Explanation of electrolysis water utilization toPWB field which is included industrial field～ Using as an environmental load reduction technique～JIPCM LLC
1505ａS2

Contents of theexplanation★ Explanation of espax electrolysis watercf. electrolysis water = e-water・ Generation principle of e-water★ Characteristics of e-water(Pros&Cons)・ Characteristics of cathode side e-water(Alkaline e-water)
・ Characteristics of anode side e-water(Acid e-water)★ Usage of alkaline e-water・ Usage, effect and attention points★ Usage of espax acid e-water( for PWB industry)・ Characteristics of espax acid e-water
・ Procedures by the PWB production
process.(Results & attention points)※ Explanation of right procedures & attention points

・ Data of actual effectiveness・ Basic conditions of using espax acid e-water
・ About running costs
・ Consideration for installation
・ Usage & maintenance note2Generation principle of espax e-water
Approx.. pH 2.7
production： 2～4L/min（The chlorine residual concentration
4～5ppm）

Vー
The power supply

Approx. pH 11.3
production : 2～4L/min

The electrolytic cell

Acid e-water

Generate O２ & Cl2Cl2Na+Alkaline e-water
H2Generate H2

ClOH-O2Brine（NaCl））

Water supply ： 4～8L/min
DI-water orSoft water

ClH+H2O

H2O＋pole－pole

The membrane film

Water(H2O)'s being electrolyzed
The anode reaction ： ２H2O → 1/2O２＋２H＋２ ＋＋２ｅ－
The cathode reaction：： ２H2O ＋２e＋２ － → Ｈ２＋２ＯＨ－

Type : J02B-GS

Characteristics of e-water(Pros & Cons)～ The point of difference between
general e-water and espax e-water ～4Characteristics of alkaline e-water

１．Possible
to remove grease.
１．
（ can be used for detergents））
・ P4009385（（Japan-domestic/ Application Nippon Steel Co.,Ltd）

２．Possible
to use silicon processing and metal
２．
processing field.
・ It has been developing by FUJI KIKO.

３．Hydrogennano bubbles exist for more than
３．
24 hours in espax alkaline e-water.
As the result, It isgood for1) ion contamination removal.
2) Antirust (not strong effect)5Evaluation of espax alkaline e-water
The remaining oil quantityµg/cm2

１．Removing grease detergency evaluation
Residual oil quantity of Cupper plate surface washed by each detergents

10.80.60.40.20 Alkaline ee-waterStandard ValueNaOH (same pH)

DIDI-watercontrol

２．Evaluation of the ion residual removal effectResidual ionic contamination of Cupper plate surface washed by each detergentsResidual ions ng/cm2

8 0 .0C a 2+K +N H 4+N a+
S O 42P O 43N O 3B rN O 2C l-

6 0 .0Standard Value
4 0 .02 0 .00 .0

e le c t r o ly z e d
N a O H s ln .
d e io n iz e d
NaOH (same pH) DIDI
Alkalineee -wwater
純水a l k a l i n ea te rwa waterte r

c o n v e n t io n a lm e th o dcontrol

6The reason why the cleaning effect is more excellent
than NaOH of the same pHPOINT★ The nano-bubble of hydrogen exists in the espax e-water?
After 5 h (Closed container)

After 24 h(Open container)

2525C

130 nm15101340 nm

5A

20frequency / %frequency / %20130 nm

1510500
1

10100

1000

10000

diameter / nm

The test cooperation ：Professor Unkai Sato by Shinshu Unv.

110100

1000

10000

diameter / nm

The grade scale measuring machine：：Otsuka Electronics
Fiber-Optical Dynamic Light-Scattering
Spectrophotometer FDLS-3000

There is stable hydrogen nano-bublles in espax alkaline e-water.
7

Characteristics of acid e-water
１．HighEffective in Killing bacteria
１．
・ 10 times of Sodium hypochlorite(NaOCl) Sol.

２．Safe& secure : human & eco-friendly
２．
・ The electrolysis product is The hypochlorousacid(HClO).

３．Can be remove oxide film of copper.（espax））
・ Using NaCl can clean Cu surface.
＊ These effects can be used for the surface cleaningof PWB.
8

Why espax acid e-water isenvironment-friendly?
HCｌｌO disappears when it reacts to the organic matter.
＝The environmental load(BOD) reduction
DI-water dilution
酸性電解水
Acidice-water純水希釈

Acidic e-watertap water dilution

Alkaline e-water DI-water dilution
アルカリ性電解水
水道水希釈
Alkalinee-water tap
water dilution★ Easy drainage treatment = Eco-friendly.

9

using e-water in the industrial field

Usage of espax acid e-water～ The main use in PWB production ～Characteristics of espax acid e-waterused in PWC
１．It doesn't form patina even if it dissolves copper.
＊Patina : CuCO３・２Cu（OH）２ ／緑青Copperbronze＊The espax acid e-water can be recycled in washing tank.
（It is necessary to add e-water to maintain pH. : about 1L/min））
11

２．Copper dissolution rate of espax acid e-water is 3 – 4times faster than same pH. chemical solution.
3.6nm/min
N=５５3nm/min

１nm/min

ＮａＣｌ e-water
Ｎａ２ＳＯ４ e-water

ＨＣｌ／pH2.48
ＨＣｌ／
Ｈ２ＳＯ４／pH2.48★ Attention ： The espax acid e-water is not so strong like sulfuric
acid/hydrogen peroxide which can dissolve metallic copper
12

The evaluation of espax acid e-water
Residual oil /10-6 g/cm-2

１．The removing grease detergency evaluation
Residual oil quantity of Cupper plate surface washed by each detergentsStandard Value

e-water
60℃

e-water
20℃

HCl Solution

HCl Solution

DIDI-water

60℃

20℃

60℃

Conventional

Residual ion /10-9 g/cm

２．The evaluation of the ion residual removal effectResidual ionic contamination of Cupper plate surface washed by each detergents
60Cl -50

NO 3 -SO 4 2 -Na +Ca 2+Standard Value

403020100

e-water
60℃

e-water
20℃

HCl Solution

HCl Solution

DIDI-water

60℃

20℃60℃

Conventional

Quantification method：
method：Ion chromatograph13

Data of actual effectiveness andconsideration using espax acid e-waterin PWB production
The specific procedures of theespax acid e-water(Diluted brine electrolysis)

14

１．PrePre-treatment process
・ before DFR laminate, PSR coating, WaterWater-soluble Flux
（Photo Solder Resist)（Dry Film Resist)１） Using espax acid e-water after polish (chemistry & physics））
・Purpose ： Remove copper dust & chemical residual
・Effect： Clean copper surface⇒⇒prevent distain

DI-water ③（40℃℃ ・１５sec））

DI-water ②

espax
acide-water

Squeezing

Squeezing

Polishequipment（chemical,machine）

DI-water ①

input

Squeezing★ Condition ： 40℃℃(Liquid temperature) &15sec. spray rinse

DFRlaminate

Ari Cut &Dry

・ Experiences ： CSP, FPC, Multi-PWB etc.15

２） Using in FPC & Semi additive Process(SAP) PWB＊ using in SPM before ＤＦＲ laminate★ Using before SPM process: Remove copper oxide film and grease（Purpose ： SPM process equalization ）Remove grease and acid film(40℃)

DI-water ③

espax
acide-water（15sec）

Squeezing

Squeezing( SPM )DI-water ②

Chemicalpolishing

Squeezing

Squeezing

espax
acide-water（15sec）

DI-water ①

input

Squeezing★ Using after SPM process: same as above + remove smuts
NextProcess
Air cut &DryDesmutting

espax alkaline e-water can beused here, too

・ Experiences ： CSP, FPC etc.16

How to remove oxide film (Movie)• Material: substrate processed by 180℃/90min.

17

Surface condition of copper processed by espax
acid e-water

The immersion in 10 min

The original copper surface

sprayed for 4 minutes.

chemical copper coating

Original

ｐH2.6 HClespax acidic e-waterespax acid e-water can achieve nano-level surface
roughening by its free chloride

18

User evaluation data
１. espax acid e-water after buff polish (2003 data)
Buff polish＋＋e-water rinse

Buff polish＋＋normal water rinse

３０µ
３０Atomic force microscope（（AFM)★ espax acid e-water can remove copper dust

after buff polishing process and fine burrs.

19

２．SPM alternative in DFR laminate pretreatment (2014））★ Overview of the pre-treatment line／／After plating process

Removal of the plating
irregularities

DI-water #4

DI-water #3

Before SPM process unit

DI-water #2

espax acid e-water
process unit

Squeezing

Squeezing

Biaxialpolishingmachine

DI-water #1

Processing conditions：： 40℃℃,16sec
Air Cut &Dry

Surface roughening
treatment★ Test results／／ Evaluation after etching
Pattern residual rate
Buffe + SPM

Buffe + e-water★ According to the result, espax acid e-water rinse can20
be used as replacement of SPM = save costs.

※ Reference：：Surface condition after treatment (previous page)
Surface observation
Brown color means discoloration by oxidation
Red and blue color describes unevenness#1 : Original (substrate after electrolytic copper plating)#2 : "substrate # 1“ + Buff process#3 : "substrate #2" + SPM(H2SO4/H2O2) rinse#4 : "substrate #2" + espax acid e-water rinse★ Smut removal after
SPM process isnecessary21

Evaluation test of DFR laminate prepre-treatment
in SAP processespax acid e-water can rough(nano-level) and clean board surface atthe same time, so can it be used as SPM rinse in DFR laminate
pretreatment process in SAP process?

１．Comparison of surface condition★ Internal evaluation testElectro-platingSPM

espax e -waterespax acidic e-water can achieve nano-level roughing.
How about DFR adhesion?

22

２．Comparison of adhesion with another rinsing method
Peel strength/Relative value＜Comparative assessment : in the case of SPM rinse =1＞＞

n=3 Average value

TEST CONDITIONS ： espax acid e-water、、40sec、、45℃℃★ According to these test data, espax acid e-water can be said tosubstitute for SPM rinse in DER laminate pre-treatment in SAP process※ we would like to recommend you to test it in actual production line.
23Considerations
In the case of evaluate espax acid e-water using existing chemical tankin your factory…..
Please be care full about following two points.

１）Washthe tank by hot water (40℃℃）
１）・ remove crystallized Cu-sulfate in the tank and pipings.
・ how to do? ： hot water cleaning (40℃℃/1hour））x 2times.
２）Processcondition for removal oxidized film
２）
① Process time ： 15 sec or more
② espax acid e-water temperature ： ４０℃
４０℃③ espax acid e-water pH ： < ｐH3.1＊ espax acid e-water replenishment is needed to avoid reducing
pH by water dragging out.
④ Quickly neutralized can prevent board oxidation and discoloration24

２．espax acid e-water & development process（（ＤＦＲ、ＰＳＲ）
・ Purpose ： prevent to tailing phenomenon of light-sensitive photo &remove residue (Desucm). As well as decreasing
Au(gold) plating failure.
（e-water works for fine scum removal like >10μ / evaluation by a user））

・Process condition ： time / at least 12 sec or more
（If process time is not enough, it can’t achieve expected results )* Liquid temperature / 40℃℃・ Experiences：： Package substrate manufacturers

Air Cut

DI-water ⑤

DI-water ④

espax
Acide-water(12sec)40℃

Squeezing

SqueezingDI-water ③

DI-water ②

Development

Squeezing

DFRorPSR

DI-water ①

Next step

Loading25

Scum removal effect in DFR Development
Running direction
Chamber No..4

Chamber No4 is used as e-water rinse chamber
DFR color is transferred to acid e-water .

Data for one month used
A company ： Short failure Rate
3.50
3.00

2.96

2.50
2.00
1.50

0.96

1.00

0.52

0.50
0.00

Before Dakutoru Rinse（13 Lot）

After Dakutoro Rinse（68Lot）

e-water 12Lot）

In this A company, failures became ppm order from % order.
=it works <L&S135μ26

Improvement of light-sensitive resin failure indeveloping water rinse section★ Improvement of tailing phenomenon⇒⇒pattern accuracy becomes good

DI-water
Tailing phenomenon

e-water
DFR development

e-water (SAP)・ espax acid e-water has neutralizing effect in DFR developing process.
Unexposed light-sensitive resin is neutralized immediately and tailingphenomenon stops. As the result, pattern accuracy going to be improved.
【Attention!!】】 espax acid water doesn’t remove light-sensitive resin tailing,it stops tailing phenomenon.

If you misunderstand it, and use e-water rinse wrong way, tailingphenomenon will occur often. → Why???

27

Misunderstanding e-water use indeveloping process••espax acid e-water doesn’t remove tailing, it can improve resolution by
preventing elution of unexposed light-sensitive resin.
If developing is not enough, it will be neutralized by espax acid e-water andtailing phenomenon will be remaining.
Developing process is carry out even
it is in water rinse chamber, becausealkali has already been swelling.

State soon after development ~ rinse

Only waterrinse

It has not been developed

Developing process stops because acid ewater neutralize soon, so it becomes
residue.
Acid e-water use.

★ It requires to confirm
developing completion point.

Residue remains. (Tailing)28

３． espax acid e-water & DFR striping
・ Purpose ：Remove striping residue and alkali burn・ Effect ： Prevent AOI simulated error（（Antirust, not strong effect)））※ Unlike H2SO4 or SPM, there is no discoloration after treatment.

espax acid e-water rinse afterstripping to clean Cu surface

Air Cut& Dry

Receivingmachine

DI-water ④

DI-water ③

espax acide-water（15sec）
40℃

Squeezing

SqueezingDI-water ②

SqueezingDI-water ①

LoadingDFR Striping
sectionLine configuration
Next step

It possible to replace these water rinse
with alkaline e-water rinse.

Experiences：： Package substrate, FPC, Multilayer substrate, etc.29

４．Finishing process（（Flux pretreatment））
・The purpose ： Abolition of SPM
５． Acid rinse after chemical copper plating(SAP)

Drag out＆Dry

Receivingmachine

Alkalinee-water ③

Alkalinee-water ②

espax acide-water（12sec）
40℃

Alkalinee-water ①Loading(Substrate after thechemical copperplating)

Squeezing・ The purpose ： Remove plating residue ＆ antirust (not strongeffect).
DFR Laminate

６． Acid rinse after Au- plating30

Basic process conditions of espax acid e-water• Process time ： >12sec or more（（recommendation 15 sec））＊ it should be more than 40 seconds in the case of roughening
treatment of the copper surface.
• Process liquid temperature ： ４０℃４０℃• Spray pressure ： 0.1Mpa or more
• Use nozzle ： use 5L / min type（（large amount of use））＊ It is necessary to increase the pump capacity.
• Management method：： < pH3.1 below（Replenishment of e-water））• After the treatment, neutralize first(Washed with water））★ If process time is not enough, it can’t work as

we expected.

31

To e-water rinse unit

DI-water③

DI-water②

espax
Acide-water

Squeezing

Squeezing

Roughening
equipment

DI-water ①

loader

Squeezing

Case example for Installation ＆ Managementunloader

Air Cut &Dry

Deionizer

pH measurement(e-water rinse unit)
e-water storage tank

Tap water orwell waterpH
measurement

Type: espaxJ02Ⅳ
Ⅳ-GS

Soft water machine32

Cost estimation
Drag out

DI-water ⑤

DI-water ④

EspaxAcide-water（12sec）
40℃

Drag out

Drag out

DI-water ③

Development

DI-water ②

DFR

DI-water ①

Input

Drag out

Example : developing process
Next step＜ 4L type espax e-water machine : 8.2hur./day for one month＞
１．Consumption
amount of Tap water （use it soften））
１．
・ 3,840L/Day About JPY691 / D××30Days= JPY20,736 / Month
２．Consumption amount1) Soft water generation ： 20㎏㎏/M About JPY2,000/M
2) For electrolysis： 20㎏㎏/M About JPY2,000/M

Total About JPY25,000/M （Electricity costs excluded））
cf. TypeJ0４
４ : Power consumption ： 3.6Kwh
For further information, please contact us.

33Considerations before use
１．E-water rinse is required large amount of acid e-water.
・Nozzle : 5L/min type, Spray : >100L/min
２．Treatment time : >12sec. Recommendation>15sec.
３．E-water temperature : 40 ℃
４．If the machine drag out lot of chemical or water, it need tomodify to drag out.＝＝Acid e-water is easily neutralized.
５．espax e-water machine must use DI water or soft water forelectrolyzation. (Prevent to attach calcium compound to negative pole)
６．Replenishing amount of espax acid water is 0.8 ~ 1L / min.
（it depends on amount of water drag out or Cu surface condition））● Caution：： if you use chamber for espax e-water treatment, which was used
SPM treatment, please wash it by hot water and remove
crystallized Cu-sulfate before use. (please refer to page 23)34

Considerations before use in overseas countries
１．Prefer to use DI-water (prevent Ca attachment)＊ Soft water can be used, but if soft water quality is no good,e-water tank might get damage.
＊ In the case using soft water, please do not forget addsalt(common salt is OK)

２．As
２． for salt for electrolyzation, please use sea salt,
or salt which is made in Japan. (please refer to following pictures)

35

Considerations for evaluation test
１．espax acid e-water treatment can’t work just soak test
board into e-water.
・ When using the espax e-water, it requires physical force.(spray andultrasonic)

２．espax acid e-water treatment works by water temperature
40℃℃. Especially, oxidized cu film removal.
・ 40℃℃ is optimum e-water treatment temperature.

３．espax acid e-water treatment test of DFR and PSRdevelopment should be done in your line.
・ Once scum is dried, it can’t be removed. So, test should be done indeveloping line to keep wet condition.
・ Break point need to be confirmed.
36

Precaution for use in e-water machine
１．There is possibility that sus parts might get rusted.
Parts which are soaked or touch acid e-water are not get
rusted, parts which are in e-water air layer, might get rusted.
(recommend to use Ti material for metal parts.
Acidic e-water use tank

Rust of Drag out part

There is no rust.

Rust has occurred in the air layer section.
37

２．MaintenanceElectrolytic cell needs to be replaced every 3000 hours (dependingon water quality)★ prevent adhesion of Ca, it must be regularly exchanged.
State of the neutral
membraneElectric current tends to flow to place where Ca is not attached, soelectric current flows only one place, then makes hole on Ti tube.

The appearance of theelectrolytic cell

Neutral membrane was broken, then electric current focuses on it and it
makes platinum plating peeled off. (5400 hours after use)38

Summary
We recommend to use espax e-water machine inelectric device industry including PWB industry asenvironmental-friendly system.
＜The espax e-water is a technology which does not giveburden to our environment.＞＞⇒ Reduction of amount of chemicals use（（Alternate alsopossible））⇒ Reduction of water consumption amount＝Water-saving⇒ Reduction of waste water amount⇒ Reduction of environmental impact

JIPCM LLC