iuof03 uses of soybean oil - ink

8/6/2019 IUOF03 Uses of Soybean Oil - Ink

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Soy InksSoy Inks

Sevim Z. ErhanSevim Z. Erhan

National Center forAgricultural Utilization

ResearchUSDA/ARS, Peoria, IL

National Center forAgricultural Utilization

ResearchUSDA/ARS, Peoria, IL

Processing and MarketProcessing and Market

Printing InksPrinting Inks

O JG NBN SD G TY

O JG NBN SD G TY



Ingredients of Printing InksIngredients of Printing Inks

•Fluid Ingredients or Vehicles

•Solid Ingredients or Pigments

•Additives

•Fluid Ingredients or Vehicles

•Solid Ingredients or Pigments

•Additives

Typical Petroleum-based

Paste ink

Typical Petroleum-based

Paste ink

50-70%

15-25%

15-20%

50-70%

15-25%

15-20%

Mineral Oil

Alkyd or HC Resin

Pigment, Additives

Mineral Oil

Alkyd or HC Resin

Pigment, Additives



Polymerization MechanismsPolymerization Mechanisms

C C C C CC C C C C

C CC CCC CC

C CC C

C CC CCC CC

C CC CCC

CCCC CCCC

C CC CCC CC

C CC CCC

C CC C

CC C CC C

Polymerization ContinuedPolymerization Continued

C C C C C CC C C C C C

C CC C

CC

C CC C

CC

+



Polymerization ContinuedPolymerization Continued

Anthraquinone Catalyst

Isomerization

Anthraquinone Catalyst

Isomerization

CH3 (CH2)4 C C CH2 C C (CH2)7 CCH3 (CH2)4 C C CH2 C C (CH2)7 COO

OHOH

HHHHHHHH

++heatheatC

C

O

O

CH3 (CH2)4 C C C C C (CH2)7 CCH3 (CH2)4 C C C C C (CH2)7 COO

OHOH

HHHHHHHH

++

C+

C

OH

O


OHOH

HHHHHHHH

++C+

C

OH

O

++C

C

O

O

HH

--


OHOH

HHHHHHHH

HH

9,12 Linoleic Acid9,12 Linoleic Acid

9,11 Linoleic Acid9,11 Linoleic Acid

--



Gel Permeation Chromatograms of Alkali Refined-

60 min-, and 105 min Heat Bodied Soybean Oil

Gel Permeation Chromatograms of Alkali Refined-

60 min-, and 105 min Heat Bodied Soybean Oil

D e t e c t o r R e s p o n s e

Retention Time

Soybean Oil, MW = 1428

60 min, MW = 2656

105 min, MW = 4991

Gel Permeation Chromatograms of 125 min-, 150 min-

and 270 min Heat Bodied Soybean Oil

Gel Permeation Chromatograms of 125 min-, 150 min-

and 270 min Heat Bodied Soybean Oil


Retention Time

125 min, MW = 6030

150 min, MW = 8851

270 min, MW = 37693



Gel Permeation Chromatograms

of Soybean Oil Factice

Gel Permeation Chromatograms

of Soybean Oil Factice


Retention Time

MW = 60423

Viscosity and Color

of Heat Bodied Soybean Oil

Viscosity and Color

of Heat Bodied Soybean Oil

0.5

1.01.5

2.0

2.5

3.0

0.5

1.01.5

2.0

2.5

3.0

Reaction Time

(hours)

Reaction Time

(hours)

G-H

R-SV-W

Z2-Z3

Z5-Z6

Gel

G-H

R-SV-W

Z2-Z3

Z5-Z6

Gel

ViscosityaViscositya

<1

2-32-3

3-4

4-5

----

<1

2-32-3

3-4

4-5

----

Color bColor b

aGardner-Holdt viscosities; gel does not flow under prescribed conditions.bGardner Color Scale

aGardner-Holdt viscosities; gel does not flow under prescribed conditions.bGardner Color Scale



Heat Bodied Oil BlendsaHeat Bodied Oil Blendsa

Vegetable Oil Component (%w/w)Vegetable Oil Component (%w/w)

25.0 (X-Y)b

15.0 (X-Y)

50.0 (X-Y)

34.0 (Z8-Z9)

70.0 (Z3-Z4)

32.5 (Z8-Z9)

25.0 (X-Y)b

15.0 (X-Y)

50.0 (X-Y)

34.0 (Z8-Z9)

70.0 (Z3-Z4)

32.5 (Z8-Z9)

Heat Bodied

1

Heat Bodied

1

aSoybean, Sunflower, Safflower, Cottonseed and Canola OilbGardner-Holdt Viscosity Scale


75.0 (G-H)

85.0 (I-J)

0.0

26.6 (U-V0)

0.0

0.0

75.0 (G-H)

85.0 (I-J)

0.0

26.6 (U-V0)

0.0

0.0

Heat Bodied

2

Heat Bodied

2

0.0

0.0

50.0

39.4

30.0

67.5

0.0

0.0

50.0

39.4

30.0

67.5

Neat

3

Neat

3

M-N

M-N

M-N

M-N

W-X

W-X

M-N

M-N

M-N

M-N

W-X

W-X

Vehicle

Viscosityb

Vehicle

Viscosityb

Gel-Oil BlendsaGel-Oil Blendsa

Composition (%w/w)Composition (%w/w)

21.5-22.543.0-45.0

45.0-47.0

47.0-50.0

51.0-53.0

21.5-22.543.0-45.0

45.0-47.0

47.0-50.0

51.0-53.0

GelGel



78.5-77.557.0-55.0

55.0-53.0

53.0-50.0

49.0-47.0

78.5-77.557.0-55.0

55.0-53.0

53.0-50.0

49.0-47.0

OilOil

M-NV

W

W-X

X-Y

M-NV

W

W-X

X-Y

Vehicle

Viscosityb

Vehicle

Viscosityb



Characteristics and Composition

Of Vehicle Oils

Characteristics and Composition

Of Vehicle Oils

110.2

188.2

0.2

4.2

0.2

2.1

63.7

19.6

5.1

1.4

1.6

0.4

0.3

110.2

188.2

0.2

4.2

0.2

2.1

63.7

19.6

5.1

1.4

1.6

0.40.3

CanolaCanola

Iodine Number

Saponification No.

Fatty Acid Comp., %

C14:0

C16:0

C16:1

C18:0

C18:1

C18:2

C18:3

C20:0

C20:1

C22:0

C22:1

Iodine Number

Saponification No.

Fatty Acid Comp., %

C14:0

C16:0

C16:1

C18:0

C18:1

C18:2

C18:3

C20:0

C20:1

C22:0

C22:1

112.4

194.9

0.8

23.4

0.5

2.4

17.7

54.1

0.3

0.3

---

---

---

112.4

194.9

0.8

23.4

0.5

2.4

17.7

54.1

0.3

0.3

---

------

CottonseedCottonseed

127.7

190.2

0.1

10.2

0.1

4.3

25.2

52.7

6.0

0.3

0.2

0.4

---

127.7

190.2

0.1

10.2

0.1

4.3

25.2

52.7

6.0

0.3

0.2

0.4---

SoybeanSoybean

133.4

190.6

---

6.0

---

5.2

19.7

66.0

0.2

0.4

0.5

0.9

---

133.4

190.6

---

6.0

---

5.2

19.7

66.0

0.2

0.4

0.5

0.9---

Sunflower Sunflower

142.3

190.0

---

6.6

---

2.4

16.8

72.2

0.5

0.3

---

0.4

---

142.3

190.0

---

6.6

---

2.4

16.8

72.2

0.5

0.3

---

0.4---

Safflower Safflower

Vehicle Color EvaluationVehicle Color Evaluation

Vehicle Color aVehicle Color a

aGardner Color ScalebGardner-Holdt Viscosity ScalecSoybean Oil Viscosities of G-V have Color Values in the Range of 1-4dContains 22-27% Picco Resin

aGardner Color ScalebGardner-Holdt Viscosity ScalecSoybean Oil Viscosities of G-V have Color Values in the Range of 1-4dContains 22-27% Picco Resin

44

4

44

4

SoybeancSoybeanc

WW-X

X-Y

WW-X

X-Y

Vehicle

Viscosityb

Vehicle

Viscosityb

56

6

56

6

CottonseedCottonseed

6-77

7

6-77

7

CanolaCanola

33-4

3-4

33-4

3-4

Safflower Safflower

3-44

4

3-44

4

Sunflower Sunflower

1414

ANPA

(soybean)d

ANPA

(soybean)d



Ink Ruboff ResistanceInk Ruboff Resistance

Ruboff Valuesas Percent BlacknessRuboff Valuesas Percent Blackness

InitialInitial

123456789

101112

1314ANPA soy ink

123456789101112

1314ANPA soy ink

Experiment

Number

Experiment

Number

10.68.47.37.48.26.07.48.68.45.36.65.1

6.84.314.1

10.68.47.37.48.26.07.48.68.45.36.65.1

6.84.314.1

After 2 hr After 2 hr

6.55.27.07.06.65.55.85.95.64.65.24.4

4.54.28.4

6.55.27.07.06.65.55.85.95.64.65.24.4

4.54.28.4

393855

208

223133132114

34240

393855

208

223133132114

34240

Improvement

(%)

Improvement

(%)

Vehicles Used in this Study:Vehicles Used in this Study:

1- Commercial petroleum based news ink vehicleRef: Ernest W. Flick

1985 “Napim Pattern Printing Ink Formula, pp. 109.

1- Commercial petroleum based news ink vehicleRef: Ernest W. Flick

1985 “Napim Pattern Printing Ink Formula, pp. 109.

2- ANPA’s partial soy oil based news ink vehicle

Ref: ANPA1988 “Manufacturing Directions for Soybean Oil-Based ANPA-Ink.” pp. 1.

2- ANPA’s partial soy oil based news ink vehicle

Ref: ANPA1988 “Manufacturing Directions for Soybean Oil-Based ANPA-Ink.” pp. 1.

3- USDA’s 100% soy oil based news ink vehiclesRef: Sevim Z. Erhan and Marvin O. BagbyU.S. Patent 5,122,188.

1992 “Vegetable Oil-Based Printing Ink”(Type I and Type II vehicles)

3- USDA’s 100% soy oil based news ink vehiclesRef: Sevim Z. Erhan and Marvin O. BagbyU.S. Patent 5,122,188.

1992 “Vegetable Oil-Based Printing Ink”(Type I and Type II vehicles)



MicroorganismsMicroorganisms

Aspergillus fumigatus (NRRL 163)

Penicillium citrinum (NRRL 1843)

Mucor recemosus (NRRL 5281)

Aspergillus fumigatus (NRRL 163)

Penicillium citrinum (NRRL 1843)

Mucor recemosus (NRRL 5281)

Experimental ProtocolExperimental Protocol

5

12

25

5

12

25

Duration of

Fermentation

Duration of

Fermentation

Mono cultures

And

Mixed cultures

Mono cultures

And

Mixed cultures

MicroorganismsMicroorganisms

USDA’s 100% soy oil-

based

ANPA’s partial soy oil-

based

Commercial mineral oil-

based

USDA’s 100% soy oil-

based

ANPA’s partial soy oil-

based

Commercial mineral oil-

based

VehiclesVehicles



Biodegradation of Soybean Oil

and Ink Vehicles

Biodegradation of Soybean Oil

and Ink Vehicles

100

P e r c e n t D e g r a d a t i o n

Soybean Oil

0

Number of Days

90

80

70

60

50

40

30

20

10

0

5 10 15 20 25 30 35

100% Soy

(USDA)

Premium

(Commercial)

Partial Soy

ANPA - Commercial

(Broad Plots Prepresents All Data Ranging from Min. to Max.)(Broad Plots Prepresents All Data Ranging from Min. to Max.)

Biodegradation of Vehicle

in Ink Formulations

Biodegradation of Vehicle

in Ink Formulations

100

P e r c e n t D e g r a d a t i o n

Soybean Oil

0

Number of Days

90

80

70

60

50

40

30

20

10

05 10 15 20 25 30 35

USDA

ANPA

Commercial



% T CO2 at 28 Days% T CO2 at 28 Days

60

50

40

30

20

10

0 P e r c e n t T h e o r e t i c a l C O 2

10 mg/lt

20 mg/lt

NAA

(ANPA)

Commercial Soy Oil-

Pigment

USDA

Type of Ink



Number of Days at 60% T CO2Number of Days at 60% T CO2

500

400

300

200

100

0

T i m e ( D a y s )

10 mg/lt

20 mg/lt

NAA

(ANPA)

Commercial Soy Oil-

Pigment

USDA

Type of Ink

Biodegradation: USDA’s 100% vegetable oil-based news ink

degraded faster and more completely than either hybrid

vegetable oil-based or petroleum based inks.

VOC Analysis: USDA’s 100% vegetable oil-based news ink

showed the lowest % VOC, followed by hybrid vegetable

oil-based ink.

Deinking: Image analysis indicated that USDA’s 100%

vegetable oil-based news ink was removed more completely

than the hybrid vegetable oil-based ink, even after 6-months

aging.



News InkNews Ink

Vehicle (Carrier and dispersant for pigment)

100% vegetable oil

No VOC’s

No petroleum

Biodegradable

Exceptionally light color

Ink

U.S. patent 5,122,188. (1992)

Mechanisms

of Paste Ink Drying

Mechanisms

of Paste Ink Drying

A.

B.

C.

D.

E.

A.

B.

C.

D.

E.

Penetration

Evaporation

Quickset

Polymerization via Oxidation

Polymerization via Radiation

Penetration

Evaporation

Quickset

Polymerization via Oxidation

Polymerization via Radiation



Type of Paste InksType of Paste Inks

A.

B.

C.

D.

A.

B.

C.

D.

Coldset

Heatset

Sheetfed

Radiation Cure

Coldset

Heatset

Sheetfed

Radiation Cure

Mechanisms and Requirements for DryingMechanisms and Requirements for Drying

-Penetration

-Evaporation; Quickset

-Quickset; Oxidation

-Radiation

-Penetration

-Evaporation; Quickset

-Quickset; Oxidation

-Radiation

Drying by PenetrationDrying by Penetration

INK:INK: Pigment/Resin/SolventPigment/Resin/Solvent

SUBSTRATESUBSTRATE

Solvent PenetratesInto Substrate


Dried Ink:Dried Ink: Pigment/Resin (Solvent)Pigment/Resin (Solvent)

SUBSTRATE (SOLVENT)SUBSTRATE (SOLVENT)



Drying by QuicksetDrying by Quickset

INK:INK: Pigment/Resin/Drying Oil*/SolventPigment/Resin/Drying Oil*/Solvent

SUBSTRATESUBSTRATE



DRIED INK:DRIED INK: Pigment/Resin/Polymerized Drying Oil* (Solvent)Pigment/Resin/Polymerized Drying Oil* (Solvent)

SUBSTRATE/SOLVENTSUBSTRATE/SOLVENT

* and/or Drying Alkyd* and/or Drying Alkyd

SET INK:SET INK: Pigment/Resin/Drying Oil*/SolventPigment/Resin/Drying Oil*/Solvent

SUBSTRATE/SOLVENTSUBSTRATE/SOLVENT

Oxygen Diffuses into Set Inkand Polymerizes Drying Oil

Oxygen Diffuses into Set Inkand Polymerizes Drying Oil

Drying by EvaporationDrying by Evaporation

INK:INK: Pigment/Resin/SolventPigment/Resin/Solvent

SUBSTRATESUBSTRATESolvent Evaporates intoHot Air and Penetratesinto Substrates

Solvent Evaporates intoHot Air and Penetratesinto Substrates

DRIED INK:DRIED INK: Pigment/Resin (Solvent)Pigment/Resin (Solvent)


Hot Air Hot Air



Drying by Oxidation

Polymerization

Drying by Oxidation

Polymerization

INK:INK: Pigment/Drying Oil*/SolventPigment/Drying Oil*/Solvent

SUBSTRATESUBSTRATESolvent Penetrates Into Substrate;Oxygen Diffuses into Ink andPolymerizes Drying Oil*

Solvent Penetrates Into Substrate;Oxygen Diffuses into Ink andPolymerizes Drying Oil*

Dried Ink:Dried Ink: Pigment/Polymerization Drying Oil* (Solvent)Pigment/Polymerization Drying Oil* (Solvent)


* and/or Drying Alkyd* and/or Drying Alkyd

Drying by Oxidation

Polymerization

Drying by Oxidation

Polymerization

1.

2.

3.

4.

1.

2.

3.

4.

Peroxide/Hydroperoxide formation;

Decomposition to form free radicals,which initiate;

Polymerization;

Termination

Peroxide/Hydroperoxide formation;

Decomposition to form free radicals,which initiate;

Polymerization;

Termination

The primary reactions:The primary reactions:



Driers (Catalysts)Driers (Catalysts)

I

II

III

IV

I

II

III

IV

Shortens the induction period

Increase the rate of oxygen absorption

Promote the peroxide formulation and decomposition

Reduce the amount of oxygen required

Shortens the induction period

Increase the rate of oxygen absorption

Promote the peroxide formulation and decomposition

Reduce the amount of oxygen required

* Metal salts of carboxylic acids* Metal salts of carboxylic acids

* Based mainly on metallic ions that have two or morestable oxidation states: e.g.,

* Based mainly on metallic ions that have two or morestable oxidation states: e.g.,

Co++ e- Co+++Co++ e- Co+++

Vehicle FormulationVehicle Formulation

Heat Polymerized Vegetable Oil

Alkali Refined Vegetable Oil

Monoester

Heat Polymerized Vegetable Oil

Alkali Refined Vegetable Oil

Monoester

(85%)

(14%)

(1%)

(85%)

(14%)

(1%)



Dryer PassDryer Pass

1

2

3

4

5

6

7

8

9

1

2

3

4

5

6

7

8

9

VehicleVehicle

Methyl linoleate

Methyl linoleate

Methyl linolenate

Methyl linolenate

Linseed oil, methyl ester


Safflower oil, methyl ester


Tung oil, methyl ester

Methyl linoleate

Methyl linoleate

Methyl linolenate

Methyl linolenate





Tung oil, methyl ester

Ester Ester

No

Yes

No

Yes

No

Yes

No

Yes

Yes

No

Yes

No

Yes

No

Yes

No

Yes

Yes

Cobalt

Drier 2%

Cobalt

Drier 2%

-

+

-

sl

-

+

+

sl

+

-

+

-

sl

-

+

+

sl

+

00

-

+

sl

+

-

+

sl

+

+

-

+

sl

+

-

+

sl

+

+

11

-

-

vsl

-

-

vsl

55

+

+

vvsl

+

+

vvsl

1010

Percent Volatile Organic Compounds

(VOC) Analysis of Sheetfed Inks


(VOC) Analysis of Sheetfed Inks

USDA IUSDA II

USDA III

Commercial I

Commercial II

Commercial III

USDA I

USDA II

USDA III

Commercial I

Commercial II

Commercial III

InkInk

1.792.59

5.25

14.59

22.92

19.68

1.79

2.59

5.25

14.59

22.92

19.68

EPA Method 24EPA Method 24

Percent VOCPercent VOC




(VOC) Analysis of Heat-set Inks


(VOC) Analysis of Heat-set Inks

USDA I

USDA II

Commercial I

Commercial II

Commercial III

Commercial IV

USDA I

USDA II

Commercial I

Commercial II

Commercial III

Commercial IV

InkInk

1.28

8.60

31.96

28.36

35.15

30.67

1.28

8.60

31.96

28.36

35.15

30.67

EPA Method 24EPA Method 24

Percent VOCPercent VOC

Heat-Set and Sheet-Fed InksHeat-Set and Sheet-Fed Inks

(1998)



Current MarketCurrent Market

News Ink

Sheetfed Ink

Heat-set Ink

News Ink

Sheetfed Ink

Heat-set Ink

>

>

>

>

>

>

500 million pounds

100 million pounds

400 million pounds

500 million pounds

100 million pounds

400 million pounds



www.ncaur.usda.govwww.ncaur.usda.gov

[email protected]@ars.usda.gov

Sevim Z. ErhanSevim Z. Erhan

Research LeaderFood and Industrial Oil ResearchUSDA/ARS/NCAUR 1815 N. University St. Peoria, IL 61604

Research LeaderFood and Industrial Oil ResearchUSDA/ARS/NCAUR 1815 N. University St. Peoria, IL 61604

Phone: 309-681-6532Fax: 309-681-6340

Phone: 309-681-6532Fax: 309-681-6340

iuof03 uses of soybean oil - ink

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