Sulfurized Ep Additives for Lubricants Dailube

20170816 General-B02E11

SULFURIZED EP ADDITIVES FOR LUBRICANTS

® DAILUBE

FINE SYNTHESIS TECHNICAL DIVISION 1

Company Name DIC Corporation DIC Building, 7-20, Nihonbashi 3-chome, Chuo-ku, Corporate Headquarters Tokyo, Japan Date of Foundation February 15, 1908 Paid-in Capital ¥96.6 billion

Number of Employees Consolidated: 20,481 Nonconsolidated: 3,510 (As of December 31, 2016) Number of Group Companies 174 (Domestic: 31, Overseas: 143) (As of December 31, 2016)

Consolidated Net Sales \751.4 billion (Fiscal year 2016) Consolidated \54.2 billion (Fiscal year 2016) Operating Income

Printing Inks Fine Chemicals Polymers Compounds Application Materials

Printing Inks Pigment Polymers Liquid Compounds Application Materials Product Div. Product Div. Product Div. Product Div. Product Div. Offset inks, Organic pigments, etc. Acrylic resins, Jet inks, etc. Industrial adhesive tapes, Gravure inks, Polyurethane resins, Hollow-fiber membrane modules, Liquid Crystal Materials Solid Compounds News inks, etc. UV-curable resins, etc. Product Div. Health foods, etc. Product Div. PPS compounds, etc. TFT LC materials, etc.

1960’s Driers for Cobalt Carboxylates Driers, Catalyst printing Inks Adhesion promoter for tires

1970’s Commencement of Lead Carboxylates Sulfurized Fats(Dark color) Dark color EP additives sulfur EP additive for Gear oil business

1990’s Development of Low odor, Light color light color EP Additives Sulfur chemicals EP additives for MWF ‘DAILUBE®” for MWF

“Polysulfide ”

Carrier Sulfur chain (Sx) Carrier

Short sulfur chain = Less number of sulfur Chemical structures of carrier = More stable polysulfide is used to control property. = Less reaction with metal

= Inactive -Size of the structure: viscosity,

solubility, sulfur content, lubricity Long sulfur chain

= More number of sulfur -Chemical structure: reactivity, = Less stable polysulfide EP performance, stability, = More reaction with metal solubility = Active

2. Adsorption onto metal surface 1. Formation of metal sulfide tribofilm →enhance lubricity(reduction of µ) anti-seizure, anti-weld, anti-wear → 3D-Structure of Sulfurized Fat

FeS Fe O Film ＋ 2 3 Sulfur bond Metal 1000℃

Metal Carboxy group

Glycerol group No Sulfur additives Add Sulfur additive →seizuring, welding occurs →FeS tribo-film prevents seizuring and welding. R R R R SーS SーS ｜｜ | | Metal surface Primary function of DAILUBE products is prevention of seizuring and welding by formation of metal sulfide tribo-film. Some DAILUBE products also have significant effect to reduce friction by adsorption onto metal surface.

Metal

No Sulfur additives Add Sulfur additive

Oiliness additives Oleic acid, stearyl alcohol

Extreme Pressure additive Cl type、P type、S type Extreme Pressure additive Oiliness molecule Zn-DTP、Mo-DTC Molecule of EP additives Metal atom Solid lubricants Metal surface MoS2、Carbon black *1 星野道男：潤滑，29，2 （1984） 91.

Type of additives Cl type P type S type

Name of additives Chlorinated Paraffin Phosphate ester Sulfurized fat Sulfurized ester Sulfurized olefin

Mechanism ＦeＣl film ＦeＰＯ film 2 ４ＦeＳ-ＦeｘＯｙ film Minimum Temp １５０℃～1) ２２０℃～3) ２００℃～2) MP of film ２５０～６５０℃ ５００～１２００℃ １１５０～１２００℃ Range of temp. １５０～３５０℃1) ２２０－５００℃ ２００～８００℃ Feature Effective from low- Effective on middle load Effective on wide range middle load Easily decomposed and of load High environmental load dissolved in water Corrosive to yellow metal characteristic odor Application Cutting, Metal foaming Metal foaming, Slideway, Cutting, Metal foaming restriction of use(EU, Gear Grease, ATF fluid Slideway, Gear Grease, Japan) Mix use with sulfur ATF fluid

1) Journal of Japan Society of Lubrication Engineers,459(1974) 2) Journal of Japan Society of Lubrication Engineers.514(1974) 3) Journal of Japan Society of Lubrication Engineers,150(1975) COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 10 Agenda of presentation

DAILUBE® PRODUCT LINE

RAW MATERIAL LIGHT COLOR DARK COLOR INACTIVE ACTIVE

GS-225 S-290 GS-110 S-285 FATS GS-320 GS-325 GS-335 S-220 GS-330 S-225 GS-215 GS-210 GS-245 GS-240 GS-255*1 GS-235S ESTERS GS-230S GS-235LS

Sulfurized fat Sulfurized ester, acid Sulfurized olefin

Type Active Inactive Active Inactive Active Inactive

Carrier size Large Medium Small (C8- (Triglycerides) (Fatty acid ester or C18hydrocarbon) Fatty acid) Sulfur content 15% 10% 17% 10% 20-40% 20-30% (Typical value)

Sulfur chain size Long Short Long Short Long Short Solubility to oil good good Excellent Excellent Excellent Excellent

Reactivity to High Low High Low High Low metal surface

EP(anti-weld) Good - Good Good - Good Excellent Good - performance Excellent Excellent Excellent Lubricity Excellent Excellent Good - Good - Moderate Moderate (friction) Excellent Excellent Water mixable - - - Acid type Good Excellent application Excellent Product line of DIC’s Sulfurized Fat

■ DIC offers an assortment of Sulfur EP Additives, consisted of four types of Fatty Chemical basis.

Sulfurized fat Lard base DAILUBE GS-110, GS-225

Lard base DAILUBE GS-320, 325 Sulfurized fat & olefin Vegetable base DAILUBE GS-330

Vegetable Base Sulfurized ester DAILUBE GS-230S, GS-235LS, GS-235S

Lard base DAILUBE GS-210, 215 Sulfurized fat & ester Vegetable base DAILUBE GS-240, GS-245, GS-255 COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 14 14 DAILUBE® GS-200 series offsets

Inactive Moderately active Active (Copper corrosion (Copper corrosion (Copper corrosion <1b) 3a~4a) 4a<)

Triglyceride/ Product-R(9%S) Product-R(15%) Product-R(18%S) Ester Product-D(10%S) GS-255(15%S)*1 Product-D(17%S) GS-240(10%S) Product-L(16%S) GS-245(16%S) Ester GS-230S(10%S) Product-R(17%S) GS-235S(17%S) GS-235LS(17%S) *1:Newly investigated

・DAILUBE® GS-240, 245, 235LS, GS-255 are made from vegetable derived raw materials.

RAW MATERIAL LIGHT COLOR DARK COLOR INACTIVE ACTIVE S-290 GS-110 GS-225 S-285 FATS GS-320 GS-325 S-220 GS-330 GS-335 S-225 GS-215 GS-210 GS-245 GS-240 GS-255*1 GS-235S ESTERS GS-230S GS-235LS

Fatty acid GS-520 GS-550 GS-420 S-120 OLEFIN IS-30 GS-440L IS-35 *1:Newly investigated COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 16 SULFURIZED OLEFIN USING VARIOUS OLEFINS

X: 4～6, R: Hydrocarbon

DAILUBE DAILUBE CONPETITIVE PRODUCT PROPERTIES UNIT GS-440L GS-420*1 C8 C12 SULFUR CONTENT % 39.5 20.0 39.4 30.0 ACTIVE SULFER % 38.6 11.5 36.0 20.0 VISCOSITY(40℃) mm2/s 48.3 52.3 44.4 110 COPPER CORROSION (5%100℃1h) 4c 4b 4c 4c

Color(ASTM) - 2.0 3.5 L3.0 L1.5

WELDING LOAD (5%) N 2893 2354 2746 2648

Last Non-seizure Load(5%) N 618 618 618 618

TGA 50%loss ℃ 222 317 225 268

*1：GS-420 consist of olefin and small amount of fatty material

DIC is providing active types of Sulfurized olefin, DAILUBE GS-440L and GS-420. GS-440L has very high EP performance and GS-420 has high heat stability.

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 17 Mixture of GS-440L with other EP additives EP performance of GS-440L with Ca-Sulfonate, ZnDDP, Phosphate, Chlorinated paraffin GS-440L/other Scar Welding Load LNSL additives Diameter*1 Dosage 5% mm N N

GS-440L 0.98 2867 618

GS-440L / 3924< CaSulfonate 0.86 392 (1617) 2 =50/50 * GS-440L / 2867 0.58 618 ZnDDP=50/50 (1470) *2 GS-440L/Ca/Zn= 0.71 2893 981 50/25/25 GS-440L / 2452 0.43 618 Phosphate=50/50 (1274) *2 GS-40L/Ca/P 0.55 3090 491 =50/25/25 GS-440L / 2698 Chlorinated 0.64 618 (1470) 2 paraffin=50/50 * *1: 1500rpm 40Kg×60min @75℃ *2: data without GS-440L - Mixture of GS-440L with other EP agent can improve performance. - Ca Sulfonate can improve Welding Load, friction coefficient and Phosphate can improve scar diameter. COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 18 Agenda of presentation

Example of Convenonal Sulfurized oleﬁn tert-carbon-type

C8 Sulfurized oleﬁn Sulfur chain 4-5

X: Sulfur Chain length X≧4 Active C12 Dialkyl polysulﬁde Sulfur chain 3 or 5 X≦3 Inactive sec-carbon-type

Raw materials having unsaturated bond e.g. Olefin, Mercaptane

Sulfurized α-oleﬁn Sulfur chain4

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 2020 PRODUCT DEVELOPMENT INACTIVE SULFURIZED OLEFIN USING VARIOUS OLEFINS Reacvity and stability can be controlled by using diﬀerent structure as raw material

Temperature vs Acve sulfur content 50% decomposion temperature

Dibenzyldisulﬁde：２７４℃

【Active Sulfur:（ASTM D1662）】 Test fluid:50g Copper powder:20g Conditions:@150℃×60min. Sulfurized olefin include tertiary carbon

IS-30 is inactive but shows high EP performance. IS-35 shows high reactivity at lower temperature but has high heat stability Carbon Sulfur structure Secondary Tertiary chain length S3 - IS-30 S4 IS-35 GS-440L

Item Unit GS-440L IS-35 IS-30 Sulfur Content % 39.5 31.2 28.8 Example of Sulfurized olefin 2 Viscosity(40℃) mm /s 47 15 20 include secondary carbon (S3) Copper 5%100℃3hr 4c (1h) 4c(1h) 1b Corrosion 100%20℃1hr 3a 4a 1b 5% 2.89 2.40 2.65 Welding load kN 10% 2.70 2.89 2.99 Example of Sulfurized olefin include tertiary carbon Last non- 5% 0.49 0.54 0.49 (n=1:S3, n=2; S4) kN seizure load 10% 0.49 0.78 0.78 Scar diameter mm 0.99 0.86 0.75 5% 400N 75℃1hr TGA ℃ 222 267 233 50% Decomposition temperature

INACTIVE SULFURIZED OLEFIN – PROPERTIES AND PERFORMANCE

DAILUBE COMPETITIVE PRODUCT PROPERTIES UNIT IS-30 C12 C4 SULFUR CONTENT % 29.1 21.3 47.8 SULFUR CHAIN LENGTH 3.0 - - ACTIVE SULFER % 27.6 5.1 14.6 VISCOSITY(40℃) mm2/s 20 71 60

COPPER CORROSION (5%100℃3h) 1b 1b 3b

(5%120℃3h) 2d 3a 4c Solubility and stability ○ (Clear：○, not clear:×） - - 10% in GrⅢOil -5℃ 5dys ○ Neat -5℃ 5days WELDING LOAD (5%) N 2648 1814 2452

Last Non-seizure Load(5%) N 490 392 618

TGA 50%loss ℃ 233 238 233

DAILUBE IS-30 has a short sulfur chain and are inactive. IS-30 has high EP performance but a moderately elevated active sulfur level.

Properties of water based fluid using IS-30

EP Welding Base Oil Mixture of Oiliness Water Stability additives Load Emulsifier Paraffinic IS-30 Oleic acid Well water N 50℃60hr a - 7.68 2.28 0.05 90 1912 ○ No odor change b 2.58 5.10 2.28 0.05 90 2354 ○ No odor change c 4.28 3.40 2.28 0.05 90 2256 ○ No odor change d 5.98 1.70 2.28 0.05 90 1236 ○ No odor change e 7.68 - 2.28 0.05 90 784 ○ No odor change

b d c a

-Similar to Oil base application, IS-30 shows similar EP performance with active type GS-440L

INACTIVE SULFURIZED OLEFIN – PROPERTIES AND PERFORMANCE in Li-Grease Properties of Li-grease in different dosage DAILUBE CONPETITIVE PRODUCT of Sulfurized olefins PROPERTIES UNIT IS-30 C12 C4 SULFUR CONTENT % 29.1 21.3 47.8 SULFUR CHAIN LENGTH 3.0 - - ACTIVE SULFER % 27.6 5.1 14.6

VISCOSITY(40℃) mm2/s 20 71 60

COPPER CORROSION (5%100℃24h) 2a 1b 3a Performances of Li-grease in different dosage WELDING LOAD (5%) N 2157 2010 2647 of Sulfurized olefins Scar diameter (5%,785N, 1hr, 1200rpm) mm 0.97 1.21 1.13 Friction Coefficient (981N,200rpm) - 0.04 0.04 0.05 Result in Li-grease（No Additive: Welding load 1177N, SD 2.0mm<, µ 0.055） - IS-30 showed similar properties to C12 in Li-grease. - IS-30 can also improve welding load and wear compare with C12. In lower sulfur content, IS-30 achieve higher performance than middle active C4 additive.

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 25 DAILUBE IS-35 Properties IS-35 GS-440L TDPS properties C10 C8 C12 Sulfur content ( mass%) 31.2 39.7 30.1 Sulfur chain length 4.0 4.5 - Active sulfur (150℃, mass%） 20.0 39.0 19.0 5%, 1h 1b 1b 1b Copper 20℃ 100%, 1h 4a 3a 1b corrosion 100℃ 5%, 1h 4c 4c 4b Heat stability (TGA, 50% wt loss) 267 222 241

IS-35 is thermally stable, highly active at lower temperature and low friction coefficient.

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 26 Tapping torque testing result of IS-35 50% IS-35 GS-440L 50%Cl DAILUBE DAILUBE Chlorinated PROPERTIES Material GS-440L IS-35 Paraffin

Carbon 900 930 1107 Tapping torque Steel *1 result Aluminum N・cm alloy Die 550 620 590 Castings 1) Circumferential velocity: 8m/min, Tap: M8×1.25, Shape of Torque (Carbon Steel) Base oil: GrⅡ 21mm2/s@40℃, Dosage 5% as sulfur or Chlorine IS-35 GS-440L

Close up of edge of Tap Aluminum alloy Die Castings - IS-35 showed lower tapping torque than GS-440L both in Carbon steel and Aluminum alloy Die Castings. - Adhered material on Tap surface was smaller when IS-35 was used. These results indicated IS-35 can react with tool and material surface effectively.

1. Corporate profile of DIC and DIC’s Sulfur business 2. Design and function of DIC’s Sulfur chemicals 3. Feature of Sulfur additives compared with Cl, P additives 4. Product line-up of DIC’s Sulfur chemicals, “DAILUBE” 5. Recent product development of “DAILUBE”; IS-30, IS-35 6. The formulation example for non-chlorine fluid Light cutting Heavy cutting IS-30 or GS-440L 2-5% GS-440L 5-10% GS-230S or 2-5% IS-35 5-10% EP Additive GS-235LS ZnDTP or phosphate Phosphate ester 0-0.5% 0.5-10% ester Corrosion inhibitor Benzotriazole 0.05-0.1% Benzotriazole 0.05-0.1% Steel Lubricity Additives Fatty oil 2-5% Sulfurized fat or fatty oil 1-10% Anti mist 0-2% 0-2% Anti oxidant 0-2% 0-2% Base oil 80-90% 65-80% * Example of sulfurized Fat: DAILUBE GS-110 or S-220 * Recommended viscosity of formulated oil is about 20cst at 40℃. * If material is stainless steel, add 1-5% of overbased CaSulfonate to heavy cutting formulation.

Light Forming Heavy Forming IS-30 or GS-440L 2-5% GS-440L 5-10% EP Additive Sulfurized fat 2-10% IS-35 5-20% ZnDTP or phosphate 5-10% ZnDTP or phosphate ester 5-10% ester Corrosion inhibitor Benzotriazole 0.05-0.1% Benzotriazole 0.05-0.1% Fatty oil 5-10% Sulfurized Fat or fatty oil 5-20% Lubricity Additives Ca Sulfonate 1-3% Ca Sulfonate 3-5% Anti mist 0-2% 0-2% Anti oxidant 0-2% 0-2% Base oil 70-90% 60-90% * Example of sulfurized Fat: DAILUBE GS-110 or S-220 * Recommended viscosity of formulated oil is about 50cst at 40℃. * If process is pressing, remove Ca sulfonate phosphate, change EP additives to sulfurized fat.

Formulation 1 Formulation 2 IS - 3 0 5.0% IS - 3 0 5.0% EP Additive Phosphate ester 0.3% Phosphate ester 0.5% Lubricty Additives Sulfrized fatty ester 5.0% Ca Sulfonate 5.0% 40℃ viscosity of formulation 1 and 2 are 7.6 and 8.0 respectively. Scar Welding Load LNSL Diameter*1 Dosage mm N N GS-440L 5% 0.98 2867 618

GS-440L/MCCP=50/50 2698 0.64 618 5% (1470) *2

Formulation 1 0.48 4414 981

Formulation 2 0.48 4905 785

*1: 1500rpm 40Kg×60min @75℃ *2: Value without GS-440L

Formulation 3 Formulation 4 GS-440L 1.0% GS-440L 2.0% EP Additive IS - 3 5 3.7% IS - 3 5 2.5% Phosphate ester 0.3% Phosphate ester 0.5% Lubricty Additives Sulfrized fat 5.7% Ca Sulfonate 5.0% 40℃ viscosity of formulation 2 and 3 are 8.8 and 7.5 respectively. Scar Welding Load LNSL Diameter*1 Dosage mm N N GS-440L 5% 0.98 2867 618

GS-440L/MCCP=50/50 2698 0.64 618 5% (1470) *2

Formulation 3 0.48 9614 785

Formulation 4 0.48 8829 785

*1: 1500rpm 40Kg×60min @75℃ *2: Value without GS-440L

RAW MATERIAL LIGHT COLOR DARK COLOR INACTIVE ACTIVE

GS-110 GS-225 S-290 FATS GS-320 GS-325 S-285 GS-330 GS-335 S-220 S-225 GS-215 GS-210 GS-245 GS-240 GS-255*1 GS-235S ESTERS GS-230S GS-235LS

OPERATIONAL EXCELLENCE

ONE UNIVAR