20170816 General-B02E11 SULFURIZED EP ADDITIVES FOR LUBRICANTS ® DAILUBE FINE SYNTHESIS TECHNICAL DIVISION 1 COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 1 Agenda of presentation 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. DIC Corporate Profile 20170816 General-B02E11 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. COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 3 Historical Highlights of DIC Sulfur Chemical Business 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 COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 4 Agenda of presentation 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 Structure of sulfur EP “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 COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 6 Function of DAILUBE® Sulfur EP additives 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. COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 7 Agenda of presentation 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 Type of additives for lubricants Fes Fe O Film ＋ 2 3 Metal 1000℃ 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. COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 9 Type of Extreme Pressure additive for Lubricants 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 ４ ＦeＳ-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 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 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 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 12 Properties of DAILUBE products 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. COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 20170816 General-B02E11 15 DAILUBE® PRODUCT LINE 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.