CN103443334B - Cathode copper plates application additive and electrolysis electroless copper bath - Google Patents
Cathode copper plates application additive and electrolysis electroless copper bath Download PDFInfo
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- CN103443334B CN103443334B CN201280015856.5A CN201280015856A CN103443334B CN 103443334 B CN103443334 B CN 103443334B CN 201280015856 A CN201280015856 A CN 201280015856A CN 103443334 B CN103443334 B CN 103443334B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
The present invention is provided forming uniform electroplated film from low current density portion to high current density portion so as to assign good glossiness, the cathode copper that will not also consume when not in use in addition plating application additive and electrolysis electroless copper bath containing the additive.Present invention addition in electroless copper bath is electrolysed includes following formulas（1）The cathode copper plating application additive of shown block polymer compound.（Wherein, in formula, R represents that the carbon number of straight or branched is 1 ~ 15 alkyl or alkenyl, and m is 1 ~ 30 integer, and n is 1 ~ 40 integer.）
Description
Technical field
The present invention relates to cathode copper plating application additive and electrolysis electroless copper bath, more particularly to being suitable as copper sulfate bath
Polishing material the cathode copper plating application additive and electrolysis electroless copper bath containing the additive.
The application is required based on Japanese patent application No. Patent 2011-070667 of on the March 28th, 2011 in Japanese publication
Priority, quoted by referring to these applications in the application.
Background technology
In the past, assigned tool glossiness plated copper film by adding polishing material into electrolysis electroless copper bath.As its polishing material,
Such as known organosulfur compound, oxygen-containing macromolecular organic compound etc.（For example, referring to patent document 1 or 2.）.As organic
Sulphur compound, commonly use NaO3SC3H6S-SC3H6SO3The disulphide based compound such as Na, in addition, as oxygen-containing macromolecular organic
Compound, use oxyalkylene polymer, polyethylene glycol, polypropylene glycol etc..
In addition, as the polishing material beyond above-claimed cpd, following formulas are used
H-（EO）a-（PO）m-（EO）b-H
Polymer that is shown, being formed to polypropylene glycol addition of ethylene oxide.It should be noted that in above-mentioned formula, EO tables
Show oxyethylene group, PO represents oxypropylene group, n=a+b.
However, glossiness of these polishing materials for using always in the past in the low current density portion of plated copper film, scattered energy
Power（つ I ま わ り）It is insufficient, so as to form coarse overlay film.As its reason, it is believed that be due to for example on stating
As hydrophobic grouping in the molecular structure of polymer shown in formula（PO）M is by both sides（EO）Clamped by n, thus as hydrophobic
The effect of group is weak.As a result, when the compound formed by the polymer is used as into the polishing material of electrolysis electroless copper bath, in low current
CURRENT DISTRIBUTION is disorderly in density portion, high current density portion, hinders uniform electro-deposition, produces fine hole（ピット）Or cloud point（く
もり）Deng so as to which bad plating occur.
In addition, the polishing material as cathode copper plating application, it is expected that it is easily managed, will not also consumed when not in use.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2005-194608 publications
Patent document 2:Japanese Unexamined Patent Publication 2008-297221 publications.
The content of the invention
Problems to be solved by the invention
Here, the present invention in view of above-mentioned existing situation and carry out, its object is to provide from low current density portion
Uniform electroplated film is formed to high current density portion so as to assign good glossiness, will not also consume when not in use in addition
Cathode copper plates application additive and the electrolysis electroless copper bath containing the additive.
The means used to solve the problem
Further investigation is repeated in order to solve above-mentioned problem in the present inventor etc., as a result finds, by that will improve
The block polymer compound of hydrophobic grouping effect is used as additive, can be from low current density portion to high current density portion shape
Into uniform electroplated film so as to assign good glossiness, the present invention is so far completed.
That is, cathode copper plating application additive of the present invention includes following formulas（1）Shown block polymer chemical combination
Thing.
[chemical formula 1]
（Wherein, in formula, R represents that the carbon number of straight or branched is 1 ~ 15 alkyl or alkenyl, and m is 1 ~ 30 integer,
N is 1 ~ 40 integer.）
In addition, electrolysis electroless copper bath of the present invention contains comprising above-mentioned formula（1）Shown block polymer compound
Additive.
Invention effect
In accordance with the invention it is possible to uniform electroplated film is being formed so as to assign from low current density portion to high current density portion
Good glossiness, it will not also consume when not in use in addition and good electroplated film can be stably formed.
Embodiment
Hereinafter, plated for the cathode copper plating application additive described in present embodiment and the cathode copper containing the additive
Bath is described in detail.
Cathode copper plating application additive described in present embodiment includes following formulas（1）Shown block polymer chemical combination
Thing.
[chemical formula 2]
Herein, formula（1）In, R represents that the carbon number of straight or branched is 1 ~ 15 alkyl or alkenyl, and m is 1 ~ 30
Integer, n are 1 ~ 40 integer.
As straight or branched carbon number be 1 ~ 15 alkyl or alkenyl be R, such as can include methyl, ethyl,
N-propyl, pi-allyl, normal-butyl, n-pentyl, n-hexyl, 1- methylhexyls, 2- ethylhexyls, n-heptyl, n-octyl, positive nonyl
Base, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base etc..
In addition, formula（1）In m and n can be appropriately configured according to above-mentioned R species.Specifically, due to hydrophobic
Property is raised with the increase of R carbon numbers, therefore m and n mol ratio are adjusted by the species according to the R, can make it
Possesses appropriate dissolubility in plating bath.In addition, m and n can be with above-mentioned formula（1）The molecular weight of shown block polymer is excellent
The mode that choosing reaches 500 ~ 2000 is set.
Such as above-mentioned formula（1）Shown such, the additive is formed for the end of oxypropylene group side by alkyl or alkenyl end-blocking
Structure.Like this, by the way that the end of oxypropylene group is blocked with alkyl or alkenyl, can improve as the hydrophobic of oxypropylene group
The effect of group.
Then, above-mentioned formula（1）The oxypropylene group of shown additive（PO）With oxyethylene group（EO）Order be certain
, typically by R-O-（PO）m-（EO）The block polymer that n-H structures are formed.Thus, as described above, end quilt is passed through
The oxypropylene group that alkyl or alkenyl end-blocking forms（（PO）m）, in above-mentioned formula（1）In, " R-O-（PO）M " part generally as
Hydrophobic grouping and work, so as to Ju You Gao Shu it is water-based.
As the effect predicted therefrom, the hydrophobic grouping of usual compound is released interface from water, therefore water-soluble
When plated application is impregnated in liquid, the plating surface application of plated application turns into interface, and tool has the water-based additives of high Shu plating surface application concentration,
The effect of additive improves.It is considered that add as a result, being played in the entirety from low current density portion to high current density portion
Add the effect of agent, therefore uniform electroplated film can be formed so as to assign good glossiness.
And then due to being such block polymer, therefore can possess by the oxyethylene group of opposite side end suitable
The dissolubility of degree, polymer compound can be dissolved well in electroless copper bath is electrolysed, stably be maintained in plating bath in addition,
Electrolysis processing can suppress when not in use through when consume.
Above-mentioned formula（1）Shown block polymer compound can for example manufacture by the following method.That is, in nitrogen
Under the non-active gas atmosphere such as gas, first, expoxy propane is set to be added with carbon number for 1 ~ 15 alkylol or alkenyl alcohol
Into reaction.After the addition reaction of expoxy propane terminates, then, oxirane is added to carry out the addition reaction of oxirane, from
And obtain formula（1）Shown block polymer compound.
Like this, block polymer compound is by making the alkylol or alkenyl alcohol that expoxy propane and carbon number are 1 ~ 15
After carrying out addition reaction, add oxirane and carry out addition reaction so as to synthesize, included thus, it is possible to be made by alkyl or alkene
Base end-blocking（PO）M additions（EO）The block body for the regulation structure that n is formed.
As the reaction temperature in the manufacture method of block polymer compound, it is not particularly limited, it is preferably set to 90 ~
160℃.By the way that reaction temperature is set into more than 90 DEG C, appropriate reaction speed can be obtained, epoxy third can effectively occur
The addition reaction of alkane and oxirane.In addition, by the way that reaction temperature is set into less than 160 DEG C, the life of accessory substance etc. can be suppressed
Into the yield of the raising block polymer compound to be generated.It should be noted that alkylol is set to be added with expoxy propane
After into reaction again addition of ethylene oxide when, it is preferred that make at above-mentioned 90 ~ 160 DEG C expoxy propane carry out addition reaction after,
First cool down once, then condition carries out the addition reaction of oxirane at the same temperatures again.
In addition, as the reaction time, it is not particularly limited, different because of reaction temperature, expoxy propane and oxirane are each
Addition reaction be preferably within 15 hours.By being set within 15 hours, the generation of accessory substance etc. can be suppressed, raising will give birth to
Into block polymer compound yield.
In addition, when carrying out addition reaction, preferably carry out under elevated pressure, pressure when starting as addition reaction, preferably
It is set to 2 ~ 5kg/cm2。
By above-mentioned formula（1）When shown block polymer compound is used as the additive of cathode copper plating, as now
Addition concentration, be preferably set to 0.05 ~ 1.0g/L.By the way that addition concentration is set into more than 0.05g/L, can be formed with abundant
The electroplated film of glossiness.In addition, by the way that addition concentration is set into below 1.0g/L, the electric current that can be used can be effectively prevented
Density range is narrow, good electroplated film can be formed uniformly from low current density portion to high current density portion.
Then, above-mentioned formula is included for the addition of（1）The cathode copper of the additive of shown block polymer compound
Plating bath and using the electrolysis electroless copper bath plating processing illustrate.As electrolysis electroless copper bath, it is not particularly limited, especially
It is preferably made copper sulfate bath.Like this, can be big by adding above-mentioned block polymer compound in copper sulfate bath
The plated copper film with excellent gloss is formed uniformly in the current density range of scope, decoration plating can be suitably used as
Plating bath used in processing.
Specifically, the composition as copper sulfate bath, such as can be made with copper sulphate（Cu2SO4•5H2O）50~
250g/L, 50 ~ 250g/L of the concentrated sulfuric acid are the plating bath formed substantially.It should be noted that generally make in copper sulfate bath containing micro-
Amount（10 ~ 200mg/L or so）Chloride ion.Specifically, such as by adding the water soluble chlorides such as NaCl it is made
Contain.
It should be noted that can be by additive known to the further addition in above-mentioned electrolysis electroless copper bath, so as to enter
One step improves glossiness, flatness.Specifically, such as organosulfur compound, organic acid amide class, oxygen-containing high score can be added
Sub- organic compound etc..
As the plating treatment conditions for having used above-mentioned electrolysis electroless copper bath, pH is set to less than 1.It is further preferred, that make
For plating temperature, 20 ~ 50 DEG C of scope is set to, as cathode-current density, is set to 0.1 ~ 8A/dm2.In addition, as anode, can
To use copper coin, insoluble anode.And then in order to form the electroplated film with glossiness evenly, preferably fully carry out
Air stirring, negative electrode shake（カソードロッキング）Deng stirring.
In addition, being plated processed material as the above-mentioned plating processing of implementation, it is not particularly limited, such as plastics etc.
The purpose that processed material implements decoration plating is plated, can compatibly use the electrolysis electroless copper bath added with above-mentioned additive.Need
It is noted that alternatively, it is also possible to implement plating with the printed wiring board with through hole, electrical and electronic parts etc. for object
Processing.Like this, the electrolysis electroless copper bath added with above-mentioned additive can extensively should in decorative use into feature purpose
With.
Embodiment
Hereinafter, illustrated for the specific embodiment of the present invention.It should be noted that the present invention is not by following any
The restriction of embodiment.
In each embodiment of the description below, the block polymer shown in table 1 is synthesized（R-O-（PO）m-（EO）n-H）, use
Electroless copper bath added with the block polymer compound as additive carries out plating processing, is carried out to separating out the electroplated film formed
Evaluation.It should be noted that being blown into air into electroless copper bath and being sufficiently stirred, particularly make sky in a manner of stirring near negative electrode
The plated application of gas contact.
[table 1]
The ＞ of ＜ embodiments 1
（The synthesis of block polymer）
Normal propyl alcohol 600g is taken into airtight reaction container（10 moles）With potassium hydroxide 5.6g（0.1 mole）, in nitrogen
Make expoxy propane 870g under atmosphere（15 moles）In 90 ~ 130 DEG C, 2 ~ 5kg/cm2Pressurization under carry out addition reaction.Expoxy propane
Addition reaction terminate after, reaction vessel is cooled down, is subsequently added into oxirane 660g（15 moles）, enter under the same conditions
Row addition reaction.
Then, the addition synthesis sorbing material into reaction vessel（Kyoward 600, Kyowa Chemical Industry Co., Ltd's system）
50g, at 70 DEG C filter after stir process within 30 minutes, obtain polyoxyethylene（15）Polyoxypropylene（15）Propyl ether 2070g.
（Plating processing and electroplated film evaluation）
Using comprising it is following composition be
Copper sulphate（Cu2SO4・5H2O） 200g/L
Concentrated sulfuric acid 50g/L
NaCl 115mg/L
Copper sulphate plating solution in addition as additive pair-（ω-sulfapropyl）- disulphide disodium salt 10mg/
L, the diazotising processed material 50mg/L of diethyl safranine and the polyoxyethylene for operating as explained above and synthesizing（15）Polyoxy third
Alkene（15）Propyl ether 0.2g/L plating bath, hull trough test instrument is used with 2A total current, 10 minutes（Ha Le セ ル Try test
Device）Carry out plating processing.It should be noted that plating treatment conditions be set to pH ＜ 1,25 DEG C of temperature, cathode-current density 0.15 ~
4A/dm2。
As a result, it is being formed uniformly the precipitation with good gloss from low current density portion to high current density portion
Thing.
In addition, even in being put into copper coin into above-mentioned hull trough test instrument and placing an evening with the state, then equally grasp
Make in the case of carrying out plating processing, can be also formed uniformly in the same manner as initial plating processing with good gloss
Precipitate.Therefore, it is known that additive even if also can stably maintaining without being consumed in plating bath when not in use.
The ＞ of ＜ embodiments 2
（The synthesis of block polymer）
Allyl alcohol is taken into airtight reaction container（2- propane -1- alcohol）580g（10 moles）With potassium hydroxide 5.6g
（0.1 mole）, make expoxy propane 870g in a nitrogen atmosphere（15 moles）In 90 ~ 130 DEG C, 2 ~ 5kg/cm2Pressurization under carry out
Addition reaction.After the addition reaction of expoxy propane terminates, reaction vessel is cooled down, is subsequently added into oxirane 660g（15 rub
You）, addition reaction is carried out under the same conditions.
Then, the addition synthesis sorbing material into reaction vessel（Kyoward 600, Kyowa Chemical Industry Co., Ltd's system）
50g, at 70 DEG C filter after stir process within 30 minutes, obtain polyoxyethylene（15）Polyoxypropylene（15）Allyl ether
2050g。
（Plating processing and electroplated film evaluation）
In example 2 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, the diazotising processed material 50mg/L of diethyl safranine and the polyoxyethylene for operating as explained above and synthesizing（15）It is poly-
Oxypropylene（15）Outside allyl ether 0.2g/L copper sulfate bath, operate, entered using hull trough test instrument similarly to Example 1
The processing of row plating.
As a result, it is being formed uniformly the precipitation with good gloss from low current density portion to high current density portion
Thing.In addition, even in being put into copper coin into above-mentioned hull trough test instrument and placing a Dinner with the state, then equally operate to enter
In the case of the processing of row plating, also the precipitation with good gloss can be formed uniformly in the same manner as initial plating processing
Thing.
The ＞ of ＜ embodiments 3
（The synthesis of block polymer）
N-butanol 740g is taken into airtight reaction container（10 moles）With potassium hydroxide 5.6g（0.1 mole）, in nitrogen
Make expoxy propane 580g under atmosphere（10 moles）In 90 ~ 130 DEG C, 2 ~ 5kg/cm2Pressurization under carry out addition reaction.Expoxy propane
Addition reaction terminate after, reaction vessel is cooled down, is subsequently added into oxirane 660g（15 moles）, enter under the same conditions
Row addition reaction.
Then, the addition synthesis sorbing material into reaction vessel（Kyoward 600, Kyowa Chemical Industry Co., Ltd's system）
50g, at 70 DEG C filter after stir process within 30 minutes, obtain polyoxyethylene（15）Polyoxypropylene（10）Butyl ether 1920g.
（Plating processing and electroplated film evaluation）
In embodiment 3 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, the diazotising processed material 50mg/L of diethyl safranine and the polyoxyethylene for operating as explained above and synthesizing（15）It is poly-
Oxypropylene（10）Outside butyl ether 0.2g/L copper sulfate bath, operate, carried out using hull trough test instrument similarly to Example 1
Plating processing.
As a result, it is being formed uniformly the precipitation with good gloss from low current density portion to high current density portion
Thing.In addition, even in being put into copper coin into above-mentioned hull trough test instrument and placing an evening with the state, then equally operate to enter
In the case of the processing of row plating, also the precipitation with good gloss can be formed uniformly in the same manner as initial plating processing
Thing.
The ＞ of ＜ embodiments 4
（The synthesis of block polymer）
N-hexyl alcohol 1020g is taken into airtight reaction container（10 moles）With potassium hydroxide 5.6g（0.1 mole）, in nitrogen
Make expoxy propane 290g under atmosphere（5 moles）In 90 ~ 130 DEG C, 2 ~ 5kg/cm2Pressurization under carry out addition reaction.Expoxy propane
Addition reaction terminate after, reaction vessel is cooled down, is subsequently added into oxirane 880g（20 moles）, enter under the same conditions
Row addition reaction.
Then, the addition synthesis sorbing material into reaction vessel（Kyoward 600, Kyowa Chemical Industry Co., Ltd's system）
50g, at 70 DEG C filter after stir process within 30 minutes, obtain polyoxyethylene（20）Polyoxypropylene（5）Hexyl ether 2130g.
（Plating processing and electroplated film evaluation）
In example 4 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, the diazotising processed material 50mg/L of diethyl safranine and the polyoxyethylene for operating as explained above and synthesizing（20）It is poly-
Oxypropylene（5）Outside hexyl ether 0.2g/L copper sulfate bath, operate, carried out using hull trough test instrument similarly to Example 1
Plating processing.
As a result, it is being formed uniformly the precipitation with good gloss from low current density portion to high current density portion
Thing.In addition, even in being put into copper coin into above-mentioned hull trough test instrument and placing an evening with the state, then equally operate to enter
In the case of the processing of row plating, also the precipitation with good gloss can be formed uniformly in the same manner as initial plating processing
Thing.
The ＞ of ＜ embodiments 5
（The synthesis of block polymer）
2-Ethylhexyl Alcohol 1300g is taken into airtight reaction container（10 moles）With potassium hydroxide 5.6g（0.1 mole）,
Make expoxy propane 174g under nitrogen atmosphere（3 moles）In 90 ~ 130 DEG C, 2 ~ 5kg/cm2Pressurization under carry out addition reaction.Epoxy
After the addition reaction of propane terminates, reaction vessel is cooled down, is subsequently added into oxirane 1100g（25 moles）, in identical bar
Addition reaction is carried out under part.
Then, the addition synthesis sorbing material into reaction vessel（Kyoward 600, Kyowa Chemical Industry Co., Ltd's system）
50g, at 70 DEG C filter after stir process within 30 minutes, obtain polyoxyethylene（25）Polyoxypropylene（3）2- ethylhexyl ethers
2500g。
（Plating processing and electroplated film evaluation）
In embodiment 5 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, the diazotising processed material 50mg/L of diethyl safranine and the polyoxyethylene for operating as explained above and synthesizing（25）It is poly-
Oxypropylene（3）Outside 2- ethylhexyl ethers 0.2g/L copper sulfate bath, operate similarly to Example 1, use hull trough test
Instrument carries out plating processing.
As a result, it is being formed uniformly the precipitation with good gloss from low current density portion to high current density portion
Thing.In addition, even in being put into copper coin into above-mentioned hull trough test instrument and placing an evening with the state, then equally operate to enter
In the case of the processing of row plating, also the precipitation with good gloss can be formed uniformly in the same manner as initial plating processing
Thing.
The ＞ of ＜ embodiments 6
（The synthesis of block polymer）
1- lauryl alcohols 1860g is taken into airtight reaction container（10 moles）With potassium hydroxide 5.6g（0.1 mole）, in nitrogen
Make expoxy propane 116g under gas atmosphere（2 moles）In 90 ~ 130 DEG C, 2 ~ 5kg/cm2Pressurization under carry out addition reaction.Epoxy third
After the addition reaction of alkane terminates, reaction vessel is cooled down, is subsequently added into oxirane 1320g（30 moles）, in identical condition
Lower carry out addition reaction.
Then, the addition synthesis sorbing material into reaction vessel（Kyoward 600, Kyowa Chemical Industry Co., Ltd's system）
50g, at 70 DEG C filter after stir process within 30 minutes, obtain polyoxyethylene（30）Polyoxypropylene（2）Lauryl ether
3200g。
（Plating processing and electroplated film evaluation）
In embodiment 6 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, the diazotising processed material 50mg/L of diethyl safranine and the polyoxyethylene for operating as explained above and synthesizing（30）It is poly-
Oxypropylene（2）Outside lauryl ether 0.2g/L copper sulfate bath, operate similarly to Example 1, use hull trough test instrument
Carry out plating processing.
As a result, it is being formed uniformly the precipitation with good gloss from low current density portion to high current density portion
Thing.In addition, even in being put into copper coin into above-mentioned hull trough test instrument and placing an evening with the state, then equally operate to enter
In the case of the processing of row plating, also the precipitation with good gloss can be formed uniformly in the same manner as initial plating processing
Thing.
The ＞ of ＜ comparative examples 1
（Plating processing and electroplated film evaluation）
In comparative example 1 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
Outside 10mg/L, the diazotising processed material 50mg/L of diethyl safranine and polyethylene glycol 0.2g/L copper sulfate bath, with reality
Apply example 1 equally to operate, plating processing is carried out using hull trough test instrument, evaluate separating out the electroplated film formed.Need
Illustrate, in the comparative example 1 and following comparative examples 2 and 3, sky mood is also blown into electroless copper bath and has been sufficiently carried out stirring
Mix.
As a result, although precipitate produces fine hole or white haze, close from low current with good gloss
Degree portion to high current density portion does not form uniform precipitate, is the electroplated film of bad order.
The ＞ of ＜ comparative examples 2
（Plating processing and electroplated film evaluation）
In comparative example 2 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
Outside 10mg/L, the diazotising processed material 50mg/L of diethyl safranine and polypropylene glycol 0.2g/L copper sulfate bath, with reality
Apply example 1 equally to operate, plating processing is carried out using hull trough test instrument, evaluate separating out the electroplated film formed.
As a result, although precipitate produces fine hole or white haze, close from low current with good gloss
Degree portion to high current density portion does not form uniform precipitate, is the electroplated film of bad order.
The ＞ of ＜ comparative examples 3
（Plating processing and electroplated film evaluation）
In comparative example 3 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, the diazotising processed material 50mg/L of diethyl safranine and gather to block obtained from polypropylene glycol addition of ethylene oxide
Compound（H-（EO）a-（PO）m-（EO）B-H, m=17, n=a+b=9）Outside 0.2g/L copper sulfate bath, with embodiment 1
Same operation, plating processing is carried out using hull trough test instrument, evaluated separating out the electroplated film formed.
As a result, although precipitate with good gloss, generates fine hole or white haze, from low current
Density portion to high current density portion does not form uniform precipitate, is the electroplated film of bad order.
The ＞ of ＜ comparative examples 4
（Plating processing and electroplated film evaluation）
In comparative example 4 except use with the addition of as additive it is double-（ω-sulfapropyl）- disulphide disodium salt
10mg/L, diethyl safranine diazotising processed material 50mg/L and to n-butanol simultaneously addition of ethylene oxide and expoxy propane and
Outside obtained atactic polymer 0.2g/L copper sulfate bath, operate, carried out using hull trough test instrument similarly to Example 1
Plating processing, evaluate separating out the electroplated film formed.
Although the as a result, terraced fields that precipitate with good gloss, is presented stepped change and separated out（Duan Di）Plating
Apply, do not separate out plating in low current density portion, be the electroplated film of bad order.
Claims (1)
1. being electrolysed electroless copper bath, it contains cathode copper plating application additive, and the cathode copper plating application additive includes following formulas
（1）Shown block polymer compound,
Wherein, formula（1）In, R represents the carbon number of straight or branched as 1 ~ 15 alkyl or alkenyl, the end with oxypropylene group side
End bonding, m are 1 ~ 30 integer, and n is 1 ~ 40 integer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-070667 | 2011-03-28 | ||
| JP2011070667A JP5363523B2 (en) | 2011-03-28 | 2011-03-28 | Additive for electrolytic copper plating and electrolytic copper plating bath |
| PCT/JP2012/057594 WO2012133225A1 (en) | 2011-03-28 | 2012-03-23 | Electro copper plating additive and electro copper plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103443334A CN103443334A (en) | 2013-12-11 |
| CN103443334B true CN103443334B (en) | 2018-02-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280015856.5A Active CN103443334B (en) | 2011-03-28 | 2012-03-23 | Cathode copper plates application additive and electrolysis electroless copper bath |
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| Country | Link |
|---|---|
| US (1) | US20130341199A1 (en) |
| JP (1) | JP5363523B2 (en) |
| KR (1) | KR101940593B1 (en) |
| CN (1) | CN103443334B (en) |
| TW (1) | TWI608130B (en) |
| WO (1) | WO2012133225A1 (en) |
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| EP3074552A1 (en) * | 2013-11-25 | 2016-10-05 | Enthone, Inc. | Electrodeposition of copper |
| US9809891B2 (en) | 2014-06-30 | 2017-11-07 | Rohm And Haas Electronic Materials Llc | Plating method |
| JP6733314B2 (en) * | 2015-09-29 | 2020-07-29 | 三菱マテリアル株式会社 | High-purity copper electrolytic refining additive and high-purity copper manufacturing method |
| US10988852B2 (en) * | 2015-10-27 | 2021-04-27 | Rohm And Haas Electronic Materials Llc | Method of electroplating copper into a via on a substrate from an acid copper electroplating bath |
| CA3119028A1 (en) | 2018-11-07 | 2020-05-14 | Coventya, Inc. | Satin copper bath and method of depositing a satin copper layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5730854A (en) * | 1996-05-30 | 1998-03-24 | Enthone-Omi, Inc. | Alkoxylated dimercaptans as copper additives and de-polarizing additives |
| JPH1088186A (en) * | 1996-09-17 | 1998-04-07 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonionic surfactant and liquid detergent composition uisng the same |
| US6776893B1 (en) * | 2000-11-20 | 2004-08-17 | Enthone Inc. | Electroplating chemistry for the CU filling of submicron features of VLSI/ULSI interconnect |
| SG144688A1 (en) * | 2001-07-23 | 2008-08-28 | Fujimi Inc | Polishing composition and polishing method employing it |
| EP1422320A1 (en) * | 2002-11-21 | 2004-05-26 | Shipley Company, L.L.C. | Copper electroplating bath |
| JP2005194608A (en) | 2004-01-09 | 2005-07-21 | Asahi Denka Kogyo Kk | Additive for electrolytic copper plating, and electrolytic copper plating bath |
| WO2006018872A1 (en) * | 2004-08-18 | 2006-02-23 | Ebara-Udylite Co., Ltd. | Additive for copper plating and process for producing electronic circuit substrate therewith |
| TW200632147A (en) * | 2004-11-12 | 2006-09-16 | ||
| US20070178697A1 (en) * | 2006-02-02 | 2007-08-02 | Enthone Inc. | Copper electrodeposition in microelectronics |
| JP4813213B2 (en) * | 2006-03-07 | 2011-11-09 | 花王株式会社 | Wrinkle removal deodorant composition |
| JP2008222946A (en) * | 2007-03-15 | 2008-09-25 | Seiko Epson Corp | Ink for inkjet recording |
| JP2008222944A (en) * | 2007-03-15 | 2008-09-25 | Seiko Epson Corp | Ink for inkjet recording |
| JP2008297221A (en) | 2007-05-29 | 2008-12-11 | Shinko Electric Ind Co Ltd | Method for producing brightener for plating |
| AU2009260327A1 (en) * | 2008-06-18 | 2009-12-23 | Dow Global Technologies Llc | Cleaning compositions containing mid-range alkoxylates |
| EP2199315B1 (en) * | 2008-12-19 | 2013-12-11 | Basf Se | Composition for metal electroplating comprising leveling agent |
| JP2010255078A (en) * | 2009-04-28 | 2010-11-11 | Adeka Corp | Electrolytic copper plating bath and electrolytic copper plating method |
-
2011
- 2011-03-28 JP JP2011070667A patent/JP5363523B2/en active Active
-
2012
- 2012-03-23 CN CN201280015856.5A patent/CN103443334B/en active Active
- 2012-03-23 WO PCT/JP2012/057594 patent/WO2012133225A1/en active Application Filing
- 2012-03-23 US US14/004,011 patent/US20130341199A1/en not_active Abandoned
- 2012-03-23 KR KR1020137026205A patent/KR101940593B1/en active IP Right Grant
- 2012-03-27 TW TW101110579A patent/TWI608130B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103443334A (en) | 2013-12-11 |
| WO2012133225A1 (en) | 2012-10-04 |
| US20130341199A1 (en) | 2013-12-26 |
| JP5363523B2 (en) | 2013-12-11 |
| KR20140013021A (en) | 2014-02-04 |
| JP2012201976A (en) | 2012-10-22 |
| KR101940593B1 (en) | 2019-01-21 |
| TWI608130B (en) | 2017-12-11 |
| TW201300581A (en) | 2013-01-01 |
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