Silicone Resins & Oligomers

Transcription

1 licone esins & ligomers

2 Adding Functionality, improving Durability and eliability licone esins & licone ligomers CNTENTS 2 What are licone esins and licone ligomers? licone esins P4-12 Structures of licone esins P4 Types of licone esins P4 Features of licone esins P4 Cure Systems of licone esins P5 elationship between Compositions and Characteristics of licone esins P5 Product List P6 Product Lineup P7 Map of Structures and Features P7 Applications P8-10 eat esistant Paints P8 Weather esistant Paints P9 esin Modifiers P9 Electrical Insulation Coatings P10 eat esistant & Electrical Insulation Binders P10 Main Products P11-12 P3 licone ligomers P13-19 Systems and Structures of licone ligomers Features of licone ligomers Types of licone ligomers Type A Product List P13 P13 P13 P14 Applications P14-15 rganic esin Modifiers oom Temperature Moisture Cure Coatings Type A Product List P16 Applications Coupling Agents Type Product List P16 P17 Main Products P18-19 Product Features & Packaging ptions P20-21 Catalysts P22 andling Precautions P23

3 What are licone esins? n a molecular level, silicone resins are primarily made up of siloxane units (--) which have a high bond energy. licone resin coatings have many useful properties including heat resistance, excellent weatherability, superior dielectric properties and water repellency. Used as esin alone Dehydration Condensation Cure Type: 1 Part Cure is available eaction Mechanism Before Curing eating over 150 C Dehydration Condensation eaction After Curing Structures of licone esins Used as rganic esin Modifiers eaction mechanism eaction condition: eating rganic resin Dehydration Condensation rganic resin Main Property & Application eat resistance Weatherability Solidify is possible loxane Structure: 3D Network structure Molecular Weight: Medium to igh Functional Groups: <eactive> lanol Groups (-), Vinyl Groups (-C=C2), ydrosilyl Groups (-) <Non-reactive> Methyl Groups, Phenyl Groups Addition Cure Type: Low Cure Shrinkage eaction Mechanism Before Curing C C C C C C C eating over 120 C + Adding Platinum Catalyst Addition eaction After Curing C C C C C C eat resistant paints Flame retardance Methyl groups or Phenyl groups Main Property & Application eat resistance Electrical Insulation Industrial paints Weatherability eat resistant paints Moisture proofing and insulation for circuit board Binders Polycarbonate flame retardants What are licone ligomers? licone oligomers are relatively low-molecular-weight silicone resins. These unique products can be used as resins on their own, they can be used to improve the properties of organic resins, or as modifiers to improve interfacial compatibility. Structures of licone ligomers Solventless (licone content 100%) loxane Structure: 3D Network structure Molecular Weight: Low Functional Groups: <eactive> Alkoxy Groups (-), Acrylic Groups, Methacrylic Groups, Epoxy Groups, Mercapto Groups and Vinyl Groups etc.. <Non-reactive> Methyl Groups, Phenyl Groups Used as resins on their own Dealcoholization-condensation Cure Type: Curable at room temperature eaction Mechanism Before Curing Adding Catalyst + Moisture in the air Dealcoholizationcondensation eaction Alkoxy Groups Methyl groups or Methyl / Phenyl groups and other organic functional groups Main Property & Application Water repellency Weatherability igh hardness After Curing Used as rganic esin Modifiers eaction Mechanism eaction condition: oom temperature or heating (catalyst should be used together) 1 Dealcoholization-condensation rganic resin 2 Dehydration Condensation rganic resin rganic resin rganic resin 3 Chemical eaction of Acrylic or Epoxy Groups Main Property & Application Adhesion Weatherability Water resistance Body coatings Floor coatings Water repellent agents Substrate & Encapsulants Adhesives Paints for construction materials 3

4 licone esins Structures of licone esins All silicone products are composed of the four units shown below. licone resins are composed mainly of T units, and cure to form hard coatings with a 3D network molecular structure. esins having D units (Di-functional) form flexible films, while those with Q units (Quadri-functional) will form films with higher hardness. Main Component M Units Mono-functional 3 1/2 D Units Di-functional 2 2/2 T Units Tri-functional 3/2 Q Units Tetra-functional 4/2 eactive groups Model of Curing licone esins Before curing eating Dehydration condensation reaction After curing Forming hard film with 3D network structure Methyl groups or Phenyl groups Features of licone esins With their molecular backbone of siloxane units, silicone resins outperform organic resins in heat resistance, weatherability and dielectric properties. Some of their special features are described below. Comparison of licone esins and rganic esins Features licone esins [Structure: -- ] rganic esins [Structure: C-C, C--C ] eat resistance Excellent 250 C Excellent 200 C Electrical properties Excellent Consistent across a wide range of temperatures Poor Decline in hot, humid conditions Low hygroscopicity igh hygroscopicity Water resistance Excellent (Due to the orientation of their -C Poor 3 ) (Absorbed water does not dissipate easily) Weatherability Excellent Excellent ultraviolet resistance Poor Flame retardancy Excellent Poor Must be used with a fire retardant Adhesiveness Excellent Particularly to inorganic materials Excellent Particularly to organic materials Mechanical strength Poor Intermolecular force: Small Excellent Intermolecular force: Strong / Crystallinity: Strong Chemical resistance Poor Vulnerable to strong acids and bases Excellent 4

5 licone esins Cure Systems of licone esins licone resins generally rely on one of two cure systems: dehydration-condensation and hydrosilylation. The majority cure by dehydration-condensation. The cure conditions and advantages of each cure systems are described below. Cure Systems Cure Conditions Features Condensation reaction Dehydration condensation Structure Containing silanol groups Catalysts Not necessary (But can be used to accelerate the reaction) eating Necessary (Methyl type: 100 C to 200 C, Phenyl type: 180 C to 250 C) ne Componet Cure Addition reaction ydrosilylation Structure Containing C=C 2 and Catalysts Necessary (Platinum based catalysts) eating Necessary (100 C to 150 C) apid Cure Low Cure Shrinkage elationship between Compositions and Characteristics of licone esins With silicone resins, the cure speed, film hardness, heat resistance and other properties can vary greatly depending on the resin s molecular weight, the types of organic substituents and functional groups it contains. The charts below show the relationship between a silicone resin s characteristics and its compositions, specifically the phenyl group content and ratio of T units to D units. Effects of Phenyl Group Content apid Cure Speed Slow ard Soft ardness ard Low Flexibility igh Excellent eat esistance Ph/ (mol%) Effects of T Unit Content Slow Cure Speed apid Soft ardness ard igh Flexibility Low Excellent eat esistance T Units/ (T Units + D Units) (mol%) 5

6 Product List Non-volatile Compatibility Cure Type content Solvent ardness with organic Main applications Features speed 105 C 3 h % resins K-220L None apid igh Low eat resistant and flame retardant binders White flake, excellent heat resistance and flame retardance, very little smoking by heatig K-220LP eat resistant and None apid igh Low Powder type of K-220L Methyl Type flame retardant binders Toluene, eat resistant and Excellent heat resistance and K-242A 50 apid igh Low isopropyl alcohol flame retardant binders flame retardance Moisture proofing and K Toluene apid Medium Low Thin hard coating insulating coatings Moisture proofing and K Toluene, xylene Slow Low Medium Solvent resistant flexible coating insulating coatings K ylene esin modification Excellent compatibility K ylene esin modification Excellent compatibility, more flexible than K-211 Moisture proofing and K Toluene, xylene Medium Medium Medium Glossy hard coating insulating coatings K ylene Slow Low Medium eat resistant paints K ylene Slow Low Medium eat resistant paints Excellent heat resistance Methyl/Phenyl Type Excellent flexibility and K ylene Slow Low Medium eat resistant paints anti-cracking properties K ylene Medium igh Medium eat resistant paints K ylene Medium Medium igh eat resistant paints Excellent heat resistance and flexibility Excellent heat resistance high hardness coating Excellent heat resistance and compatibility with organic resins A None Medium Medium Medium Molding None Medium Medium Medium Molding K None esin modification K-216 Propyl / Phenyl Type None esin modification Solventless, addition cure type, excellent curability and low shrinkage Solventless, addition cure type, 1 part, high Tg White flake, high phenyl content, excellent compatibility Solid shape, solventless, excellent compatibility ylene, ES-1001N 45 diacetone alcohol, eat resistant paints n-butanol Modified Epoxy ES-1002T esins 60 Toluene eat resistant paints ylene, ES eat resistant paints Excellent anti-corrosion property diacetone alcohol Modified Alkyd K ylene eat resistant paints Excellent flexibility and adhesion esins K PGMAC 2 eat resistant paints Modified PGMAC 2 (23%) K MMBAC 3 (13%) eat resistant paints Polyester esins isopropyl alcohol (4%) PGMAC 2 (20%) K MMBAC 3 (10%) eat resistant paints isobutyl alcohol (10%) K-114B ubber Type 50 Ligroin Moisture proofing and insulating coatings Excellent anti-corrosion property, heat resistance and weatherability Excellent anti-corrosion property and chemical resistance Excellent flexural resistance, heat resistance and weatherability etains glossy appearance under high temperature Excellent releasability and non-stick property Wax-like soft coating, Finished coating can be removed easily with solvents 1 Active ingredient 2 Propyleneglycol monomethylether acetate 3 3-Methyl-3-methoxybutyl acetate 6

7 licone esins Product Lineup Methyl licone esins Methyl / Phenyl licone esins Methyl silicone resins are a type of silicone resin in which the organic substituent groups consist entirely of methyl groups. These resins form very hard films with excellent moistureproofing properties, dielectric properties, water repellency, and release properties. In methyl phenyl silicone resins, the organic substituent groups consist of methyl groups and phenyl groups. These resins form coatings with excellent heat resistance, mechanical strength, and glossiness. Methyl Type K-220L K-220LP K-242A K-251 Modified Alkyd esin K-5206 Methyl/Phenyl Type K-112 K-211 K-212 K-255 K-271 K-272 K-282 K-300 K A K-480 rganic resin-modified licone esins rganic resin-modified silicone resins are silicone resins that have been hybridized with other organic resins. They form coatings with the advantages of organic resins (such as mechanical strength and chemical resistance), plus the features associated with silicone resins. Modified Epoxy esins ES-1001N ES-1002T ES-1023 Modified Polyester esins K-5230 K-5234 K-5235 Map of Structures and Features K-220L 1 K-220LP 1 K-242A 1 K-300 K K A K-311 K-112 K-271 K-272 K-282 igh ardness Low igh Low T Units / D Units atio 2 Low Compatibility with rganic esins Low Phenyl Group Content 2 igh apid Cure Speed Slow igh igh Low T Units / D Units atio 2 Phenyl Group Content 2 Low igh 1 Methyl silicone resin, contains no phenyl groups. 2 T Units / D Units atio and phenyl content are key factors determining hardness, cure speed and compatibility with organic resins, but not all products fit this pattern. 7

8 Applications eat esistant Paints With their excellent heat resistance, silicone resins are commonly used as paint vehicles for high temperature applications (200 C and higher) that are too hot for regular organic resin-based paints. They show good compatibility with common inorganic pigments, and owing to their excellent weatherability and moisture resistance, silicone resins can stand up to the punishment of outdoor exposure. eat resistant paints come in a variety of product types and compositions depending on the intended application, substrate material and usage temperatures. Many heat resistant paints, are in fact made using silicone resins. Weight Loss Data under igh Temperature (Methyl/Phenyl Type) (in air) eat esistance Comparison Data with rganic esins (under 250 C) licone resins Weight (%) Gloss retention ratio (%) licone modified alkyd resins Epoxy resins 60 Condensation Me thermal decomposition Temperature ( C) Ph thermal decomposition eating time (h) Alkyd resins Muffler Applications When combined with the right fillers and organic resins, silicone resins can be used for applications in a wide range of temperatures. Engine ven 600 C 500 C Pot 400 C eater Iron 300 C Plant Equipment 200 C Kettle ot-water eater Electric ice Cooker Frying Pan 8

9 licone esins Weather esistant Paints Traditional exterior coatings can deteriorate through exposure to UV rays, heat and water, all resulting in a loss of luster and/or chalking. owever silicone resins are not broken down by UV rays, heat or water. They have much better weatherability than regular organic resins and are commonly used as vehicles for exterior paints. Changes of Weather esistance Comparison Data with rganic esins Gloss retention ratio (%) Alkyd resins licone resins licone modified alkyd resins Time (h) The graph above shows the gloss retention as tested by weatherometer. With an organic resin (alkyd), the drop is dramatic. But the silicone resin and silicone-modified alkyd resin retain much of their original luster. Sunlight Absorption Comparison Data with rganic esins Illuminance (W/m) Absorption band of Methyl/Phenyl silicone Absorption band of organic resins Methyl silicone is not affected by sunlight, because sunlight passes through. Wavelength of the sunlight Wave length (nm) Much of the sunlight reaching the earth s surface is at wavelengths of 300 nm and higher. Most organic resins are susceptible to damage by light in this area of the spectrum. In contrast, Methyl silicone resins absorb almost no light in the UV spectrum, while Methyl/Phenyl silicone resins absorb only light in the spectrum below 280 nm, which means that sunlight has almost no effect. esin Modifiers licone resins with a high phenyl content have excellent compatibility with organic resins and can be used to imbue them with the many features of silicones. For example, K-480 can be added to polycarbonate during compounding to improve flame resistance. This and other silicone resins are attracting attention as a safer, more eco-friendly alternatives to conventional antimony, halogen or phosphate based fire retardants. Flame etardancy of Polycarbonate when Compounded with K-480 Limiting oxygen index (LI) % licone added: 5 phr PC alone PC plus straight-chain Methyl silicone PC plus K-480 Weight-average molecular weight of silicone: around 60,000 (Data on PC resin provided by NEC Corp.) Flame etardant Mechanism licone Polycarbonate (PC) Fire Fireproof layer Burning Extinction Sx Sx Excellent dispersion Dissolves & disperses in PC licone migrates easily to the surface licone moves quickly to the burning surface Interaction between PC and phenyl groups in the silicone Flame-retardant layer forms 9

10 Applications Electrical Insulation Coating licone resins retain high volume resistivity (over Ω cm) over a wide temperature range (room temp. to 200 C), and their dielectric properties show little dependence on temperature. In addition, they absorb very little moisture due to the orientation of the methyl groups at the surface of the coating. Features like these are why silicone resins are so often used to protect electronic components. Coefficient of moisture permeability (g/m 2 /24 h) K-114B: Film Thickness vs. Moisture Permeability Volume resistivity (Ω cm) 1.E+18 1.E+16 1.E+14 1.E+12 1.E+10 Temperature Dependence of Volume esistivity licone modified alkyd resins licone resins Alkyd resins 1.E Film thickness (mm) [esin + Glass cloth] Logarithmic temperature (1,000/T) Electrical Properties of Films K-251 K-255 K-114B K-112 Volume resistivity 1 Initial Ω cm Moisture absorption elative permittivity 1 Dielectric dissipation factor 1 50 z ,000 z ,000 z z ,000 z ,000 z Film thickness: 100 µm to 200 µm 2 Moisture absorption: measured after being left for 4 days at 85 C/85% eat esistant & Electrical Insulation Binders Dry Blend With their excellent heat resistance and dielectric properties, and because they do not soften when heated, silicone resins are used as binders for molding with powdered metals and other materials. And with the increasing popularity of hybrid and electric vehicles and photovoltaics, demand for silicone resins to be used as binders for coil molding are on the rise. Solution Blend K-220L K-220L Solvent Grinding Mix with filler Curing agents may also be added Dissolve in solvent Add fillers Solvent elimination Curing agents may also be added Melt Blend K-220L eating Melt Filler addition Cool Curing agents may also be added Powder silicone resin 10

11 licone esins Main Products K-220L, K-220LP Solid licone esins K-220L and K-220LP are solid silicone resins that undergo rapid crosslinking when heated. They are used as binders for inorganic materials, and can be used in molding to produce items with outstanding heat resistance, flame retardance and solvent resistance. nce solid silicone resins come in solid form, the choice of solvent is up to the user. K-220L and K-220LP will dissolve in toluene, xylene, isopropyl alcohol and other solvents. < Application Examples > Binders for mica laminated plate (Support structure for nichrome wire for irons, hair dryers and toasters; heat resistant washers, electrical insulation for high temperature instruments, thermal insulation boards, partition boards for microwave ovens) Flame retardant paints Binders for electrical & electronic components Paints for resistors Powder coatings General Properties K-220L K-220LP Appearance White flake White powder content wt% 3 3 Softening point C Gelation time 200 C s K-480 Solid licone esin for rganic esin Modification K-480 is a solid silicone resin designed for the modification of organic resins. It has especially excellent compatibility with polycarbonate resin (PC), and can be added to PC to improve flame retardance without sacrificing moldability, impact resistance or moisture resistance. < Application Examples > Flame retarder for polycarbonate (PC) Stress relaxation for epoxy resin General Properties K-480 Appearance White flake Softening point C 90 Active ingredient % 100 Properties of Polycarbonate esin (PC) when Compounded with K-480 PC alone PC with brominated flame retardant PC with K-480 Flexural strength kgf/cm Flexural modulus kgf/mm Impact strength kgf cm/cm eat deflection temperature C ockwell hardness Melt flow g/min Flame retardance UL94 1 V-2 V-0 V-0 1 Test piece thickness: 1.57 mm 11

12 licone esins Main Products K-251 Ultra igh Molecular Weight licone esin K-251 is a methyl silicone resin with a very high molecular weight. Common methyl silicone resins Very hard film Easy to crack eat cure is necessary K-251 The coating film is hard to crack. Forms the coating film by air drying alone Forms the harder coating film by heating General Properties K-251 Appearance Colorless transparent liquid Non-volatile content 105 C x 3 h % 20 Viscosity at 25 C mm 2 /s 18 Specific gravity at 25 C 0.92 Acid value < 2 Solvent Toluene Film Properties Clear coating Curing condition 25 C x 1 day 150 C x 30 min Film thickness µm 8 8 Pencil hardness B F Substrate: Polished steel sheet Common grade silicone resin Poor film forming properties when dried K-251 Forms a high quality film by air drying alone Low molecular weight eat cure or Catalyst igh molecular weight eat cure or Catalyst Easy to crack due to high crosslinking density Forms a harder coating. The collection of large molecules translates to excellent crack resistance, film-forming ability, and toughness A, licone esins for Mold making It is a line of silicone resins for mold making A and exhibit excellent heat resistance and have 100 % silicone content is easy to handle owing to the 1 part curability and higher Tg A (2 part addition cure silicone resin) Excellent heat resistance (1 part addition cure silicone resin) Excellent heat resistance and low-water absorption Comparison Chart of Cured Physical Properties eat resistance Tg Durability Properties of Molding A Epoxy Alicyclic epoxy Cure system Addition cure Acid anhydride cure Standard curing conditions 105 C x 2 h C x 2 h 200 C x 16 h (Tack-free time 1 h) 105 C x 2 h C x 2 h ardness Shore D Flexural modulus MPa 1, ,940 3,020 Tg C Volume change % after cure Boiling water absorption Before boiling Transparent Transparent Pale yellow Transparent Whitening Whitening (Transparent after 24 h) No change No change Appearance After boiling Transparency Water resistance Water absorption ratio % Molding examples Cure shrinkage A Epoxy Alicyclic epoxy Column (φ 8.0 mm) Sheet (Thickness: 0.2 mm) 12

13 licone ligomers Systems and Structures of licone ligomers licone oligomers is a term used for silicone resins with relatively low molecular weights and whose molecules have a 3D network structure. They generally consist of dimers and trimers and have molecular weights up to around 1,000. Their molecules can be functionalized with a variety of functional groups including methyls, phenyls, alkoxysilyls and reactive functional groups. Position of licone ligomer Model of Chemical Structure Tetramer Monomer Dimer Trimer lane licone ligomer lane Coupling Agent Polymer licone esin Low Molecular Weight igh Alkoxysilyl Groups Methyl Groups, Phenyl Groups and eactive Groups etc. Features of licone ligomers licone oligomers offer the following advantages, which are linked to their structures. Solventless They contain no solvents, and they release less alcohol when curing than do monomers. Used as rganic esin Modifier Compatibility with rganic esins wing to the low molecular weight, they have excellent compatibility. Low Volatile Content Even in high temperature conditions, there is little evaporation and the active ingredients function as designed. Large Number of eaction tes More effective than monomers, as there are more sites for reaction with the intended material. Used as esins oom-temperature Cure When used with a curing agent, silicone oligomers cure at room temperature by reacting with moisture in the air. igh ardness Their relatively low molecular weights mean they will form very hard coatings. Water epellency licone oligomers, especially those having methyl groups, form films with excellent water repellency. Types of licone ligomers licone oligomers can be categorized into three major groups, depending on whether or not they contain alkoxysilyl groups and reactive groups. Each type has different functions, and can be used for different purposes and applications. Classification of licone ligomers : eactive Groups (Epoxy, Methacrylate, Mercapto ) Containing Not Containing Type Modified licone Fluids Straight licone Fluids Type A Type A Not Containing Containing A : Alkoxysilyl Groups 13

14 Type A Alkoxysilyl Groups: Containing / eactive Groups: Not Containing Type A products contain alkoxysilyl groups, but no reactive groups. They may have methyls alone, or have both methyls and phenyls. Their structure is comparable to that of a silicone resin. Methyl Type Methyl silicone oligomers hydrolyze easily, and can be used as room-temperature/moisture-cure coating agents when used with the proper curing agent. They will form very hard coatings with excellent water repellency. Methyl/Phenyl Type These products have excellent compatibility with organic resins, so they can be used with organic resins as modifiers or as reactive diluents. They can also impart flexibility to coating which is curable due to the reaction with moisture under room temperature. And the coating is made up of methyl oligomers and catalyst. : eactive Groups (Epoxy, Methacrylate, Mercapto ) Not Containing Containing Type Modified licone Fluids Straight licone Fluids Type A Type A Not Containing Containing A : Alkoxysilyl Groups Product List eactive groups Alkoxy group Viscosity efractive index Alkoxy group at 25 C mm 2 /s at 25 C content wt% Features KC-89S Methyl Methoxy Low DP (degree of polymerization) K-515 Methyl Methoxy Medium DP K-500 Methyl Methoxy Medium DP Methyl Methoxy igh DP Methyl Methoxy Improves flexibility Methyl Methoxy Improves flexibility, thick coatings K-401N Methyl/Phenyl Methoxy Low phenyl content Methyl/Phenyl Methoxy Improves flexibility K-510 Methyl/Phenyl Methoxy Forms high hardness coatings K-9218 Methyl/Phenyl Methoxy Forms medium hardness coatings K-213 Methyl/Phenyl Methoxy igh phenyl content Applications rganic esin Modifiers Type A silicone oligomers contain alkoxysilyls, which are useful in and of themselves, or which can be hydrolyzed to form silanols. These oligomers can be used to modify organic resins to improve their heat resistance and weatherability. Alcoholic hydroxyl groups in the organic resin react with alkoxysilyls to release alcohol (dealcoholization condensation), or with silanols to release water (dehydration condensation). Typically, methyl oligomers are used with water-based organic resins, and phenyl oligomers are used with solvent-based organic resins. eaction mechanism Dealcoholization condensation Dehydration condensation rganic resin rganic resin rganic resin rganic resin Advantages of licone-modified rganic esins Acrylic esins Through silicone modification, we get the excellent solvent resistance, chemical resistance and durability of acrylic resins plus the weatherability and heat resistance of silicone. Modified acrylic resins are commonly used in paints for construction materials. Polyester esins Through silicone modification, we get the excellent flexural resistance of polyester resins plus the weatherability and heat resistance of silicone. Modified polyester resins are used to produce paints for construction materials, industrial uses, paints for home appliances that operate at high temperatures. Epoxy esins Through silicone modification, we get the excellent corrosion resistance of epoxy resins plus the weatherability and heat resistance of silicone. Modified epoxy resins are used in paints that provide protection against acids and other substances with strong staining potential. Alkyd esins licone modification improves the weatherability of alkyd resins. Modified alkyd resins cure at room temperature and are used in paints for storage tanks, ships, bridges and other things that are exposed to the elements. Model of esin Modification K-500 KBM-503 Improving Adhesion Acrylic esins Improving Weatherability Substrate Improving Adhesion KBM-503 Improving Weatherability K

15 licone ligomers oom Temperature Moisture Cure Coatings Model of after cure 2 Part Type When used with a curing agent, Type A oligomers can be used as oom-temperature/moisture-cure coating agents. They are used as auto body coatings, floor coatings, and in a wide array of other applications. Cross linking system By using different combinations of oligomers and curing agents, the user has considerable control over the cure speed as well as the hardness, flexibility and thickness of the cured coating. With the choices available, the user can find the right formula for specific purposes and applications. Coating Properties btained with Different Combinations of Products and Curing Agents Catalyst Film thickness Tack-free Flexural strength/ Pencil hardness (Additive amount) % µm at 25 C min Impact resistance K-500 D-20 (2) ± K-500 D-20 (4) ± to K-500 D-9740 (5) D-20 (3) K-500/ (=80/20) D-20 (2) F + +: Excellent ±: Satisfactory : Poor Substrate: polished steel sheet, Cure conditions: 25 C/70% 7 days (Tack-free time varies depending on temperature and humidity) 1 Part Type (Pre-blended) We offer a range of Type A products which come pre-blended with the optimal curing agents. With these products, no mixing of curing agents is involved. They can be applied to metal, stone, wood and plastic, where they will cure to form coatings with excellent weatherability and water repellency. K-400 is a special high hardness formula, is rapid curing, and K-401 offers excellent flexural strength and impact resistance. Product List eactive Viscosity efractive index Tack-free Pencil hardness groups at 25 C mm 2 /s at 25 C at 25 C min /curing days Features K-400 Methyl to 60 5/2g8/7 Forms high hardness coatings Methyl to 10 5/1 apid cure, Finished coating can be recoated. K-401 Methyl/Phenyl to 60 3/7 Excellent flexural strength and impact resistance Substrate: polished steel sheet, Film thickness = 10 µm, cured at 25 C/70% (Tack-free time varies depending on temperature and humidity) Exterior coatings for vehicles Floor coatings 15

16 Type A Alkoxysilyl Groups: Containing / eactive Groups: Containing Type A oligomers contain alkoxysilyl groups and organic reactive functional groups, meaning they can be used to promote adhesion between organic and inorganic materials. Think of them as oligomeric type coupling agents. eaction Mechanisms on Coupling Agents < Before reaction > < eaction model > Before hydrolysis After hydrolysis rganic resin Chemical bonding ydrogen bonding Inorganic material Chemical bonding : eactive Groups (Epoxy, Methacrylate, Mercapto ) Not Containing Containing Type Modified licone Fluids Straight licone Fluids Type A Type A Not Containing Containing A : Alkoxysilyl Groups : Functional groups which bind chemically to inorganic materials (glass, metal, silica stone etc..) Methoxy groups Ethoxy groups χ: Functional groups which bind chemically to organic materials such as synthetic resins Vinyl groups Epoxy groups Methacrylic groups Mercapto groups Product List eactive groups Alkoxy group Viscosity efractive index Alkoxy group at 25 C mm 2 /s at 25 C content wt% Features K-517 Epoxy Methoxy/Ethoxy Epoxy equivalent 830 g/mol A Epoxy Methoxy/Ethoxy Epoxy equivalent 350 g/mol Epoxy Methoxy Epoxy equivalent 590 g/mol K-516 Epoxy/Methyl Methoxy Epoxy equivalent 280 g/mol K-518 Mercapto Methoxy/Ethoxy Mercapto equivalent 800 g/mol Mercapto Ethoxy Mercapto equivalent 850 g/mol K-519 Mercapto/Methyl Methoxy Mercapto equivalent 450 g/mol K-513 Acrylate/Methyl Methoxy Acrylic equivalent 210 g/mol Methacrylate/Methyl Methoxy Methacryl equivalent 230 g/mol K-511 Vinyl/Phenyl Methoxy Vinyl equivalent 530 g/mol Applications Coupling Agents A key difference between these products and monomeric silane coupling agents lies in their volatility. Graph on the right is a graph comparing an acrylic oligomer to a silane coupling agent when the two are heated. With the oligomer, the active ingredient remains in place even at high temperatures, to better aid with adhesion. Comparison Data of Volatile Content of Acrylic ligomer (K-513) and lane Coupling Agent (KBM-5103) Volatile content (%) KBM K Temperature ( C) 3 h 16

17 licone ligomers Type Alkoxysilyl Groups: Not Containing / eactive Groups: Containing licone oligomers contain only epoxy groups as their reactive functional groups, and can be formulated to cure by way of an acid anhydride, photo-cationic or thermal-cationic curing system. licone oligomers cure using the same mechanisms as epoxy resins do, while offering excellent heat resistance and high Tg (gloss-transition temperature) that are characteristic of siloxane bonds. The cyclosiloxane-based oligomers exhibit low shrinkage during curing. : eactive Groups (Epoxy, Methacrylate, Mercapto ) Containing Not Containing Type Modified licone Fluids Straight licone Fluids Not Containing Type A Type A Containing Features A : Alkoxysilyl Groups licones which contain reactive functional groups elatively low molecular weights, and good compatibility with other materials Cure with light or heat when an acid generator is added Cure with heat when an acid anhydride- or amine-based curing agent is added K-470 has excellent cure properties and will be very hard & strong after curing. K-470 exhibits low shrinkage during curing. Product List General Properties Basic Structure of K-470 K Number of epoxy functional groups 4 2 Viscosity at 25 C mpa s 3, Epoxy equivalent g/mol Comparison Data of Cured Materials K-470 Epoxy Alicyclic epoxy Cure system Acid anhydride curing ardness Shore D Comparison Chart of Cured Materials Flexural modulus MPa 2,590 2,940 3,020 Curing shrinkage ratio (ydrometer method) % Adhesion Durability Tg Boiling water absorption ratio % Tg C Coefficient of liner expansion ( 10-5 /K) < Tg > Tg Water absorption ratio Volume change Transmissivity eat resistance K-470 Epoxy Alicyclic epoxy 17

18 Gloss retention ratio (%) Main Products Type A K-510 Methyl/Phenyl Group-containing Alkoxy ligomer K-510 is a Methyl/Phenyl silicone oligomer that contains methoxy groups. Because it has phenyls, K-510 has excellent compatibility with organic resins. K-510 can be mixed with organic resin containing groups that can react with methoxysilyls or be used in a methanol-releasing reaction to produce resins with improved heat resistance, weatherability and chemical resistance. K-510 can also be used as a reactive diluent. < Application Examples > Imparting siloxane structure of silicone oligomers into polyester resins, weatherability is improved. eaction mechanism Dealcoholization-condensation Polyester resin Polyester resin Weatherability Test esult of licone Modified Polyester esin licone content 50% licone content 30% licone content 0% 40 Dehydration Condensation Polyester resin Polyester resin ,000 Time (h) Test method: Sunshine weatherometer Polyester esin Modification with licone ligomers Polyester resin 70 wt. parts K wt. parts eaction (110 C-125 C x 30 min) PGM-AC Stop reaction Filtration, Adjusting Non-volatile Content licone Modified Polyester esins (Non-volatile content: about 50%) PGM-AC: Propylene glycol monomethylether acetate Tetraisopropyltitanate wt. parts General Properties K-510 Appearance Colorless transparent liquid Viscosity at 25 C mm 2 /s 100 Specific gravity at 25 C 1.16 efractive index at 25 C Methoxy content wt% 17 Active ingredient % 100 Film Properties Cure condition 285 C x 1 min 285 C x 10 min Pencil hardness 2 4 Adhesion (cross cut adhesion test) 100/ /100 Impact resistance Dupont test cm Min. 50 Min. 50 MEK rubbing times 100 Min. 100 ylene rubbing times 10 Min. 100 MEK: Methyl ethyl ketone Type A In K-516 and K-517, the organic functional groups (epoxy groups) and hydrolysable groups (alkoxy groups) are contained within the same molecule. This allows them to be used as coupling agents to enhance bonding between organic resins and inorganic materials. In addition, these oligomers can react with the active hydroxyl groups in an organic resin to form a copolymer. The organic resin will then be hydrophilic and have durable anti-stain properties and improved weatherability. < Application Examples > Coupling agents ydrophilic anti-stain agents K-516/K-517 Epoxy Group-containing Alkoxy ligomers General Properties K-516 K-517 Appearance Pale yellow transparent liquid Pale yellow transparent liquid Viscosity at 25 C mm 2 /s Specific gravity at 25 C efractive index at 25 C Epoxy content g/mol Active ingredient %

19 licone ligomers Type A K-500 Methyl Group-containing Alkoxy ligomer K-500 is methyl silicone oligomer that contains methoxy groups. This oligomer can be mixed with organic resin containing groups that can react with methoxysilyls or be used in a methanol-releasing reaction to produce resins with improved heat resistance, weatherability and chemical resistance. Water-borne resin application is available. < Application Examples > Modification via dehydration-condensation or dealcoholization-condensation. esults in improved adhesion to substrates and enhanced weatherability. Model of esin Modification Acrylic esins MMA etc. K-500 KBM-503 Water Polymerization initiator Surfactant KBM-503 KBM wt. parts 5-10 wt. parts 1-2 wt. parts wt. parts a few parts Improving Weatherability Improving Weatherability K-500 K-500 Stirring (Emulsifying) Copolymerization (eating) Cooling p Adjustment (p around 8) Improving Adhesion Substrate Improving Adhesion General Properties licone Modified Acrylic Emulsion (Non-volatile content: around 30-50%) K-500 Features Medium degree of polymerization Appearance Colorless transparent to pale yellow cloudy liquid Viscosity at 25 C mm 2 /s 25 Specific gravity at 25 C 1.15 efractive index at 25 C Methoxy content wt% 28 Active ingredient % 100 Type A K-513 Acrylate Group-containing Alkoxy ligomer In K-513, the organic functional groups (acrylic groups) and hydrolysable groups (methoxy groups) are contained within the same molecule. This allows K-513 to be used as a coupling agent to enhance bonding between organic resins and inorganic materials. < Application Examples > Coupling agents General Properties Appearance K-513 Colorless to pale yellow transparent liquid Viscosity at 25 C mm 2 /s 35 Specific gravity at 25 C 1.15 efractive index at 25 C Acrylic equivalent g/mol 210 Active ingredient %

20 Product Features & Packaging ptions Category licone esins licone ligomers Product name Type Appearance Non-volatile content Active ingredient Viscosity at 25 C Specific gravity at efractive index at Standard curing conditions 105 C 3 h % % mpa s 25 C 25 C K-220L White flake K-220LP Methyl Type White powder K-242A Colorless transparent liquid mm 2 /s 1.04 eat cure C 20 min K-251 Colorless transparent liquid oom temperature cure 2 25 C 20 min K-112 Colorless transparent to pale yellow translucent liquid mm 2 /s 1.06 oom temperature cure 2 25 C 15 min K-211 Colorless to pale yellow transparent liquid K-212 Colorless transparent liquid K-255 Colorless to pale brown transparent liquid mm 2 /s 1.02 oom temperature cure 2 25 C 20 min K-271 Pale yellow transparent liquid eat cure C 60 min K-272 Pale yellow transparent liquid eat cure 250 C 60 min Methyl/Phenyl Type K-282 Colorless to pale yellow transparent liquid eat cure C 60 min K-300 Colorless transparent to pale yellow cloudy liquid mm 2 /s 1.05 eat cure C 60 min K-311 Pale yellow transparent liquid mm 2 /s 1.06 eat cure C 60 min A Pale yellow transparent liquid 100 2, eat cure C 20 min Pale yellow transparent liquid 100 1, eat cure C 180 min (Tack-free 1h) K-480 White flake 100 K-216 Propyl/Phenyl Type Pale yellow transparent solid ES-1001N Pale yellow transparent liquid eat cure C 30 min ES-1002T Modified rganic esin Epoxy esins Pale yellow transparent liquid eat cure C 60 min ES-1023 Pale yellow transparent liquid eat cure C 30 min K-5206 Alkyd esins Pale yellow transparent liquid oom temperature cure 2 25 C 30 min K-5230 Colorless to yellow transparent liquid eat cure C 30 min K-5234 Pale yellow transparent liquid eat cure 180 C 20 min Polyester esins K-5235 Colorless to pale yellow transparent liquid eat cure C 20 min K-114B ubber Type Colorless transparent liquid 50 1,000 mm 2 /s 0.86 oom temperature cure 2 25 C 20 min KC-89S Colorless transparent liquid mm 2 /s K-515 Colorless transparent liquid mm 2 /s K-500 Methyl Type Colorless transparent to pale yellow cloudy liquid mm 2 /s Colorless transparent liquid mm 2 /s Colorless to pale yellow transparent liquid mm 2 /s Colorless transparent to pale brown cloudy liquid mm 2 /s K-401N AColorless transparent liquid mm 2 /s Colorless transparent liquid mm 2 /s K-510 Methyl/Phenyl Type Colorless transparent liquid mm 2 /s K-9218 Colorless to pale yellow transparent liquid mm 2 /s K-213 Colorless to pale yellow transparent liquid mm 2 /s K-400 Colorless to pale yellow transparent liquid mm 2 /s oom temperature cure 2 25 C min Methyl Type Colorless to pale yellow transparent liquid mm 2 /s oom temperature cure 2 25 C 5-10 min Coatings K-401 Methyl/Phenyl Type Pale yellow transparent liquid mm 2 /s oom temperature cure 2 25 C min K-517 Pale yellow transparent liquid mm 2 /s A Epoxy Type Colorless transparent to yellow cloudy liquid mm 2 /s Pale brown transparent liquid mm 2 /s K-516 Epoxy/Methyl Type Pale yellow transparent liquid mm 2 /s K-518 AColorless to pale red transparent liquid mm 2 /s Mercapto Type Colorless transparent to pale red cloudy liquid mm 2 /s K-519 Mercapto/Methyl Type Colorless transparent liquid mm 2 /s K-513 Acrylic/Methyl Type Colorless to pale yellow transparent liquid mm 2 /s Methacrylic/Methyl Type Colorless transparent liquid mm 2 /s K-511 Vinyl/Phenyl Type Colorless to pale yellow transparent liquid mm 2 /s K-470 Colorless transparent liquid 100 3, Alicyclic Epoxy Type Colorless to pale yellow transparent liquid Conditions until material becomes ethanol resistant 2 Time until material is no longer tacky 3 Propyleneglycol monomethylether acetate 4 3-Methyl-3-methoxybutyl acetate 5 2 L round cans 6 Fiber drums 7 Mini-drums 8 Paper bags 9 Glass bottles L round cans 20

21 Product Features & Packaging ptions Solvent Main applications Features UN hazard Packaging classification 1L cans 18L cans 200L drums None eat resistant and flame retardant binders White flake, excellent heat resistance and flame retardance, very little smoking by heating Not applicable 1 kg 5 10 kg 6 None eat resistant and flame retardant binders Powder type of K-220L Not applicable 1 kg 5 10 kg 6 Toluene, isopropyl alcohol eat resistant and flame retardant binders Excellent heat resistance and flame retardance UN kg 20 kg kg Toluene Moisture proofing and insulating coatings Thin hard coating UN kg 15 kg 160 kg Toluene, xylene Moisture proofing and insulating coatings Solvent resistant flexible coating UN kg 16 kg ylene esin modification Excellent compatibility UN kg 18 kg 180 kg ylene esin modification Excellent compatibility, more flexible than K-211 UN kg 18 kg 200 kg Toluene, xylene Moisture proofing and insulating coatings Glossy hard coating UN kg 20 kg kg ylene eat resistant paints Excellent heat resistance and flexibility UN kg 20 kg kg ylene eat resistant paints Excellent heat resistance UN kg 20 kg kg ylene eat resistant paints Excellent flexibility and anti-cracking properties UN kg 20 kg kg ylene eat resistant paints Excellent heat resistance high hardness coating UN kg 18 kg 200 kg ylene eat resistant paints Excellent heat resistance and compatibility with organic resins UN kg 20 kg kg None Molding Solventless, addition cure type, excellent curability and low shrinkage Not applicable 1 kg 18 kg None Molding Solvent less, addition cure type, 1 part, high Tg Not applicable 1 kg 18 kg None esin modification White flake, high phenyl content, excellent compatibility Not applicable 1 kg 5 20 kg 8 None esin modification Solid shape, solvent less, excellent compatibility Not applicable 1 kg 10 kg 6 ylene, diacetone alcohol, n-butanol eat resistant paints Excellent anti-corrosion property, heat resistance and weatherability UN kg 18 kg kg Toluene eat resistant paints Excellent anti-corrosion property and chemical resistance UN kg 18 kg kg ylene, diacetone alcohol eat resistant paints Excellent anti-corrosion property UN kg 18 kg kg ylene eat resistant paints Excellent flexibility and adhesion UN kg 16 kg kg PGMAC 3 eat resistant paints Excellent flexural resistance, heat resistance and weatherability UN kg 18 kg kg PGMAC 3 (23%), MMBAC 4 (13%) isopropyl alcohol (4%) eat resistant paints etains glossy appearance under high temperature UN kg 18 kg 200 kg PGMAC 3 (20%), MMBAC 4 (10%) isobutyl alcohol (10%) eat resistant paints Excellent releasability and non-stick property UN kg 18 kg kg Ligroin Moisture proofing and insulating coatings Wax-like soft coating, Finished coating can be removed easily with solvents UN kg 15 kg kg None Coatings, resin modification Low DP (degree of polymerization) Not applicable 1 kg 20 kg kg None Coatings, resin modification Medium DP UN kg 18 kg 200 kg None Coatings, resin modification Medium DP UN kg 18 kg kg None Coatings, resin modification igh DP Not applicable 1 kg 18 kg 200 kg None Coatings, resin modification Improves flexibility UN kg 18 kg 200 kg None Coatings, resin modification Improves flexibility, thick coatings Not applicable 1 kg 18 kg None Coatings, resin modification Low phenyl content UN kg 18 kg None Coatings, resin modification Improves flexibility Not applicable 1 kg 18 kg None esin modification Forms high hardness coatings Not applicable 1 kg 18 kg 200 kg None esin modification Forms medium hardness coatings Not applicable 1 kg 18 kg 200 kg None esin modification igh phenyl content Not applicable 1 kg 18 kg 200 kg None Coatings Forms high hardness coatings UN kg 18 kg kg None Coatings apid cure, Finished coating can be recoated UN kg 9 18 kg 10 None Coatings Excellent flexural and impact resistance UN kg 18 kg None Coupling agents Epoxy equivalent 830 g/mol Not applicable 1 kg 16 kg None Coupling agents Epoxy equivalent 350 g/mol UN kg 18 kg None Coupling agents Epoxy equivalent 590 g/mol Not applicable 1 kg 16 kg None Coupling agents Epoxy equivalent 280 g/mol Not applicable 1 kg 18 kg None Coupling agents Mercapto equivalent 800 g/mol UN kg 16 kg None Coupling agents Mercapto equivalent 850 g/mol UN kg 18 kg None Coupling agents Mercapto equivalent 450 g/mol Not applicable 1 kg 16 kg None Coupling agents Acrylic equivalent 210 g/mol Not applicable 1 kg 18 kg None Coupling agents Metacryl equivalent 230 g/mol Not applicable 1 kg 18 kg None Flame retardant, coupling agents Vinyl equivalent 530 g/mol Not applicable 1 kg 18 kg None Molding Low cure shrinkage, Epoxy equivalent 200 g/mol Not applicable 1 kg 18 kg None Molding Crack resistance, Epoxy equivalent 290 g/mol Not applicable 1 kg 18 kg 21

22 Catalysts Active Metal Type ingredient content Solvent % % Applicable products and cure conditions Applicable products Structure eating Additive amount wt% Features Phosphoric D Isopropyl alcohol esin lanol groups Necessary 5 to 10 Very high activity acid type A Phosphoric acid type 100 D-25 Titanium type D-20 Titanium type esin lanol groups Necessary ligomer (TypeA) Alkoxysilyl groups Not necessary esin lanol groups Necessary ligomer (TypeA) Alkoxysilyl groups Not necessary esin lanol groups Necessary ligomer (TypeA) Alkoxysilyl groups Not necessary 10 to 50 igh activity, can accelerate curing; contains reactive diluent 0.5 to 3 igher activity than D-20 2 to 5 Mild reactivity D-175 Titanium type 50 8 Toluene D-9740 Aluminum type CAT-AC Aluminum type 50 4 Toluene esin lanol groups Necessary Solvent diluting type 3 to 5 ligomer (TypeA) Alkoxysilyl groups Not necessary (Easy to use) esin lanol groups Necessary Forms high hardness 0.5 to 5 ligomer (TypeA) Alkoxysilyl groups Not necessary coatings esin lanol groups Necessary Solvent diluting type 0.5 to 10 ligomer (TypeA) Alkoxysilyl groups Not necessary (Easy to use) Amine KP n-butanol type Modified epoxy resins Epoxy groups Not necessary 5 to 15 Mild reactivity D-15 Zinc type 27 4 ylene, mineral turpentine esin lanol groups Necessary 1 to 3 Low reactive type D-31 Iron type 70 8 Mineral turpentine esin lanol groups Necessary 1 to 5 Low reactive type eaction Mechanism of Metal Catalysts M 2 1 ydrolysis Alkoxysilane Alcohol is released 2 Dealcoholization Condensation eaction M (Intermediate) M 3 Exchange eaction loxane Bonds Formed lanol M = Metal atom 22