K-FLEX Polyester Diol Selection Guide For High Performance VOC Compliant Coatings

Transcription

1 SPECIALTY CHEMICALS Polyester Diol Selection Guide For High Performance VOC Compliant Coatings

2 Formulating High Solids Coatings % active polyester diols are used primarily as modifiers for acrylic, alkyd, epoxy and polyester formulations with isocyanate or melamine crosslinkers. The low molecular weight and narrow molecular distribution of these diols allows for the formulation of higher solids coatings and high compatibility with difficult resins and solvents. Primary hydroxyl groups provide high reactivity for lower temperature cure. Typical modification levels are 5% to 15% on total resin solids. Formulate lower VOC coatings Lower cure temperature Increase flexibility & maintain hardness Maintain higher crosslink density Improve adhesion Excellent resistance properties Excellent compatibility Compatibilization & Solubility Most polyester resins have poor solubility in exempt solvents. Solubility in Oxsol 1 and t-butyl acetate are particularly difficult. The image below represents 33% replacements of polyester A&B to achieve solubility. polyester diols are soluble at 10-50% by weight in Oxsol, acetone, propylene carbonate, dimethyl carbonate and t-butyl acetate. polyester diols are very effective at compatibilizing other resins to achieve solubility in these exempt solvents. This is demonstrated in the adjacent image with two commercial resins (A&B) and Oxsol. compatibilization of other resins in Oxsol Identical results when used in t-butyl acetate Viscosity Reduction diols provide efficient viscosity reduction with low levels of solvent due to their narrow molecular weight distribution. Viscosity reduction of 188 with exempt solvents including Oxsol, t-butyl acetate and acetone are demonstrated in the graph to the right. A spray viscosity is possible with 188 at about 90% solids in acetone or about 80% solids in t-butyl acetate. Ketones and esters are very efficient solvents for viscosity reduction of the polyester diols. Viscosity cp (25 C) % Solvent Acetone t-butyl Acetate Oxsol

3 Solventborne High Solids 2K PU Coatings The formulation below demonstrates the performance of a high solids 2K acrylic polyurethane coating modified with 188, a light stable, high Tg (-32 C) polyester polyol. 188 modification is at 14% on TRS and VOC is reduced from 3.40 to 2.83 lbs./gal. Film Performance - Benefits Improved impact resistance Improved water resistance Major reduction in viscosity & VOC Maintained hardness Improved flexibility Description Weight % Joncryl Acrylic Resin 15.6 Titanium Dioxide MP Acetate K-SPERSE 152 Component 1 Grind Grind King Formulation API-17 Pigment Solvent Dispersant Description See Grind Acrylic 36.8 Modification 40.5 Joncryl 906 Acrylic Resin Polyester Diol M-2P Acetate Solvent BYK Wetting Agent Tinuvin HALS Tinuvin 1130 UV Absorber DBTDL (10 % in PM acetate) Catalyst Component 2 Desmodur 5 N-3300 Isocyanate resin Modification: 14% based on TRS Cure & Application Conditions FILM PROPERTIES 188 Cure Schedule: 30 minutes/80 C + 1 week ambient MEK Resistance (2X Rubs) + + Dry Film Thickness: 25µ ( mils) Substrate: Bonderite 6 0 Pendulum hardness, cycles Pencil hardness Reverse impact (image below) < Both the control and the modified system exhibited % crosshatch adhesion FAIL: 160 in-lbs (Magnified) FAIL: 160 in-lbs 188 PASS: 160 in-lbs 2

4 Compliance with Exempt Solvents - ZERO VOC 2K PU Topcoat diols have excellent solubility across a broad range of solvents including PC, DMC, TBA and PCBTF. Certain exempt solvents and resins were once incompatible with each other (see image on Page 1) resulting in poor appearance and poor performance. The addition of a polyester diol would compatibilize the resin and exempt solvent, resulting in improved film properties. Formulation of API-17 on Page 2 is based on conventional solvents. The VOC decreased from 3.40 to 2.83 lbs./gal. with a 188 modification. The solvents in API-17 were replaced with exempt solvents to obtain a Zero VOC formulation (API-18) described below. modification is at 14% on TRS. King Formulation API-18 Component 1 Description Acrylic XM-337 XM-366 XM-332 Grind (see API-18)* Resin, TiO2, Oxsol Joncryl 906-AC Acrylic Resin Polyester Diol Oxsol Exempt Solvent t-butyl Acetate Exempt Solvent BYK 310 Wetting Agent Tinuvin 123 HALS Tinuvin 1130 UV Absorber K-KAT XK-635 Catalyst Component 2 Basonat 7 HI- Isocyanate Resin * API-18 is similar to API-17 (Page 2), replacing Joncryl 906 with Joncryl 906-AC and MP Acetate with Oxsol Cure & Application Conditions FILM PROPERTIES XM-337 XM-366 XM-332 Cure Schedule: 1 month ambient Pendulum hardness, cycles Dry Film Thickness: 25µ Pencil hardness Pencil hardness Substrate: Bonderite 0 Reverse impact, in-lbs H-2H H-3H H-3H 2H-3H Direct impact, in-lbs % crosshatch adhesion & MEK 2X Rubs (all films in API-18 Formulation) 3

5 ZERO VOC 2K Polyurethane - Floor Coating Modification of this filled % non-volatile 2K polyurethane floor coating formulation (PI-13) demonstrates higher hardness, tensile strength, elongation, elastic modulus, tear strength and improved gasoline and transmission fluid stain resistance. was added at 10% on TRS and it partially replaced the branched polyether-polyester triol and linear polyether diol, as can be seen in the images below. King Formulation PI-13 Component 1 Sovermol Sovermol 1052 Description Polyether/PE Triol Polyether Diol Modification Cure & Application Conditions Cure Schedule: 2 weeks ambient Dry Film Thickness: 3 mm Substrate: 2K PU castings Polyester Diol Efka 9 SI 2008 De-aerator Barium Sulfate Filler Component 2 Basonat HI- Isocyanate K-KAT 6212 Catalyst FILM PROPERTIES Shore D hardness 53 XM Tensile strength, psi Elongation 1, , , Gasoline Soak, 30 Hours Elastic modulus 5,951 10,067 5,013 Break/load - Die C, pli Tear strength - Die C, psi Taber abrasion, wear index Crockmeter Taber Abrasion and Crockmeter: Lower number = Better performance XM % on TRS Transmission Fluid, 3 Day Spot Test Exposure days Exposure days XM-337 4

6 VOC Compliant Melamine Systems In the King formulation below (HS-19), 188 polyol is used as a modifier to provide improved flexibility, hardness and chemical resistance of a high solids polyester/melamine coating. Additionally, the modified systems resulted in better water resistance and a major viscosity reduction. King Formulation HS-19 Application Conditions Coating Type: Polyester/Melamine Cure Schedule: 15 minutes/121 C Dry Film Thickness: 20-25µ Substrate: Bonderite 0 Material Polymac 10 HS Cymel Methyl Ethyl Ketone Description Polyester Resin Melamine Crosslinker Polyester Diol Solvent % on TRS % on TRS % on TRS Catalyst: NACURE % on TRS 2-Butoxy Ethanol Solvent Film Performance - Benefits Significant improvement in impact resistance Major reduction in viscosity Maintained hardness Improved MEK resistance Better blushing resistance CHARACTERISTICS HS /K-188/Cymel /-/ % on TRS 23% on TRS 54/18/28 46/23/ % on TRS 33/34/33 Total resin solids, weight % Pencil hardness Brookfield viscosity (cps), 25 C FILM PROPERTIES Pencil hardness H-2H H-2H H-2H H-2H MEK Resistance (2X Rubs) Pencil hardness 90 Crosshatch adhesion Direct impact (in-lbs) Reverse impact (in-lbs) Water soak, C MD/9 Blushed MD/9 MD/9 MD/9 5

7 Product Recommendations The polyester diols have been separated and presented in two different charts below. The top chart includes polyester diols with similar hydroxyl numbers in the 220 to 265 range. When comparing these similar hydroxyl number diols, we observe a positive correlation between Tg, viscosity, film hardness, moisture resistance and exterior durability. These values tend to increase with increasing Tg. This correlation can be seen in the top chart below. The bottom chart includes polyester diols with lower hydroxyl numbers, ranging from 122 to 140. Due to the lower hydroxyl numbers, there is a lower crosslinker demand (isocyanate or melamine) compared to the resins in the above table. Both A307 and typically provide good flexibility. System Type Hydroxyl # as Supplied* Viscosity 25 C (cp) Tg Attributes / Uses High Crosslinker Demand HARDER XM SB, WB, % NV SB, WB, % NV ,000 10, Provides increased toughness and chemical resistance for solvent based and high solids systems. Highest Tg and modulus. Improves flexibility while maintaining hardness. Also improves salt spray, humidity resistance and exterior durability. Most versatile. 148 SB % NV 235 3, Improves flexibility and gloss. Increases solids at lower viscosity. Good flow and leveling. Recommended for primers. XM-366 SB, WB, % NV 265 2, Newest polyester with medium hardness. Great flexibility and gloss. SOFTER A308 XM-332 SB, %NV SB, % NV , Medium hardness with great flexibility. Best for mar and scratch resistance. Lowest viscosity for lowest VOC. Softer films. Low temperature impact resistance. *All products supplied % active except Lowest XM-332 Viscosity / Tg & Film Hardness A308 XM XM-337 Highest Low Crosslinker Demand A307 SB 140 5, Flexibility modifier with lower crosslinker demand ** SB 122 3, Offering longer pot life, improved adhesion and flexibility. Lower crosslinker demand. **Supplied 90% solids in xylene / n-butyl acetate 6

8 Polyester Diol Selection Guide Notes: Trademark References 1. OXSOL Makhteshim Agan 2. JONCRYL BASF 3. BYK BYK 4. TINUVIN BASF 5. DESMODUR Covestro 6. BONDERITE ACT 7. BASONAT BASF 8. SOVERMOL BASF 9. EFKA BASF 10. POLYMAC Polynt 11. CYMEL Allnex Contact Information Global Headquarters Tech. Service, R&D, and Sales King Industries, Inc. 1 Science Rd. Norwalk, CT 06852, USA Phone: European Tech. Sales Office King Industries, International Science Park XH Amsterdam The Netherlands Phone: Asia-Pacific Tech. Sales Office Synlico Tech Co., Ltd. 42 Ju Lin Ya Yuan RichMond Hill (Juhaoyuan) Zhongshan, China Phone: SPECIALTY CHEMICALS The conditions of your use and application of our products, technical assistance and information (whether verbal, written or by way of product evaluations), including any suggested formulations and recommendations, are beyond our control. Therefore, it is imperative that you test our products, technical assistance and information to determine to your own satisfaction whether they are suitable for your intended uses and applications. Such testing has not necessarily been done by King Industries, Inc. ("King"). The facts, recommendations and suggestions herein stated are believed to be reliable; however, no guaranty or warranty of their accuracy is made. EXCEPT AS STATED, THERE ARE NO WARRANTIES, EXPRESS OR IMPLIED, OF MERCHANTABILITY, FITNESS OR OTHERWISE. KING SHALL NOT BE HELD LIABLE FOR SPECIAL, INCIDENTAL, CONSEQUENTIAL OR EXEMPLARY DAMAGES. Any statement inconsistent herewith is not authorized and shall not bind King. Nothing herein shall be construed as a recommendation to use any product(s) in conflict with patents covering any material or its use. No license is implied or granted under the claims of any patent. Sales or use of all products are pursuant to Standard Terms and Conditions stated in King sales documents. _Polyesters_TVS10/17

9 SPECIALTY CHEMICALS Urethane Diol Selection Guide For High Performance VOC Compliant Coatings

10 Urethane Diols are low molecular weight (MW) diols with an aliphatic urethane backbone and a narrow MW distribution. They allow the formulation of higher solids, lower VOC waterborne coatings. They have been developed to help achieve VOC compliance with the added benefit of improved film performance. Their low molecular weight provides a higher crosslink density yielding harder films with greater exterior durability.

11 Formulating with Urethane Diols The aliphatic urethane backbone of Urethane Diols provides excellent light stability. It also allows the incorporation of aliphatic urethane functionality without the use of isocyanates. The urethane diols are used primarily as modifiers for melamine and isocyanate crosslinked coatings. They are compatible with polyester, polyether, acrylic and alkyd resins. UD Amino Crosslinked Systems Blocked Isocyanates 2K Polyurethanes Prepolymer Synthesis urethane diols are soluble in most polar organic solvents and in water. They are not soluble in more hydrophobic solvents like aliphatic or aromatic hydrocarbons. However, varying levels of hydrophobic solvents can be tolerated depending on the solubility parameters of the other solvents present. Advantages in Waterborne Coatings Urethane Diols act as cosolvents by reducing the viscosity of the system. They can be used to replace volatile cosolvents in order to increase solids, increase crosslink density, improve flow and leveling and yield higher gloss. Additionally, urethane diols enable the reduction or replacement of amine in the coating, resulting in lower VOC and faster cure of melamine baking systems. Higher hardness Lower VOC (higher solids) Excellent chemical resistance Excellent hydrolytic stability Improved wet adhesion Excellent gloss Product Supplied Hydroxyl # On Solids Viscosity 25 C (cps) 88% active urethane diol UD-350W 350 4,000 in water for WB coatings Attributes / Uses Higher solids, improved flow, gloss, hardness and resistance properties. UD % active urethane diol for SB coatings 350 9,000 Increases application solids and hardness. Improves chemical resistance, exterior durability and hydrolytic stability. UD-320- % active urethane diol 350 7,000 at 50 C Prepolymer synthesis. For water or solvent. Preparation of polyester urethanes. % active urethane diol XM-386 for SB and WB coatings ,000 All primary hydroxyl groups. Excellent low temperature cure response. Good moisture resistance. 2

12 Formulating with UD-350W for Waterborne Coatings UD-350W is an aqueous solution of an aliphatic, low molecular weight urethane diol oligomer. It is recommended as a modifier for amino crosslinked water soluble and emulsified acrylic, alkyd, urethane and polyester resins. It is used to increase solids, increase crosslink density and to improve film/resistance properties and flow/leveling. King Formulation UDW-12 Acrylic Melamine Emulsion Performance Description Pounds Joncryl Acrylic Emulsion 41.8 AMP 2 95 Grind Surfynol (Versum) Ti-Pure 4 R-960 Amine Wetting Agent Rutile TiO Water Diluent 48.6 Letdown Description Acrylic Urethane diol modification of a white acrylic/melamine emulsion (below) demonstrated several advantages, including improved flow/leveling, resulting in higher gloss, improved gloss retention, higher solids (lower VOC) and improved resistance properties seen below. Modification levels of 5, 10 and 15% were evaluated. Optimum levels of 5 and 10% are detailed below and on Page 4. Modification Acrylic//HMMM Composition % 70/0/30 65/5/30 57/10/33 Grind See Grind Joncryl 540 Acrylic Emulsion HMMM Crosslinker Butoxyethanol Solvent UD-350W Urethane Polyol Modifier - NACORR 1552 Corrosion Inhibitor and Accelerator 1.3 Water Diluent Total VOC Reduction, Co-solvent Replacement (Joncryl 540/HMMM) 75 VOC (g/l) % Solids 40 0 HMMM % UD-350W Modification on TRS 25 VOC % Solids 3

13 UD-350W - Waterborne Gloss Performance UD-350W urethane diol provides improved wetting over various substrates, as well as improved flow and leveling. The end result is higher gloss waterborne coatings. Gloss Enhancement & QUV Resistance 60 Gloss % UD-350W Modification on TRS Initial Gloss 1,200 QUV Hours UD-350W - Waterborne Performance The urethane backbone of the urethane diols provides excellent hydrolytic stability for long term storage in waterborne formulations. This excellent hydrolytic stability also provides improvements in the humidity, salt spray and boiling water resistance of fully crosslinked films. The results shown demonstrate these improvements in water reducible polyester/hmmm baking enamel. King Formulation UDW 16 HMMM Crosslinked Baking Enamel Humidity Resistance (350 hrs) 60 Gloss % Reflectance Salt Spray Resistance (350 hrs) Blisters* Salt Spray Resistance (350 hrs) mm Creep Boiled Water Resistance (1 hour) Blisters* Polymac 5 WR D 2 8D Water Reducible Polyester (UDW-16) UD-350W Total F 1 % on TRS No Attack *Blister Rank (ASTM D714): 10 = no blister, 1 = large blister D = Dense, M = Medium, F = Few Total 4

14 Formulating with UD-320 for Solventborne Coatings UD-320 is a high solids, aliphatic, low molecular weight urethane diol. It is soluble in polar organic solvents and has broad compatibility with acrylic, polyester and alkyd resins. When used to modify a 2-component polyurethane, it will increase hardness and flexibility. UD-320 will increase the hardness and humidity resistance of a melamine crosslinked system. Typical applications include general industrial and automotive OEM coatings. The formulation below illustrates the effect of UD-320 diol modification of a high solids automotive acrylic melamine coating. Benefits include higher solids, higher hardness and improved adhesion, chemical resistance, gloss and Florida exposure. Material Acrylic Resin King Formulation UD-3 Description Acrylic Resin Acrylic 64.2 UD-320 Modification 7% 13% 19% Urethane Diol Total HMMM Crosslinker NACURE 5528 Blocked Catalyst DISPARLON L Leveling Agent Xylene Solvent Methanol Solvent Total Characteristics Acrylic / / Mel 69/0/31 61/7/32 52/13/35 44/19/37 60 min., 110 C % Solids Viscosity, 25 C (cps) Cure & Application Conditions FILM PROPERTIES 7% 13% 19% Cure Schedule: 20 min / 120 C Pencil Hardness, Cycles F-H F-H H-2H H-2H Dry Film Thickness: 37.5µ % Crosshatch Adhesion Pencil hardness Substrate: Iron Phosphated CRS Reverse impact, in-lbs Direct impact, in-lbs

15 Film Properties - Chemical Resistance, QUV, Florida Exposure The control formulation was modified with 7% and 13% UD-320 for testing chemical resistance. With each modification level, we increased the melamine content slightly, to accommodate the high hydroxyl number of the UD-320. A 24 hour spot test was conducted to evaluate the chemical resistance to ethanol, n-butanol, xylene and gasoline. For each of these solvents tested, we see an improvement in the chemical resistance with a UD-320 modification. In addition, the chemical resistance increases with modification level. 24 Hour Spot Test, Tukon Hardness Tukon Hardness (Knoop, 25g) Ethanol n-butanol Xylene Gasoline 0% UD-320 7% UD % UD-320 Florida Exposure Study - Gloss Retention & Crack Resistance 60 Gloss Results - Florida Exposure (7.5 years) Modification with 7% UD-320 drastically improved long term gloss stability in harsh environments as shown in the chart to the right. 60 Gloss years 7.5 years 0% UD-320 7% UD-320 Florida Exposure - Checking (crack) Resistance 12 The chart to the right demonstrates improved checking resistance with UD-320 modification versus the acrylic control after 90 months (7.5 years) exposure in Florida at 5 South without UV stabilizers. Modification at the 7% level provided the best overall cracking resistance. Checking (cracking) Months 0% UD-320 7% UD-320 6

16 Urethane Diol Selection Guide Notes: Trademark References 1. Joncryl NACURE XC-269 Steam Resistance BASF 2. AMP 3. Versum Dow Evonik 4. Ti-Pure Chemours 5. Polymac Polynt Contact Information Global Headquarters Tech. Service, R&D, and Sales King Industries, Inc. 1 Science Rd. Norwalk, CT 06852, USA Phone: European Tech. Sales Office King Industries, International Science Park XH Amsterdam The Netherlands Phone: Asia-Pacific Tech. Sales Office Synlico Tech Co., Ltd. 42 Ju Lin Ya Yuan RichMond Hill (Juhaoyuan) Zhongshan, China Phone: SPECIALTY CHEMICALS The conditions of your use and application of our products, technical assistance and information (whether verbal, written or by way of product evaluations), including any suggested formulations and recommendations, are beyond our control. Therefore, it is imperative that you test our products, technical assistance and information to determine to your own satisfaction whether they are suitable for your intended uses and applications. Such testing has not necessarily been done by King Industries, Inc. ("King"). The facts, recommendations and suggestions herein stated are believed to be reliable; however, no guaranty or warranty of their accuracy is made. EXCEPT AS STATED, THERE ARE NO WARRANTIES, EXPRESS OR IMPLIED, OF MERCHANTABILITY, FITNESS OR OTHERWISE. KING SHALL NOT BE HELD LIABLE FOR SPECIAL, INCIDENTAL, CONSEQUENTIAL OR EXEMPLARY DAMAGES. Any statement inconsistent herewith is not authorized and shall not bind King. Nothing herein shall be construed as a recommendation to use any product(s) in conflict with patents covering any material or its use. No license is implied or granted under the claims of any patent. Sales or use of all products are pursuant to Standard Terms and Conditions stated in King sales documents. _UD_TVS11/17