KR102582786B1 - Electrolytic plating solution additives and their uses - Google Patents

Abstract

In the additive for electrolytic plating solution containing a diallylamine-based (co)polymer, the organic nature of the entire polymer is improved while maintaining the metal affinity of the diallylamine-based (co)polymer, and the uniform electrodeposition over a wide current range is achieved. Provided is an additive for an electrolytic plating solution that can improve electrodeposition properties, particularly in a high current region. The problem is to provide an electrolytic plating solution additive containing a diallylamine-based (co)polymer having a structural unit (I) derived from a diallylamine-based compound (i) having a structure represented by the following general formula (1):

(However, in the above formula (1), R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, provided that R ¹ and R ² are not hydrogen at the same time, and R ³ and R ⁴ are, each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.).

Description

Electrolytic plating solution additives and their uses

The present invention relates to an electrolytic plating solution additive containing a diallylamine-based (co)polymer having a structural unit having a specific structure and its use, and more specifically, to a composition derived from a diallylamine-based compound having a specific structure. By having a unit, an electrolytic plating solution additive that can improve the organic nature of the entire polymer while maintaining metal affinity and can significantly improve the throwing power in electrolytic plating, an electrolytic plating solution containing the same, and an electrolytic plating solution using the same It relates to a method of manufacturing an electrolytic plating attachment member.

Diallylamine-based (co)polymers having structural units derived from diallylamine-based compounds such as diallyldialkylammonium chloride, diallylalkylamine hydrochloride, and diallyldialkylammonium alkyl sulfate, and these diallylamine-based The copolymer of the compound and sulfur dioxide has metal affinity derived from the ammonium group and organicity derived from the polymer main chain, and can stabilize the metal surface, so it is used for the purpose of improving the throwing power in electrolytic plating, etc. , is used as an electrolytic plating solution additive (for example, see Patent Document 1 and Patent Document 2).

There is a need to further improve the performance of such diallylamine-based (co)polymers as an electrolytic plating solution additive. For example, if leveling performance at high current density can be improved, it becomes possible to set the operating current range high, shorten the time required to obtain the target film thickness, and improve the productivity of the plating process. . Methods for improving the performance of electrolytic plating solution additives include changing the chain length of the alkyl group, copolymerizing a third component, and changing the addition salt.

The method of changing the chain length of the alkyl group is mainly carried out for the purpose of improving the organic nature of the entire polymer. However, if the chain length is increased, the polymerization property deteriorates extremely and no significant performance improvement is observed. This may be due to the fact that the extended alkyl group inhibits the reactivity of the ammonium group, which electrochemically affects the formed plating film.

In the method of copolymerizing the third component, there are few monomers with excellent copolymerizability, and when, for example, sulfur dioxide is copolymerized, depolymerization of the synthesized high molecular weight body is likely to occur due to the electron-withdrawing property of the sulfonyl group, and stability is deteriorated. There is. In addition, the options for addition salts were limited, and there were certain limits to the change in performance just by changing them.

Japanese Patent Publication No. 2008-88524 Japanese Patent Publication No. 2006-45621

In view of the limitations of the above background technology, the present invention provides an additive for an electrolytic plating solution containing a diallylamine-based (co)polymer, which maintains the metal affinity of the diallylamine-based (co)polymer while maintaining the metal affinity of the diallylamine-based (co)polymer. The task is to realize an additive for plating solution that can improve the organic properties of and improve the spreading properties over a wide current range, especially in the high current range.

As a result of intensive studies to solve the above problems, the present inventors have found that diallylamine-based compounds having structural units with a specific structure, more specifically, at least one methallyl group or 2-alkylamine-based compound such as allylmethallyldialkyl ammonium salt, etc. By polymerizing a diallylamine-based compound having a methylene butane group, a diallylamine-based (co)polymer with improved organic properties of the entire polymer while maintaining metal affinity is obtained, and the diallylamine-based (co)polymer is By using an electrolytic plating solution containing additives, it was discovered that the throwing power in a wide current range, especially in a high current range, could be improved, and the present invention was completed.

That is, the present invention relates to the following [1].

[One]

An electrolytic plating solution additive containing a diallylamine-based (co)polymer having a structural unit (I) derived from a diallylamine-based compound (i) having a structure represented by the following general formula (1).

[Formula 1]

(However, in the above formula (1), R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, provided that R ¹ and R ² are not hydrogen at the same time, and R ³ and R ⁴ are, Each is independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.)

Hereinafter, [2] to [8] are each one of the preferred embodiments of the present invention.

[2]

The electrolytic plating solution additive according to [1], wherein the diallylamine-based compound (i) has a structure represented by the following general formula (1').

[Formula 2]

(However, in the above formula (1'), R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.)

[3]

The electrolytic plating solution additive according to [1] or [2], wherein the diallylamine-based (co)polymer further has structural unit (II) derived from sulfur dioxide.

[4]

The electrolytic plating solution additive according to any one of [1] to [3], wherein the proportion of structural unit (I) among all structural units of the diallylamine-based (co)polymer is 10 mol% or more.

[5]

An electrolytic plating solution containing the electrolytic plating solution additive according to any one of [1] to [4].

[6]

The electrolytic plating solution according to [5], further containing a copper compound.

[7]

A method for producing an electrolytic plated member, comprising the step of immersing the member in the electrolytic plating solution according to [5] or [6] and depositing a metal on the member.

[8]

The method for manufacturing an electrolytic plating attachment member according to [7], wherein the electrolytic plating attachment member is an electrical and electronic component.

According to the present invention, an additive for an electrolytic plating solution is provided that can improve the spreading uniformity in a wide current range, especially in a high current range, and provides the additive required to obtain the target film thickness while maintaining plating quality such as uniformity. By shortening the time, a remarkable technical effect of high practical value, such as improving the productivity of the electrolytic plating process, is realized. In addition, this excellent throwing power is also advantageous when performing electrolytic plating on a member of a complex shape or when filling non-penetrating holes with metal plating.

The electrolytic plating solution, which is a preferred form of the present invention, and the method for producing the electrolytic plating attachment member also realize the same remarkable technical effects of high practical value as described above.

Figure 1 is a GPC chart of the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide obtained in Synthesis Example 1.
Figure 2 is an infrared spectral diagram of the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide obtained in Synthesis Example 1.
Figure 3 is a GPC chart of the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide obtained in Synthesis Example 2.
Figure 4 is an infrared spectral diagram of the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide obtained in Synthesis Example 2.
Figure 5 is a GPC chart of the copolymer of allylmethallyldiethylammonium chloride and sulfur dioxide obtained in Synthesis Example 3.
Figure 6 is an infrared spectral diagram of the copolymer of allylmethallyldiethylammonium chloride and sulfur dioxide obtained in Synthesis Example 3.
Figure 7 is a schematic diagram of the appearance of the test piece for the hull cell test used in Examples 1 to 2 and Comparative Examples 1 to 3.
Figure 8 is a photograph showing the results of the Hull cell test of Example 1.
Figure 9 is a photograph showing the results of the Hull cell test of Example 2.
Figure 10 is a photograph showing the results of the Hull cell test of Comparative Example 1.
Figure 11 is a photograph showing the results of the Hull cell test of Comparative Example 2.
Figure 12 is a photograph showing the results of the Hull cell test of Comparative Example 3.

Component unit (Ⅰ)

The electrolytic plating solution additive of the present invention contains a diallylamine-based (co)polymer having a structural unit (I) derived from a diallylamine-based compound (i) having a structure represented by the following general formula (1).

[Formula 3]

However, in the above formula (1), R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, provided that R ¹ and R ² are not hydrogen at the same time, and R ³ and R ⁴ are each It is independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.

The term “(co)polymer” in the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention indicates that it may be a homopolymer or a copolymer, and therefore, the diallylamine of the first invention of the present application The system (co)polymer may be composed only of the structural unit (I) derived from the diallylamine-based compound (i) of the structure represented by the above general formula (1), or may contain other structures in addition to the structural unit (I). It may further have a structural unit having, for example, a structural unit (II) derived from sulfur dioxide.

(i) Diallylamine-based compounds

The structural unit (Ⅰ) constituting all or part of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention is derived from the diallylamine-based compound (i) having a structure represented by the following general formula (1): It is induced.

[Formula 4]

In the general formula (1), R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms. However, R ¹ and R ² are not hydrogen at the same time, and in this respect, it is different from diallylamine-based compounds used in the prior art.

R ¹ and R ² are not hydrogen at the same time, and therefore at least one of R ¹ and R ² is an alkyl group having 1 to 2 carbon atoms, so that the organic nature of the entire polymer can be improved, and the throwing power in electrolytic plating can be improved. Significant technical effects, such as significant improvements, can be realized. From the viewpoint of improving the organic nature of the entire polymer, R ¹ and R ² are preferably large groups as long as they satisfy the above conditions and do not inhibit the reactivity of the ammonium group.

On the other hand, from the viewpoint of polymerizability of the diallylamine-based (co)polymer, it is preferable that only one of R ¹ and R ² is an alkyl group, and in particular, one of R ¹ and R ² is a methyl group and the other is hydrogen. desirable.

R ³ and R ⁴ are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms. Examples of the alkyl group having 1 to 2 carbon atoms include methyl group and ethyl group.

Since R ³ and R ⁴ are relatively small groups such as hydrogen or an alkyl group having 1 to 2 carbon atoms, R ³ and R ⁴ are suppressed from inhibiting the electrochemical reactivity of the ammonium group, thereby maintaining sufficient metal affinity as an electrolytic plating solution additive. You can. In addition, it is advantageous in terms of polymerizability, and the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention can be polymerized with high quantitativeness sufficient for practical use.

On the other hand, from the viewpoint of improving the organic nature of the polymer as a whole, R ³ and R ⁴ are preferably large groups, as ^long as they satisfy the conditions ^of the first invention and do not inhibit the reactivity of the ammonium group, and the It is particularly preferable that both are methyl groups or ethyl groups.

In the above general formula (1), X ^- is a counter ion. X ^- may be an anion, and there are no other restrictions, but it is preferably an anion derived from an organic acid or an inorganic acid. For example, halogen ions such as Cl ^- , Br ^- , I ^{- ,} sulfonic acid ions such as methanesulfonate ion, ethanesulfonate ion, and propanesulfonate ion, and alkyl ions such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion. Sulfate ions, acetic acid ions, etc. can be preferably used.

(i') Allylmethallylamine compound

From the viewpoint of polymerizability, etc., it is preferable to use an allylmethallylamine compound (i') having a structure represented by the following general formula (1') as the diallylamine compound (i).

[Formula 5]

In the general formula (1'), R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms. Examples of the alkyl group having 1 to 2 carbon atoms include methyl group and ethyl group.

Since R ⁵ and R ⁶ are each relatively small groups such as hydrogen or an alkyl group having 1 to 2 carbon atoms, R ⁵ and R ⁶ are suppressed from inhibiting the electrochemical reactivity of the ammonium group, and the diallylamine system of the present embodiment (co. ) The polymer can be polymerized with high quantification that is sufficient for practical use.

On the other hand, from the viewpoint of improving the organic nature of the entire polymer, it is preferable that R ⁵ and R ⁶ are large groups, as long as they satisfy the above conditions and do not inhibit the electrochemical reactivity of the ammonium group, and both R ⁵ and R ⁶ This methyl group or ethyl group is particularly preferable.

In the general formula (1'), X ^- is a counter ion. X ^- may be an anion, and there are no other restrictions, but it is preferably an anion derived from an organic acid or an inorganic acid. For example, halogen ions such as Cl ^- , Br ^- , I ^{- ,} sulfonic acid ions such as methanesulfonate ion, ethanesulfonate ion, and propanesulfonate ion, and alkyl ions such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion. Sulfate ions, acetic acid ions, etc. can be preferably used.

The allylmethallylamine-based compound (i') has one allyl group bonded to a nitrogen atom and one methallyl group, as shown in the general formula (1'). By having one allyl group and one methallyl group, the organic nature of the entire polymer can be improved compared to the diallylamine-based (co)polymer of the prior art using a diallylamine-based compound having two allyl groups.

On the other hand, by having one allyl group and one methallyl group, polymerization can be performed with higher quantitative performance and the reactivity of the ammonium group can be improved.

Other constituent units

The diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention has other structures in addition to the structural unit (Ⅰ) derived from the diallylamine-based compound (i) having the structure represented by the general formula (1) above. It may have a structural unit with .

There is no particular limitation on the structural unit having a different structure, and other monomers copolymerizable with the diallylamine-based compound (i) can be appropriately used to the extent that it does not conflict with the purpose of the present invention and the use as an electrolytic plating solution additive, and a different structure can be formed. A structural unit having can be introduced. By introducing a structural unit having an appropriate different structure, the polymerizability of the allylmethallylamine-based copolymer of the present embodiment can be improved, or the characteristics of the copolymer can be controlled to some extent.

Representative examples of other monomers copolymerizable with the diallylamine compound (i) include sulfur dioxide, diallylamine compounds other than the diallylamine compound (i) (i.e., compounds having a diallylamine skeleton), and Examples include cationic monomers including salts, dicarboxylic acids, unsaturated carboxylic acids, anionic monomers including unsaturated sulfonic acids and their salts, and (meth)acrylamide-based monomers, but are not limited to these.

Examples of diallylamine-based compounds and salts thereof other than the allylmethallylamine-based compound (i) include quaternary ammoniums such as diallyldimethylammonium, diallylmethylethylammonium, and diallyldiethylammonium, diallylamine, and diallylamine. Examples include sulfonate salts or alkyl sulfate salts of allylmethylamine, diallylethylamine, or diallylpropylamine. Also, diallyl dimethyl ammonium methyl sulfate, diallyl ethyl methyl ammonium methyl sulfate, diallyl diethylammonium methyl sulfate, diallyl dimethyl ammonium ethyl sulfate, diallyl ethyl methyl ammonium ethyl sulfate, diallyl diethylammonium. Ethyl sulfate, diallylamine, diallylmethylamine, diallylethylamine, and diallylpropylamine can also be exemplified.

Examples of the dicarboxylic acids and salts thereof include itaconic acid, citraconic acid, mesaconic acid, maleic acid, fumaric acid, and methylenemalonic acid, and all or part of the hydrogen in these carboxyl groups is Na, K, NH ₄ , 1/ Examples include compounds substituted with at least one selected from 2Ca, 1/2Mg, 1/2Fe, 1/3Al and 1/3Fe. Examples of the unsaturated carboxylic acids, unsaturated sulfonic acids and salts thereof include metal salts such as (meth)acrylic acid, (meth)allylsulfonic acid, and Na salts thereof.

The diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention has other structures in addition to the structural unit (Ⅰ) derived from the diallylamine-based compound (i) having the structure represented by the general formula (1) above. There is no particular limitation on the ratio of structural unit (I) in the embodiment having the structural unit with , it is preferable that it accounts for 10 mol% or more of the total structural units.

The proportion of structural unit (I) in the total structural units of the diallylamine-based (co)polymer of the present embodiment is more preferably 20 mol% or more, and particularly preferably 50 mol% or more.

There is no particular upper limit to the proportion of structural unit (Ⅰ) in the total structural units of the diallylamine-based (co)polymer of the present embodiment, and therefore, there is no problem even if the entire structural unit is structural unit (Ⅰ). For example, For example, if it is 90 mol% or less, it is preferable because polymerization becomes easier.

(Ⅱ) Constituent units derived from sulfur dioxide

As a structural unit having a structure other than structural unit (I), structural unit (II) derived from sulfur dioxide is particularly preferable.

Since sulfur dioxide is relatively easy to copolymerize with the diallylamine-based compound (i) having the structure represented by the above general formula (1), by introducing the structural unit (II) derived from sulfur dioxide, the allylmethallylamine-based compound of the present embodiment is obtained. The copolymer can be polymerized relatively easily or with a relatively narrow molecular weight distribution by appropriately setting the copolymerization ratio.

Structural unit (II) in the diallylamine-based (co)polymer in the present embodiment is derived from sulfur dioxide having a structure represented by the following structural formula (2).

[Formula 6]

The proportion of the structural unit (II) derived from sulfur dioxide in the total structural units of the diallylamine-based (co)polymer in the present embodiment is preferably 10 mol% or more. In particular, when the proportion of structural unit (II) derived from sulfur dioxide is 40 mol% or more, the diallylamine-based copolymer in this embodiment can be polymerized relatively easily and with a relatively narrow molecular weight distribution.

The proportion of structural unit (II) derived from sulfur dioxide is more preferably 10 mol% or more, and particularly preferably 40 mol% or more.

There is no particular upper limit to the proportion of structural unit (II) derived from sulfur dioxide, but from the viewpoint of ensuring room for the presence of structural unit (I) to realize the effect of the present invention, it is usually 60 mol% or less, and is preferably It is 50 mol% or less.

There is no particular limitation on the ratio of the structural unit (I) derived from the diallylamine-based compound (i) and the structural unit (II) derived from sulfur dioxide in the diallylamine-based copolymer in the present embodiment. It can be done at any ratio if possible. From the viewpoint of increasing the molecular weight of the copolymer, it is preferable that the number of both structural units is not significantly different, for example, structural unit (Ⅰ) derived from diallylamine-based compound (i) and structural unit (Ⅰ) derived from sulfur dioxide. The ratio of unit (II) is preferably 0.7:1 to 1.3:1. The ratio is more preferably 0.8:1 to 1.2:1, and particularly preferably 0.9:1 to 1.1:1.

The diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention preferably has a weight average molecular weight Mw of 1000 or more, or a degree of polymerization of 5 or more, as determined by GPC measurement. The reason for saying “or” is that since there is a close relationship between the weight average molecular weight and the degree of polymerization, it is not necessarily necessary to evaluate all of these physical properties, and evaluating any one may be sufficient.

There is no particular limitation on the weight average molecular weight Mw of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention, but it is preferably 1000 or more because it is suitable for use as an electrolytic plating solution additive.

In an attempt to improve the organic nature of the entire polymer, the diallylamine-based (co)polymer of the prior art in which the chain length of the alkyl group in the diallylamine-based compound is extended is poor in polymerizability, so the weight average molecular weight Obtaining a diallylamine-based (co)polymer with a Mw of 1000 or more was not necessarily easy.

The weight average molecular weight Mw of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention is more preferably 1,000 to 1,000,000, and even more preferably 1,000 to 300,000.

The weight average molecular weight Mw of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention can be measured by gel permeation chromatography (GPC method), and more specifically, for example, in this application. It can be measured by the method described in the examples.

There is no particular limitation on the degree of polymerization of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention, but, like the weight average molecular weight Mw, the polymerization degree is preferably 5 or more from the viewpoint of being suitable for use as an electrolytic plating solution additive.

In an attempt to improve the organic nature of the entire polymer, conventional diallylamine-based (co)polymers in which the chain length of the alkyl group in the diallylamine-based compound is extended are poor in polymerizability, so the degree of polymerization is 5 or higher. Obtaining a diallylamine-based (co)polymer is not necessarily easy.

The degree of polymerization of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention is more preferably 5 to 300, further preferably 5 to 200, and especially preferably 5 to 300.

The degree of polymerization of the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention can be obtained from the weight average molecular weight obtained by the GPC method above using the following calculation formula.

Degree of polymerization = weight average molecular weight/unit molecular weight

Here, the unit molecular weight (unit M _W ) is the molecular weight per unit of repeating unit in the polymer. When the polymer is a copolymer, that is, when the polymer has two or more types of structural units derived from different monomers, the molecular weight and ratio of each structural unit are multiplied (the total is 1), and then the weighted average of these is calculated. , is taken as the unit molecular weight.

By dividing the weight average molecular weight by this unit molecular weight, the degree of polymerization (average number of repeating units) can be obtained.

There is no particular limitation on the method for producing the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention, but for example, it is preferable to produce it by the following method.

(Method for producing diallylamine-based (co)polymer)

A method for producing the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention includes the step of polymerizing a monomer raw material containing a diallylamine-based compound (i) having a structure represented by the following general formula (1): It is preferable to use a method for producing a diallylamine-based (co)polymer.

[Formula 7]

(However, in the above formula (1), R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, provided that R ¹ and R ² are not hydrogen at the same time, and R ³ and R ⁴ are, Each is independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.)

According to the above method, diallylamine-based (co)polymers with high organicity of the entire polymer, including the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention, can be polymerized with high quantitative accuracy.

The diallylamine-based compound (i) having the structure represented by the general formula (1) in the above production method is the same as that already described in relation to the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention. do.

The monomer raw material to be polymerized in the above production method contains the diallylamine-based compound (i). Therefore, the monomer raw material may be composed only of the diallylamine-based compound (i), or may contain other copolymerizable monomers in addition to the diallylamine-based compound (i). Here, other copolymerizable monomers are the same as those described in “Other structural units” above in relation to the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention.

Also in the above production method, it is preferable to use sulfur dioxide as another copolymerizable monomer.

When the monomer raw material contains other copolymerizable monomers in addition to the diallylamine compound (i), the proportion of the diallylamine compound (i) in the monomer raw material is preferably 10 mol% or more.

A preferable diallylamine system in which the proportion of the diallylamine-based compound (i) in the monomer raw material is 10 mol% or more, and the proportion of structural unit (I) derived from the diallylamine-based compound (i) is 10 mol% or more. (Co)polymers can be produced more efficiently.

In the above production method, the degree of polymerization in the step of polymerizing the monomer raw material containing the diallylamine compound (i) is preferably 5 or more. When the degree of polymerization in this process is 5 or more, a diallylamine-based (co)polymer with a molecular weight suitable for use as an electrolytic plating solution additive can be obtained.

The degree of polymerization in the above step is more preferably 5 to 100, further preferably 5 to 200, and particularly preferably 5 to 300.

In order to improve polymerizability and to set the degree of polymerization in the above step to 5 or more, an allylmethallylamine-based compound (i') having a structure represented by the following general formula (1') is used as a diallylamine-based compound (i'). It is desirable to use .

[Formula 8]

(However, in the above formula (1'), R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.)

The details of the allylmethallylamine-based compound (i') having the structure represented by the following general formula (1') are the same as those described above with respect to the diallylamine-based (co)polymer constituting the electrolytic plating solution additive of the present invention. same.

In the above production method, it is preferable that the yield in the step of polymerizing the monomer raw material containing the diallylamine compound (i) is 70% or more. When the yield in this process is 70% or more, a diallylamine-based (co)polymer with high organicity of the entire polymer can be produced more efficiently.

Also from the viewpoint of improving yield, it is preferable to use an allylmethallylamine-based compound (i') having a structure represented by the above general formula (1') as the diallylamine-based compound (i').

In the above production method, the yield in the step of polymerizing the monomer raw material containing the diallylamine compound (i) is more preferably 60% or more, and particularly preferably 80% or more.

In the above production method, the conditions of the process for polymerizing the monomer raw material containing the diallylamine compound (i), i.e., solvent, monomer concentration, temperature, pressure, time, etc., are similar to those of the conventional diallylamine compound (i). It is possible to apply the conditions used in the production of the polymer, and can be appropriately adopted from these.

As a solvent during polymerization, a polar solvent such as water is preferably used. Polar solvents other than water include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid or their aqueous solutions, organic acids such as formic acid, acetic acid, propionic acid, and lactic acid or their aqueous solutions, alcohols, dimethyl sulfoxide, and dimethylformamide. , and further aqueous solutions of inorganic salts such as zinc chloride, calcium chloride, and magnesium chloride, etc., but are not limited to these.

The concentration of the monomer varies depending on the type of monomer, solvent, or dispersion medium, but is usually 5 to 95 mass%, and 10 to 70 mass% is preferable.

In the production method of this embodiment, it is preferable to use a polymerization initiator. Examples of preferred polymerization initiators include ammonium persulfate, 2,2'-azobis(2-methylpropionamidine), 2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionate), 2,2'-azobis [2-(2-imidazoline-2-yl)propane] and the like.

There is no particular limitation on the amount of the polymerization initiator used, and it can be appropriately set from the viewpoint of reaction speed, reaction stability, etc., but it is preferable to use 0.1 to 30% by mass, and 1 to 10% by mass relative to the total mass of monomers. Particularly desirable.

The polymerization temperature is generally 0 to 100°C, preferably 5 to 80°C, and the polymerization time is generally 20 to 150 hours, preferably 30 to 100 hours. Polymerization is carried out in an atmosphere of an inert gas such as nitrogen, although it does not cause any major problems in polymerization even in the air.

The (co)polymer obtained as a result of the step of (co)polymerizing the monomer raw material containing the diallylamine-based compound (i) is subjected to separation and washing treatment as necessary, and the (co)polymer is converted to diallylamine. It is recovered as a system (co)polymer. The (co)polymer may be recovered as a solid content, or may be recovered as a solution or dispersion.

Electrolytic plating solution additives

The above-described diallylamine-based (co)polymer has high organicity throughout the polymer, has a sufficient molecular weight, and sufficiently maintains the reactivity of the ammonium group. Therefore, the diallylamine-based (co)polymer has a high level of compatibility with the organic nature of the polymer as a whole and metal affinity, and when used as an electrolytic plating solution additive, it adsorbs to the convexities on the surface of the plated body and forms the convexities. It is excellent in the flattening effect that suppresses plating precipitation, and can significantly improve the throwing power in electrolytic plating over a wide current density range.

The throwing power in electrolytic plating can be evaluated by a Hull cell test, and more specifically, for example, by a Hull cell test under the conditions described in the examples of this application.

The electrolytic plating solution additive of the present invention can be added to the electrolytic plating solution in an amount of usually 0.01 to 250 ppm by mass, preferably 0.1 to 100 ppm by mass, based on the mass of the diallylamine-based (co)polymer. . Here, since the addition amount is 0.01 mass ppm or more, the plating surface can be sufficiently flattened. Additionally, since the amount used is 250 ppm by mass or less, no improvement in the selective suppression effect is observed.

The electrolytic plating solution using the electrolytic plating solution additive of the present invention is not particularly limited and includes copper plating, silver plating, gold plating, partial gold plating, zinc plating, black chrome plating, hard chrome plating, glossy nickel-tin cobalt alloy plating, and glossy plating. It can be preferably used in various electrolytic plating solutions such as nickel-chromium plating, tin plating, nickel-tin plating, and nickel plating, but it can be especially preferably used in so-called electrolytic copper plating solutions containing a copper compound.

As components other than the electrolytic plating solution additive mixed in the electrolytic copper plating solution, the same components as those in the conventionally known electrolytic copper plating solution can be used. For example, copper salts that are sources of copper include copper sulfate, copper acetate, copper fluoroborate, and copper nitrate, and inorganic acids that are electrolytes include sulfuric acid, phosphoric acid, nitric acid, hydrogen halide, sulfamic acid, and boric acid. , fluoroboric acid, etc. can be cited as preferred examples.

The electrolytic copper plating solution of this embodiment is particularly preferably a plating solution based on copper sulfate and sulfuric acid. In this case, the copper metal concentration of copper sulfate/pentahydrate is in the range of 5 to 200 g/l, preferably 10 to 100 g/l, and sulfuric acid is in the range of 1 to 100 g/l, preferably 5 to 50 g/l. It is usually more efficient to do it within.

Moreover, chloride ions can also be used in the electrolytic copper plating solution of this embodiment. Chloride ions are preferably blended in the plating solution so as to be 20 to 200 mg/L, and it is more preferable to be blended so as to be 20 to 150 mg/L. The chloride ion source is not particularly limited, but for example, NaCl or HCl can be used.

Other additives known to be able to be added to the electrolytic copper plating solution can be arbitrarily used in the electrolytic copper plating solution of this embodiment within the range that does not impair the purpose of the present invention. Other additives include anthraquinone derivatives; Cationic surfactant; Nonionic surfactant; Anionic surfactant; Amphoteric surfactant; Alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid; Alkanesulfonate such as sodium methanesulfonate; Alkanesulfonate esters such as ethyl methanesulfonate; Hydroxyalkanesulfonic acids such as isethionic acid; Hydroxyalkane sulfonate; Hydroxyalkane sulfonic acid ester; Hydroxyalkanesulfonic acid organic acid esters, etc. can be mentioned.

In the electrolytic copper plating solution of this embodiment, components other than the above components are usually water. Therefore, it is usually provided in the form of an aqueous solution or dispersion containing the required amount of the above ingredients.

The method for manufacturing an electrolytic plated member, which includes the step of immersing the member in an electrolytic plating solution containing the electrolytic plating solution additive of the present invention and precipitating a metal on the member, has excellent spreading properties of the plating layer and has a high practicality. It is a manufacturing method that has value.

Taking the case of using the electrolytic copper plating solution, which is the preferred embodiment described above, as an example, the method is carried out in the same manner as the conventional electrolytic copper plating method, except that a copper plating solution to which the electrolytic plating solution additive of the present invention is added is used as the electrolytic copper plating solution. can do. For example, the temperature of the electrolytic copper plating solution is 15 to 50°C, preferably 20 to 30°C, and the current density is preferably in the range of 1.0 to 30 A/dm2, preferably 2.0 to 10 A/dm2. . The plating time can be appropriately set by a person skilled in the art depending on conditions such as desired film thickness, current density, uniformity of the plating film, and whether plating is continuous. Additionally, as a method of stirring the plating solution, air stirring, rapid liquid stirring, mechanical stirring using a stirring blade, etc. can be used.

The electrolytic plating member obtained according to the above embodiment has a high uniformity of the plating layer even when the member has a complex shape, and is particularly desirable as an electrical and electronic member, and has high technical and economic value. The manufacturing method of the above-mentioned embodiment can manufacture such an electrolytic plating attachment member in a relatively short time and at low cost, and in this respect also has high technical and economic value.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Additionally, the scope of the present invention is not limited by these examples in any sense.

The evaluation methods and measurement methods for each physical property and characteristic in each Example/Comparative Example are as follows.

(1) Weight average molecular weight of the copolymer

The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC method) using a Hitachi L-6000 type high-performance liquid chromatograph.

The eluent flow pump was Hitachi L-6000, the detector was a Shodex RI-101 differential refractive index detector, and the columns were Shodex Asahipak's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS-620HQ (exclusion limit molecular weight 200). (only) connected in series was used. The sample was prepared at a concentration of 0.5 g/100 ml as an eluent, and 20 μl was used. For the eluent, a 0.4 mol/L aqueous sodium chloride solution was used. The column temperature was 30°C, and the flow rate was 1.0 mL/min. As a standard material, obtain a calibration curve using polyethylene glycol with molecular weights of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000, etc., and calculate the weight average molecular weight (Mw) of the copolymer based on the calibration curve. ) was obtained.

(2) Polymerization yield of copolymer

From the peak area ratio obtained by GPC method, it was calculated according to the following formula.

(3) Structural analysis by infrared spectroscopy (FT-IR)

Measurement was performed using a Fourier transform infrared spectrophotometer FT-720 FREEXACT-II (manufactured by Horiba Corporation) by the total reflection method using diamond ATR.

(Synthesis Example 1)

(Synthesis of allylmethallyldimethylammonium chloride)

1 mole of dimethylallylamine and 102.06 g of dilution water were added to a 300 ml four-necked flask equipped with a stirrer, thermometer, and glass stopper, and the temperature was raised to 40°C. 0.95 mol of metallyl chloride was added dropwise over 3.5 hours. The temperature was maintained at 50°C to 55°C during dropping. After the dropwise addition was completed, the temperature was raised to 60°C, and the reaction was continued overnight. After adjusting the pH to 10.56 with a 25% aqueous sodium hydroxide solution, unreacted dimethylallylamine was distilled off using an evaporator. 90 g of dilution water was added to obtain 274.16 g of the target product. Quantification of ammonium salt by the phosphotungstic acid method showed concentration: 62.84%, molecular weight: 173.68 (theoretical molecular weight: 175.70). No residual amine was detected in the potentiometric titration.

(Synthesis of copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide-1)

Into a 100 mL three-necked flask equipped with a stirrer, thermometer, and glass stopper, 0.12 mol of allylmethallyldimethylammonium chloride and 6.71 g of dilution water synthesized above were injected, and 0.12 mol of sulfur dioxide was injected at 30°C or lower. Polymerization was started at 26°C by adding 0.2 mol% of ammonium persulfate based on the total number of moles of monomers. While maintaining the temperature at 25 to 30°C, 0.3, 0.5, and 0.5 mol% (total 1.5 mol%) of ammonium persulfate was additionally added every hour. 1 hour after addition, the temperature was raised to 60°C, and the reaction was continued overnight. Polymerization was terminated by adding 50 g of dilution water. GPC yield: 98.3%, Mw: 3,780 (Mw/Mn: 1.39). The GPC chart obtained in this measurement is shown in Figure 1.

The solid content was measured, and 93.8 g of a colorless solution with a solid content concentration of 30.09% was obtained. A portion of the solution was collected, reprecipitated with isopropyl alcohol, and then dried under reduced pressure. The infrared spectral spectrum of the obtained white powdery solid is shown in FIG. 2. In the infrared spectroscopic spectrum, absorption around 1,300 and 1,125 cm ^-1 derived from the sulfonyl group was confirmed.

It was confirmed that a copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide was obtained with high polymerization yield.

(Synthesis Example 2)

(Synthesis of copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide-2)

Into a 100 mL three-necked flask equipped with a stirrer, thermometer, and glass stopper, 0.12 mol of allylmethallyldimethylammonium chloride synthesized in Synthesis Example 1, 3.02 g of dilution water, and 0.012 mol of 35% hydrochloric acid were charged, and the mixture was stirred at 30°C or lower. After 0.12 mol of sulfur dioxide was injected, polymerization was started by adding 0.2 mol% of ammonium persulfate based on the total number of moles of monomers at 25°C. While maintaining the temperature at 25 to 30°C, 0.3, 0.5, and 0.5 mol% (total 1.5 mol%) of ammonium persulfate was additionally added every hour. 24 hours after addition, the temperature was raised to 60°C, and the reaction was continued overnight. Polymerization was terminated by adding 50 g of dilution water. GPC yield: 100%, Mw: 14,113 (Mw/Mn: 1.43). The GPC chart obtained in this measurement is shown in Figure 3.

The solid content was measured, and 92.6 g of a colorless solution with a solid content concentration of 31.76% was obtained. A portion of the solution was collected, reprecipitated with isopropyl alcohol, and then dried under reduced pressure. The infrared spectral spectrum of the obtained white powdery solid is shown in FIG. 4. In the infrared spectroscopic spectrum, absorption around 1,300 and 1,125 cm ^-1 derived from the sulfonyl group was confirmed.

It was confirmed that a copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide was obtained with high polymerization yield.

(Synthesis Example 3)

(Synthesis of allylmethallyldiethylammonium chloride)

0.8 mol of diethylallylamine and 94.72 g of dilution water were charged into a 300 mL four-necked flask equipped with a stirrer, thermometer, and glass stopper, and the temperature was raised to 50°C. 0.76 mol of metallyl chloride was added dropwise over 2 hours. The temperature was maintained at 50°C to 55°C during dropping. After completion of the dropwise addition, the temperature was gradually raised to 60°C, 70°C, 85°C, and 90°C, and the reaction was continued for 3 days. The lower layer was separated using a separatory funnel, the pH was adjusted to 11 with a 25% NaOH aqueous solution, and unreacted diethylallylamine was distilled off using an evaporator. NaCl that was appropriately diluted and precipitated was filtered using a decanter and a Kiriyama funnel (7 microns) to obtain 39.76 g (yield 18.9%) of a light brown solution with a pH of 7.7. In the quantification of ammonium salt by the phosphotungstic acid method, concentration: 73.77%, molecular weight: 202.57 (theoretical molecular weight: 203.75). No residual amine was detected in the potentiometric titration.

(Synthesis of copolymer of allylmethallyldiethylammonium chloride and sulfur dioxide)

Into a 100 mL three-necked flask equipped with a stirrer, thermometer, and glass stopper, 0.1 mol of allylmethallyldiethylammonium chloride and 10.61 g of dilution water synthesized above were injected, and 0.1 mol of sulfur dioxide was injected at 30°C or lower. , polymerization was started by adding 0.2 mol% of ammonium persulfate based on the total number of moles of monomers at 21°C. While maintaining the temperature at 25 to 30°C, 0.3, 0.5, and 0.5 mol% (total 1.5 mol%) of ammonium persulfate was additionally added every hour. 1 hour after addition, the temperature was raised to 60°C, and the reaction was continued overnight. Polymerization was terminated by adding 50 g of dilution water. GPC yield: 98.5%, Mw: 3,033 (Mw/Mn: 1.42). The GPC chart obtained in this measurement is shown in Figure 5.

The solid content was measured, and 91.3 g of a solution with a solid content concentration of 29.28% was obtained. A portion of the solution was collected, reprecipitated with isopropyl alcohol, and then dried under reduced pressure. The infrared spectral spectrum of the obtained white powdery solid is shown in FIG. 6. In the infrared spectroscopic spectrum, absorption around 1,300 and 1,125 cm ^-1 derived from the sulfonyl group was confirmed.

It was confirmed that a copolymer of allylmethallyldiethylammonium chloride and sulfur dioxide was obtained with high polymerization yield.

Evaluation tests as leveling agent for electrolytic copper plating

(Example 1)

Using a Hull cell tester, the leveling properties in electrolytic copper plating were evaluated when the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 1 was used as an electrolytic plating solution additive under the following conditions. did.

(i) Concentration of each component in the plating solution

ㆍCopper sulfate pentahydrate: 75 g/ℓ

ㆍSulfuric acid: 190 g/ℓ

ㆍChloride ion: 50 mg/ℓ

ㆍPEG (polyethylene glycol, weight average molecular weight 4000): 100 mg/ℓ

ㆍSPS (3,3'-dithiobis(sodium 1-propanesulfonate)): 5 mg/ℓ

ㆍCopolymer of allylmethallyldimethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 1: 10 mg/ℓ

(ii) Plating conditions

ㆍCurrent value: 2 A

ㆍPlating time: 20 minutes

ㆍLiquid temperature: room temperature

ㆍAgitating method: Air agitation

(iii) Evaluation method

In a 267 ml Hull cell container (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.), the plating solution (i) above was added up to the marked line, and a degreased test piece (material: brass. The outline is shown in Figure 7. In the figure, the dots indicate blood. This is the plating part, and the hatched part is the gloss range measurement part.) was immersed, and electrolytic copper plating was performed under the conditions of (ii) above. After that, the appearance of the plated test piece was visually judged, and the range of current density with a mirror gloss was measured. The current density depends on the lateral position of the test piece, and its value is as shown in FIG. 7.

The appearance of the test piece after the hull cell test is shown in Figure 8. A plating film with mirror gloss was obtained over a current density range of 11.22 to -0.28 (A/dm2), and high throwing power was obtained over a wide current density range.

(Example 2)

Except that instead of the copolymer of allylmetallyldimethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 1, the copolymer of allylmetallyldiethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 3 was used at 10 mg/L. In addition, a Hull cell test was conducted in the same manner as in Example 1.

The appearance of the test piece after the hull cell test is shown in Figure 9. A plating film with mirror gloss was obtained over a current density range of 9.01 to -0.28 (A/dm2), and high throwing power was obtained over a wide current density range.

(Comparative Example 1)

Instead of the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 1, a copolymer of diallyldimethylammonium chloride and sulfur dioxide (manufactured by Nittobo Medical Co., Ltd., brand name: PAS-A-5) was used at 10 mg/day. A Hull cell test was conducted in the same manner as in Example 1 except that ℓ was used.

The appearance of the test piece after the hull cell test is shown in Figure 10. A plating film with mirror luster was obtained over a current density range of 7.78 to -0.28 (A/dm2). The current density range in which high throwing power was obtained was narrower than that of the Examples, and especially in the high current density region, high throwing power was not obtained.

(Comparative Example 2)

Instead of the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 1, a polymer of diallyldimethylammonium chloride (manufactured by Nittobo Medical Co., Ltd., brand name: PAS-H-5L) was used at 10 mg/L. A Hull cell test was conducted in the same manner as in Example 1 except for the exceptions.

The appearance of the test piece after the hull cell test is shown in Figure 11. Although a plating film with mirror gloss was obtained over a current density range of 5.56 to -0.28 (A/dm2), some unevenness was confirmed. The current density range in which high throwing power was obtained was considerably narrower than that of the Examples, and especially in the high current density region, high throwing power was not obtained.

(Comparative Example 3)

A Hull cell test was conducted in the same manner as in Example 1, except that the copolymer of allylmethallyldimethylammonium chloride and sulfur dioxide synthesized in Synthesis Example 1 was not used.

The appearance of the test piece after the hull cell test is shown in Figure 12. A plating film with mirror gloss was obtained over a range of current densities of 3.35 to -0.28 (A/dm2), but a significant portion remained semi-gloss. The current density range in which high throwing power was obtained was considerably narrower than that of the Examples, and especially in the high current density region, high throwing power was not obtained.

The results of Examples 1 to 2 and Comparative Examples 1 to 3 are summarized in Table 1.

The additive for electrolytic plating solution of the present invention and its preferred embodiments have high practical value, exceeding the limitations of the prior art, by significantly improving the productivity of electrolytic plating and realizing good electrolytic plating for members of complex shapes. By realizing technical effects, it has high utility value and high availability in various fields of industry, including the electrical and electronics industry, communications industry, industrial machinery industry, and transportation machinery industry, which require high-quality plating with high productivity. .

Claims (8)

Containing a diallylamine-based (co)polymer having a structural unit (I) derived from a diallylamine-based compound (i) and a structural unit (II) derived from sulfur dioxide having a structure represented by the following general formula (1), Electrolytic plating solution additive.

(However, in the above formula (1), R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, provided that R ¹ and R ² are not hydrogen at the same time, and R ³ and R ⁴ are, Each is independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.) According to claim 1,
An electrolytic plating solution additive in which the diallylamine-based compound (i) has a structure represented by the following general formula (1').

(However, in the above formula (1'), R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms, and X ^- is a counter ion.) According to claim 1,
An electrolytic plating solution additive, wherein the ratio of structural unit (I) to all structural units of the diallylamine-based (co)polymer is 10 mol% or more. An electrolytic plating solution containing the electrolytic plating solution additive according to any one of claims 1 to 3. According to claim 4,
An electrolytic plating solution further containing a copper compound. A method for producing an electrolytic plated member, comprising the step of immersing the member in the electrolytic plating solution according to claim 4 and depositing a metal on the member. According to claim 6,
A method of manufacturing an electrolytic plating attachment member, wherein the electrolytic plating attachment member is an electrical and electronic component. delete