymer of the amine compound and the epoxy compound is an amine compound represented by formula (iii);

(In formula (iii), A is an alkyl group having 1 to 6 carbon atoms, B is NR ₇ R ₈ , and R ₅ , R ₆ , R ₇ and R ₈ are alkyl groups having 1 to 3 carbon atoms.)
with an epoxy compound represented by formula (iv),

(In formula (iv), Z is a linear alkyl having 2 to 6 carbon atoms and m is an integer of 1 to 9, or Z is a branched alkyl having 2 to 4 carbon atoms and m is an integer of 1 to 3 and they may also have one or more glycidyl groups and/or hydroxy groups.)
A copper sulfate plating solution characterized by being a polymer. A copper sulfate plating solution containing a compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom,
The compound has the following formula (1) in the molecular formula excluding hydrogen atoms in the whole or repeating units

The ratio (X) of the number of nitrogen atoms in the total number of atoms represented by the relative molecular weight (Mw) is the following formula (2) or (3)

is a compound that satisfies
The compound is a polymer of an amine compound and an epoxy compound,
The polymer of the amine compound and the epoxy compound is the following (a) to (h)
(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

A copper sulfate plating solution characterized by being any one of a polymer of an amine compound and an epoxy compound described in . A compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom,
The compound has the following formula (1) in the molecular formula excluding hydrogen atoms in the whole or repeating units

The ratio (X) of the number of nitrogen atoms in the total number of atoms represented by the relative molecular weight (Mw) is the following formula (2) or (3)

A compound that satisfies
The compound is a polymer of an amine compound and an epoxy compound,
A polymer of the amine compound and the epoxy compound is an amine compound represented by formula (iii);

(In formula (iii), A is an alkyl group having 1 to 6 carbon atoms, B is NR ₇ R ₈ , and R ₅ , R ₆ , R ₇ and R ₈ are alkyl groups having 1 to 3 carbon atoms.)
with an epoxy compound represented by formula (iv),

(In formula (iv), Z is a linear alkyl having 2 to 6 carbon atoms and m is an integer of 1 to 9, or Z is a branched alkyl having 2 to 4 carbon atoms and m is an integer of 1 to 3 and they may also have one or more glycidyl groups and/or hydroxy groups.)
A compound characterized by being a polymer. A compound containing at least a nitrogen atom, a hydrogen atom, and a carbon atom,
The compound has the following formula (1) in the molecular formula excluding hydrogen atoms in the whole or repeating units

The ratio (X) of the number of nitrogen atoms in the total number of atoms represented by the relative molecular weight (Mw) is the following formula (2) or (3)

is a compound that satisfies
The compound is a polymer of an amine compound and an epoxy compound,
The polymer of the amine compound and the epoxy compound is the following (a) to (h)
(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

A compound characterized by being any polymer of an amine compound and an epoxy compound described in . An additive for a copper sulfate plating solution containing the compound according to claim 3 or 4 . A copper sulfate plating method for an object to be plated, comprising treating the object to be plated with the copper sulfate plating solution according to claim 1 or 2 . 7. The method of copper sulfate plating on an object to be plated according to claim 6 , wherein the object to be plated has vias and/or circuit patterns. A method of filling vias in an object to be plated, comprising treating an object to be plated having vias with the copper sulfate plating solution according to claim 1 or 2 . A method for forming a circuit pattern on an object to be plated, comprising treating an object to be plated having a circuit pattern with the copper sulfate plating solution according to claim 1 or 2 .

Images