New Developed Materials for Advanced Electro-Ceramics 1．Background MLCC development trends are moving towards thinner green sheet. Accordingly, Customers are demanding binder resins which improve green sheet strength, lamination properties, etc. 2．New Polyvinyl Acetal Resin for conductive paste Development Progress Sekisui Chemical’s ongoing R&D program has developed a new polyvinyl acetal resin for use as a temporary binder for screen printing pastes. SEKISUI’s New Resin exhibits excellent screen-printing characteristics and offers advantages over traditional alternatives. Properties Properties of New Resin, General PVB and Ethyl cellulose STD-100 are compared below： TableⅠ Properties Properties New Resin General PVB Ethyl cellulose Screen-printing ○ × ◎ Adhesion ◎ ◎ × Thermal decomposition ○ ○ △ Dispersion of powders ◎ ◎ ○ Flexibility ○ ○ △ Quality stability ◎ ◎ × Delivery stability ◎ ◎ △ Screen Printing Characteristics SEKISUI New Resin exhibits excellent screen printing characteristics, giving crisp, clean lines, without defects or stringing. Three types of binders were compared (SEKISUI New Resin, general PVB and ethyl cellulose). Scanning Electron Microscope photographs of screen printed pastes are shown below. Paste composition Metal : Ni (average of particle size : 0.4 µm) Ceramics : BaTiO3 (average of particle size : 0.1 µm) Solvent : α-terpineol Dispersing agent* : Lauric acid diethanol amide (obtained from Kao corporation) Binder :  SEKISUI New Resin ： good screen-printing characterisitics  General PVB ： poor screen-printing characterisitics  Ethyl cellulose (commonly used binder for screen-printing ) New Resin General PVB Ethyl cellulose OK Defects Present OK Adhesion between Conductive Layer and Green Sheet Adhesion was evaluated by measuring adhesion strength after heat pressing. Test conditions and results are shown below： Conductive Layer ： same as for screen printing tests above Green Sheet ： BaTiO3, ethanol/toluene, PVB FigureⅠ Adhesion srength conductive layer green sheet Tensile strength(gf/cm2) 50 40 30 New Resin 20 STD-100 Heater 10 0 40 60 80 100 120 140 Press and Release temperature(℃) SEKISUI New Resin is superior to STD-100 for adhesion strength. Thermo Gravimetric Properties Thermal decomposition characterisitics were determined by residual carbon measurement after fired firing at 450℃ in air. (FigureⅡ) FigureⅡ TG-curve 100 100 New Resin 10 STD-100 residual(wt%) 1 0.2 0.22 0.18 0.1 0.06 0.02 0.02 0.01 0 50 100 150 200 time(min) The Residue for SEKISUI New Resin is lower than for Ethyl-cellulose. SEKISUI CHEMICAL CO., LTD. 3. New plasticizer 「G-260」 for Green Sheet Scope To develop suitable plasticizers for Polyvinyl Butyral(PVB) Resins in ceramic binder applications. Characteristics （See TableⅠ） a) Excellent plasticizing characteristics for PVB Resins b) low volatilisity （ → easy handling ） c) low environmental impact ( G-260 is non-phthalic acid derivative ) TableⅠ Comparison with other plasticizers General plasticizer G-260 properties DOP DBP DOA Plasticizing Characteristics ○ ○ ◎ ◎ Low-volatilisity ○ × △ ○ Includes Phthalic Acid derivatives？ yes(×) yes(×) no(○) no(○) ※DOP(Dioctyl Phthalate), DBP(Dibutyl Phthalate), DOA(Dioctyl Adipate) Flow Temperature Comparison With Other Plasticizers Pressure Method ： Test material is made by dissolving specified １００kg/cm2 amounts of PVB resin (SEKISUI's BM-S) and plasticizer in a solvent of Ethanol/Toluene at 50wt%/50wt%. The film Heating up （thickness approx. 60 microns） is cast on 6℃/min. PET film and dried at the specified sample temperature. Using this film sample, the Flow-Temperature (Tf) is measured using the SHIMADZU Flow Tester. Φ1mm×10mm -3 Tf (Flow Temperature) = Temperature at Flow Speed 1×10 ml/sec FigureⅠ Flow Temperature of BM-S/Plasticizer＝100/30 100 Drying Conditions BM-SZ only Flow Rate ×１０ (cm /s） 3 DOP(60℃×20min.) -4 DOA(60℃×20min.) 10 DBP(60℃×20min.) G-260(60℃×20min.) 1 60 70 80 90 100 110 120 130 140 150 160 170 180 Ｔｅｍｐ． （℃） TableⅡ Flow Temperature of BM-S/Plasticizer＝100/30 BM-S BM-S/DOP BM-S/DBP BM-S/DOA BM-S/G-260 only 100/30 100/30 100/30 100/30 Ｔｆ 149℃ 95℃ 91℃ 86℃ 88℃ ※Drying Condition ： 60℃×20min. Low Tf → Softer PVB → Higher Plasticizing Ability FigureⅡ Volatility Comparison for Tf (Drying condition changed) Drying Conditions 100 Flow Rate ×１０ (cm /s） BM-SZ only 3 DOP(140℃×20min.) -4 10 DOA(140℃×20min.) DBP(140℃×20min.) G-260(140℃×20min.) 1 60 70 80 90 100 110 120 130 140 150 160 170 180 Ｔｅｍｐ． （℃） TableⅢ Volatility Comparison for Tf BM-S BM-S/DOP BM-S/DBP BM-S/DOA BM-S/G-260 only 100/30 100/30 100/30 100/30 Ｔｆ’ 149℃ 102℃ 149℃ 110℃ 100℃ ※Drying Condition ： 140℃×20min. Tf (Flow Temperature) increases when the PVB/Plasticizer film is dried at 140℃ for 20 minutes. This is caused by plasticizer volatilization. Plasticizer DBP in particular, may volatilize completely. In contrast, plasticizer G260 shows very low volatility. Result ： G-260 shows ： • Excellent Plasticizing Characteristics For PVB Resins • Low-Volatility Conclusion SEKISUI Addresses Customer Demands With The Development Of Advanced New Materials For Advanced Electro-Ceramics. SEKISUI CHEMICAL CO., LTD.