ZIEHM CHRISTOPHER (US)
HICKEN RYAN (US)
TARNG MING-REN (US)
US3575910A | 1971-04-20 | |||
US5171638A | 1992-12-15 |
DATABASE WPI Week 201768, Derwent World Patents Index; AN 2017-64068B, XP002804088
DATABASE WPI Week 201756, Derwent World Patents Index; AN 2017-37343X, XP002804089
WHAT IS CLAIMED IS: 1. A method comprising: a) forming a pre-emulsion by combining a monomer composition with a siloxane- containing composition in water, the monomer composition including one or more monomers selected from the group consisting of (meth)acrylic acid monomers, (meth)acrylic monomers, vinyl functional monomers, and combinations thereof; and b) polymerizing the pre-emulsion by combining the pre-emulsion with a radical initiator in a reactor to form a reaction mixture that polymerizes into an emulsion polymer. 2. The method of claim 1 wherein the vinyl functional monomers are selected from the group consisting of styrene, vinyl acetate monomers, vinyl ester monomers, and combinations thereof. 3. The method of claim 1 wherein the siloxane-containing composition includes siloxanes and polysiloxanes functionalized with amino, hydroxyl, epoxy, vinyl, or acrylate groups. 4. The method of claim 1 wherein the siloxane-containing composition includes a compound having structure 1, 2, or 3: wherein: a, b, and m are each independently 0 to 100. R1, R2, R3 are each independently C1-10 alkyl, C6-14 aryl, C6-15 heteroaryl, -NH2, , -R4-OH, -R4- NH2, epoxy group, vinyl group, hydrogen, or acrylate group; and R4 is a C1-10 alkenylene group. 5. The method of claim 4 wherein R1, R2, R3 are each independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or allenyl groups. 6. The method of claim 1 wherein the siloxane-containing composition includes a compound having structure 4, 5, 6, 7, or 8: 7. The method of claim 1 wherein the radical initiator is selected from the group consisting of organic peroxides, azo-compounds, metal iodides, metal alkyls, persulfates, and combination thereof. 8. The method of claim 1 wherein the monomer composition includes one or more monomers selected from the group consisting of acrylic acid, methacrylic acid, and combinations thereof. 9. The method of claim 1 wherein the monomer composition includes one or more monomers selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl methacrylate, methyl methacrylate, butyl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and combinations thereof. 10. The method of claim 1 wherein the monomer composition includes butyl acrylate, ethyl hexyl acrylate, methyl methacrylate, acrylic acid, and methacrylic acid. 11. The method of claim 1 wherein step b) includes a seeding step in which a portion of the pre-emulsion and a predetermined amount of initiator are added to reaction mixture and allowed to react for a first predetermined time period at a first predetermined temperature. 12. The method of claim 11 wherein the first predetermined time period is from about 10 minutes to 2 hours and the first predetermined temperature is from about 70 ºC to about 100 ºC. 13. The method of claim 11 wherein an additional amount of the pre-emulsion and the radical initiator is added to the reaction mixture over a second predetermined time period at a second predetermined temperature with mixing. 14. The method of claim 13 wherein the second predetermined time period is from about 1 hour to 10 hours and the second predetermined temperature is from about 70 ºC to about 100 ºC. 15. The method of claim 13 further comprising adding a neutralizing agent to the reaction mixture. 16. The method of claim 1 wherein a final siloxane-containing resin emulsion is a composition that includes all of components that have been added to the reaction mixture such that the monomer composition is present in an amount from about 25 to 65 weight percent of the final siloxane- containing resin emulsion, the siloxane-containing composition is present in an amount from about 0.05 to 25 weight percent of the total weight of the final siloxane-containing resin emulsion, and the radical initiator is present in an amount from about 0.05 to 2 weight percent of the total weight of the final siloxane-containing resin emulsion, with the balance being water. 17. A paint composition comprising the emulsion polymer made by the method of claim 1, the paint composition forming a coating with burnish and mar resistance. 18. A method comprising: a) forming a pre-emulsion by combining water with a monomer composition including one or more monomers selected from the group consisting of (meth)acrylic acid monomers, (meth)acrylic monomers, vinyl acetate monomers, vinyl ester monomers, styrene monomers, and combinations thereof; b) polymerizing the pre-emulsion by combining the pre-emulsion with a radical initiator in a reactor to form a reaction mixture that polymerizes into an emulsion polymer; and c) combining the emulsion polymer with a siloxane-containing emulsion to form a siloxane-containing resin emulsion, the siloxane-containing emulsion including a siloxane-containing composition. 19. The method of claim 18 wherein the siloxane-containing composition includes siloxanes and polysiloxanes functionalized with amino, hydroxyl, epoxy, vinyl, or acrylate groups. 20. The method of claim 18 wherein the siloxane-containing composition includes a compound having structure 1, 2, or 3: wherein: a, b, and m are each independently 0 to 100 and need not be an integer as to describe an average structure; R1, R2, R3 are each independently C1-10 alkyl, C6-14 aryl, C6-15 heteroaryl, -NH2, , -R4-OH, -R4- NH2, epoxy group, vinyl group, hydrogen, or acrylate group; and R4 is a C1-10 alkenylene group. 21. The method of claim 20 wherein R1, R2, R3 are each independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, hydrogen, or allenyl groups. 22. The method of claim 18 wherein a final siloxane-containing resin emulsion is a composition that includes all of components that have been added to the reaction mixture such that the monomer composition is present in an amount from about 25 to 65 weight percent of the final siloxane- containing resin emulsion, the siloxane-containing composition is present in an amount from about 0.05 to 25 weight percent of the total weight of the final siloxane-containing resin emulsion, and the radical initiator is present in an amount from about 0.05 to 2 weight percent of the total weight of the final siloxane-containing resin emulsion, with the balance being water. 23. A paint composition comprising the emulsion polymer made by the method of claim 18, the paint composition forming a coating with burnish and mar resistance. |
wherein: a, b, and m are each independently 0 to 100, need not be an integer as to describe an average structure. R 1 , R 2 , R 3 are each independently C 1-10 alkyl, C 6-14 aryl, C 6-15 heteroaryl, -NH 2 , OH, -R 4 - OH (i.e, an alcohol group), -R 4 -NH 2 (i.e, an amine group), epoxy group, vinyl group, or acrylate group; and R 4 is a C 1-10 alkenylene group. In a refinement, each of the R 1 , R 2 , R 3 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, allenyl, or other alkyl groups or chains. It should be appreciated that the R 1 on different silicon atoms of the same molecule need not be the same, R 2 on different silicon atoms of the same molecule need not be the same, and R 3 on different silicon atoms of the same molecule need not be the same. More specific siloxanes are provided by formula 4, 5, 6, 7, and 8:
wherein a, b, m, and n are each independently 0 to 100 (need not be an integer as to describe an average structure). Examples of such siloxane-containing materials include, but are not limited to, BYK’s Silclean 3700, Silclean 3701, Silclean 3710, Silclean 3720, Siltech’s Silmer® OH series, Siltech’s OHT series, Siltech’s ACR series, Siltech’s OH ACR series, Siltech’s NH series, Siltech’s EP(C) series, Siltech’s VN series, Siltech’s TMS series, as well as functional silicones commercially available from Gelest, Inc. [0044] In one variation, the step of polymerizing the pre-emulsion in each of the embodiments includes a seeding step in which a portion of the pre-emulsion and a predetermined amount of initiator are added to the reaction mixture and allowed to react for a first predetermined time period at a first predetermined temperature. In a refinement, the first predetermined time period is from about 2 minutes to 2 hours and the first predetermined temperature from about 70 ºC to about 100 ºC. In this variation, an additional amount of the pre-emulsion and the radical initiator is added to the reaction mixture over a second predetermined time period at a second predetermined temperature with mixing. In a refinement, the second predetermined time period is from about 1 hour to 10 hours, and the second predetermined temperature from about 70 ºC to about 100 ºC. A chaser is then added to the reaction mixture at a third predetermined temperature over a third predetermined time period. The polymerization is then allowed to complete over a third predetermined time period. The chaser can potentially scavenge any unreacted monomer. In a refinement, the third period of time is from about 2 minutes to 2 hours and the third temperature from about 40 ºC to about 70 ºC. After the mixture is allowed to cool (typically to room temperature), a neutralizing agent (e.g., ammonia) and optional additional additives can be added to the reaction mixture. [0045] As set forth above, the emulsion polymerization is initiated by radical initiators that generate free radicals upon exposure to heat or light, which initiate polymerization. The radical initiator can be a water-soluble initiator or an oil-soluble initiator. Water-soluble initiators are preferred. Suitable water-soluble radical initiators include, but are not limited to, persulfates (e.g., potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof), oxidation- reduction initiators, and combinations thereof. The oxidation-reduction initiator can be the reaction product of persulfates (e.g., potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof) and reducing agents. Examples of reducing agents include sodium metabisulfite and sodium bisulfite; and 4,4′-azobis(4-cyanopentanoic acid) and its soluble salts (e.g., sodium, potassium). Suitable oil-soluble radical initiators include, but are not limited to, azo-compounds such as 2,2′-azobis(isobutyronitrile)) and2,2′-azobis(2,4-dimethylpentanenitrile. Additional radical initiators can be organic peroxides, metal iodides, and metal alkyls, and combinations thereof. Moreover, the radical initiators set forth herein can also be used for the chaser. It should be appreciated that each of the combinations of the initiators set forth above can also be used. [0046] As set forth above, the monomers include (meth)acrylic acid monomers and (meth)acrylic monomers. The (meth)acrylic acid monomers include acrylic acid, methacrylic acid and substituted derivatives thereof. Examples of the (meth)acrylic monomers include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl methacrylate, methyl methacrylate, butyl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and combinations thereof. In a refinement, the monomer composition includes butyl acrylate, ethyl hexyl acrylate, methyl methacrylate, acrylic acid, and methacrylic acid. [0047] A “final siloxane-containing resin emulsion” as used herein refers to a composition that includes all of the components that have been added to the reaction mixture of the methods set forth herein including the neutralizing agent and any additives set forth herein. In a variation, the final siloxane-containing resin emulsion includes the monomer and polymer composition in an amount from about 25 to 65 weight percent of the final siloxane-containing resin emulsion, the siloxane- containing composition in an amount from about 0.05 to 25 weight percent of the total weight of the final siloxane-containing resin emulsion, and the radical initiator in an amount from about 0.05 to 2 weight percent of the total weight of the final siloxane-containing resin emulsion with the balance being water. In a refinement, the chaser is present in an amount from about 0.05 to 2 weight percent of the total weight of the final siloxane-containing resin emulsion. In a further refinement, the neutralizer is present in an amount of about 0.05 to 5 weight percent of the total weight of the final siloxane-containing resin emulsion. In a further refinement, the biocide is present in an amount of 0.01-0.40 percent of the total weight of the final siloxane-containing resin emulsion. In still a further refinement, a surfactant is present in an amount from 0.5 to 5 weight percent of the total weight of the final siloxane-containing resin emulsion. [0048] In another embodiment, an acrylic emulsion formed by the methods set forth above is provided. The acrylic emulsion includes water, an acrylic polymer or copolymer, and siloxane composition residues (i.e., siloxane residues). The acrylic polymer or copolymer includes residues of the one or more monomers set forth above. In a refinement, the siloxane composition residues are incorporated into the acrylic polymer or copolymer. In another refinement, the siloxane composition residues are dispersed in water along with the acrylic polymer or copolymer. Typically, siloxane composition residues are present in an amount from 0.5% to 25% of the weight of the first acrylic polymer or copolymer. Characteristically, the acrylic polymer or copolymer is formed by polymerizing the monomer compositions set forth above. Consistent with the methods set forth above, the acrylic emulsion can include the adhesion promoter, the defoamer, the biocide, the initiator, the chaser, and the neutralizing agent, or residues of each of these components. Details of the siloxane composition, the siloxane composition, and all other components of the acrylic emulsion are the same as set forth above. [0049] In another embodiment, a paint composition that includes the siloxane-containing emulsion set forth above is provided. In addition to the siloxane-containing emulsion, the paint composition can include a pigment composition. In a refinement, the pigment composition is a solvent acrylic-based colorant. In another refinement, the pigment compositions include a dye or pigment in a solvent system. Examples of such solvent systems include nonionic and anionic dispersing and wetting agents and polyglycol. Specific useful pigment compositions are the Chromaflo Chroma- Chem Pigment Dispersions from Chromaflo Technologies (e.g., 1852 Transparent Yellow Oxide, 1054 Transparent Red Oxide, 9956 Carbon Black, 2075 Raw Umber, 5558 Phthalo Green Blue, etc.). Other useful pigments include dispersions of carbon black. Typically, the pigment composition is present in an amount of at least 0, 0.1, 0.5, 1, or 2 weight percent and at most 10, 7, 6, 5, or 4 weight percent of the total weight of the paint composition. [0050] In a variation, the paint composition includes titanium oxide in an about from about 1 to 50 weight percent of the total weight of the paint composition. [0051] In a variation, the paint compositions set forth herein include a mildewcide. Typically, the mildewcide is present in an amount from about 1 to 4 weight percent of the total weight of the paint composition. In a refinement, the mildewcide is present in an amount from about 1 to 3 weight percent of the total weight of the paint composition. In another refinement, the mildewcide is present in an amount from about 1.5 to 2.5 weight percent of the total weight of the paint composition. An example of a useful mildewcide is 3-iodo-2-propynyl butylcarbamate (“IPBC”). [0052] In typical applications, the paint composition can include one or more additives in relatively low amounts in order to provide important properties to the paint composition. Typical additives include rheology modifiers, surfactants, suspending agents, defoamers, organic solvents, dispersants, coalescents, light stabilizers (e.g., Hindered amine light stabilizer such as Tinuvin® 292), biocides and combinations thereof. In a variation, the additives are collectively present in an amount from about 0.1 to 20 weight percent. In a refinement, the additives are collectively present in an amount from about 1 to 20 weight percent. It should be appreciated that other well-known additives can be utilized to provide additional properties. In a refinement, each of the following additives are independently optionally present in an amount greater than 0.01, 0.05, 1.0, 2.0, 3.0 or 4.0 weight percent of the total weight of the paint composition and in an amount less than, 20.0, 15.0, 10.0, 9.0, 8.0, 7.0, or 6.0 weight present of the total weight of the paint composition: rheology modifiers, surfactants, defoamers, organic solvents, dispersants, coalescents, light stabilizers, and biocides. [0053] In a variation, the paint composition set forth above are made by a two-step process - the grind and the letdown. In the grind step, the solvent (water), dispersant, defoamer, and pigments are mixed together. In the letdown step, the siloxane-containing emulsion, the mildewcide, if present, the rheology modifier, if present, and the biocide, if present, are added to the grind product. [0054] The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims. [0055] Resin formula 1 – Conventional Latex [0056] Table 1 provides the amount of material used for a conventional emulsion. [0057] Table 1. Conventional resin emulsion composition [0058] The following procedure is followed for forming the conventional resin emulsion composition. Add all components of the reactor charge to a sealed reactor kettle flushed with nitrogen. Stir while pre-emulsion is prepared. To prepare pre-emulsion, mix water, surfactant, and sodium carbonate at 150 rpm for 10 minutes until everything is dissolved and homogenous. Turn the mixer speed up to 500 rpm and add the remaining components. Once all components have been added, stir pre-emulsion for 30 minutes to ensure stable emulsification. Prepare initiator by dissolving persulfate in water, and load into a syringe pump connected to the reactor. Heat reactor charge to 80°C while stirring and then feed in 5% pre-emulsion. Wait for the kettle to reach 80°C again and then add 5% initiator solution to seed the latex. Allow reactor to exotherm, and fully react over ~15 minutes or until the temperature stabilizes after the exotherm. Increase temperature to 85°C. Feed pre-emulsion at a steady rate over 4 hours while simultaneously feeding in initiator over 4.5 hours. After feeding, hold the reactor at temperature for 30 minutes and then cool reactor to 45-55°C. Dissolve chaser feeds separately into water and load into separate syringes. Add syringes to a syringe pump connected to the reactor. Feed chaser solutions simultaneously into the reactor for 20 minutes at 45-55°C. Hold reaction at temperature for 20 minutes after the chaser solution feeding. Cool to room temperature and add neutralizer and biocide. Filter the latex, using a 150 micron filter, into a container for storage. [0059] Resin formula 1A-C – Conventional Latex Post-Modification [0060] In a variation of Resin formula 1, the latex is taken and reacted post-synthetically to a chemically compatible siloxane that will react with exposed groups on the latex. This can possibly form a siloxane shell around the polymer. The following procedure is followed for forming this conventional resin emulsion composition: [0061] Resin formula 1A [0062] To 100g of Resin 1, add 2g of Silmer® EP Di-50 and stir for 5 minutes. Allow to sit overnight before testing or using to allow the epoxy siloxane to react with the latex. [0063] Resin formula 1B [0064] To 100g of Resin 1, add 2g of Silmer® NH C50 and stir for 5 minutes. Allow to sit overnight before testing or using to allow the amino siloxane to react with the latex. [0065] Resin formula 1C [0066] To 100g of Resin 1, add 2g of Silclean 3700 and stir for 5 minutes. Allow to sit overnight before testing or using to allow the alcohol siloxane to react with the latex. [0067] Resin formula 2 – Emulsified Siloxane [0068] Siloxane emulsification for addition to later stage latex is formed from the composition of Table 2. [0069] Table 2. Siloxane post-emulsification resin composition [0070] The following procedure is followed for forming the siloxane post-emulsification resin composition. Add all components of the reactor charge to a sealed reactor kettle flushed with nitrogen. Stir while pre-emulsion is prepared. To prepare pre-emulsion, mix water, surfactant, and sodium carbonate at 150 rpm for 10 minutes until everything is dissolved and homogenous. Turn the mixer speed up to 500 rpm and add the remaining components. Once all components have been added, stir pre-emulsion for 30 minutes to ensure stable emulsification. Prepare initiator by dissolving persulfate in water, and load into a syringe pump connected to the reactor. Heat reactor charge to 80°C while stirring and then feed in 5% pre-emulsion. Wait for the kettle to reach 80°C again and then add 5% initiator solution to seed the latex. Allow reactor to exotherm, and fully react over ~15 minutes or until the temperature stabilizes after the exotherm. Increase temperature to 85°C. Feed pre-emulsion at a steady rate over 4 hours while simultaneously feeding in initiator over 4.5 hours. After feeding, hold the reactor at temperature for 30 minutes and then cool reactor to 45-55°C. Dissolve chaser feeds separately into water and load into separate syringes. Add syringes to a syringe pump connected to the reactor. Feed chaser solutions simultaneously into the reactor for 20 minutes at 45-55°C. Hold reaction at temperature for 20 minutes after chaser feeding. Meanwhile in a separate container, emulsify all components of siloxane mixture with a stirrer at 500 rpm for 30 minutes. Then, add the siloxane solution to the reactor and mix for 10 minutes. Cool to room temperature and add neutralizer and biocide. Filter the latex, using a 150 micron filter, into a container for storage. [0071] Resin formula 3 - Pure siloxane addition into the monomer pre-emulsion [0072] Table 3 provides the amount of material used for the siloxane-containing emulsion. [0073] Table 3. Siloxane-containing emulsion resin composition [0074] The following procedure is followed for forming the siloxane-containing emulsion resin composition. Add all components of the reactor charge to a sealed reactor kettle flushed with nitrogen. Stir while pre-emulsion is prepared. To prepare pre-emulsion, mix water, surfactant, and sodium carbonate at 150 rpm for 10 minutes until everything is dissolved and homogenous. Turn the mixer speed up to 500 rpm and add the remaining components. Once all components have been added, stir pre-emulsion for 30 minutes to ensure stable emulsification. Prepare initiator by dissolving persulfate in water, and load into a syringe pump connected to the reactor. Heat reactor charge to 80°C while stirring and then feed in 5% pre-emulsion. Wait for the kettle to reach 80°C again and then add 5% initiator solution to seed the latex. Allow reactor to exotherm, and fully react over ~15 minutes or until the temperature stabilizes after the exotherm. Increase temperature to 85°C. Feed pre-emulsion at a steady rate over 4 hours while simultaneously feeding in initiator over 4.5 hours. After feeding, hold the reactor at temperature for 30 minutes and then cool reactor to 45-55°C. Dissolve chaser feeds separately into water and load into separate syringes. Add syringes to a syringe pump connected to the reactor. Feed chaser solutions simultaneously into reactor for 20 minutes at 45-55°C. Hold reaction at temperature for 20 minutes. Cool to room temperature and add neutralizer and biocide. Filter the latex, using a 150 micron filter, into a container for storage. [0075] Incorporation of the siloxane into the latex can demonstrate increased burnish and mar resistance, but first needs to be tested for uniform film formation from the following testing method: [0076] For resin film appearance check, a 3 mil drawdown is prepared on a Leneta 3B chart. The panel is then allowed to air dry overnight and is then observed by the following criteria. Orange peel: this term refers to a wavy appearance occurring throughout the paint film. This is due to the thickness varying due to the coating’s surface interactions. Fisheyes refer to a phenomenon where the coating develops scattered holes where no coating is present, and only the substrate is observed. The severity here is judged based on the number and size of the fisheyes, with less/smaller holes being less severe than many large holes. [0077] Table 4. Resin wet and dry film appearance studies of different siloxane incorporation methods in neat resin [0078] The conventional resin, resin 1, showed the best film appearance. Post-addition of siloxane into finished latex, 1A-1C, resulted in the most severe fisheyes and orange peel. Post-addition of emulsified siloxane emulsification, resin 2, resulted in fewer defects compared to 1A-1C. Addition into the monomer pre-emulsion, resin 3, showed the best results for film appearance when incorporating siloxane. It can be seen that the order addition of siloxane products is very critical for the development of a defect-free resin film and its application in either clear or pigmented coatings. [0079] The investigation into how these three different siloxane addition methods influence the film appearance for architectural coatings was evaluated in a flat white and semi-gloss deep color paint formulations. [0080] White Color Flat Paint Formula [0081] The following procedure is followed for forming the white color flat paint formula: The mill container is mixed at high speed with pigment grinding blade capable of high shearing. Starting with water, add each ingredient in the listed order, allowing 5 minutes to mix between ingredients, then 30 minutes at the end to fully disperse pigments (Table 5). Following this, transfer ingredients to letdown container (Table 6), and continue to add the rest of the ingredients in order while stirring. Stir for 20 minutes before removing paint from the letdown. Let sit 30 minutes before testing. [0082] Table 5. Mill Composition [0083] Table 6. Letdown Composition [0084] Deep Color Semi-Gloss Paint Formula [0085] The following procedure is followed for forming the deep color semi-gloss paint formula: The mill container is mixed at high speed with pigment grinding blade capable of high shearing. Starting with water, add each ingredient in the listed order, allowing 5 minutes to mix between ingredients, then 30 minutes at the end to fully disperse pigments (Table 7). Following this, transfer ingredients to letdown container (Table 8), and continue to add the rest of the ingredients in order while stirring. Stir for 20 minutes before removing paint from the letdown. Let sit 30 minutes. Add 120g of BASF CL yellow oxide colorant dispersion to paint and shake vigorously for 5 minutes. Allow to sit 5 minutes or more before testing. [0086] Table 7. Mill composition. [0087] Table 8. Letdown composition [0088] Incorporation of the siloxane-emulsified latex into the finished coating demonstrates increased burnish and mar resistance from the following testing methods: 1. Cheesecloth burnish ASTM 6736. 2. Concentrated abrasive cleaner burnish. A 7 mil drawdown is prepared on a black vinyl chart and cured for 7 days. The gloss is measured before and after burnish testing using a BYK Gardner gloss meter. A concentrated solution of an abrasive cleaner is applied to a sponge, placed inside a sponge holder, and ran for 30 cycles on a Gardner scrub abrasion tester. The panel is rinsed with water and left to dry before measuring gloss after burnish testing. 3. Denim Transfer/Burnish Resistance. A 7 mil drawdown is prepared on a black vinyl chart and cured for 7 days. A piece of denim is folded over itself and ran across the panel by hand with a consistent, even force for 30 cycles. The excess residue is wiped off the panel upon completion. The test is evaluated by visual appearance and factors such as scratching, gloss change, and color transfer. 4. Rubber Stopper Mar Resistance. A 7 mil drawdown is prepared on a black vinyl chart and cured for 7 days. A black rubber stopper is run across the panel by hand with a consistent, even force for 30 cycles. The excess residue is wiped off the panel upon completion. The test is evaluated by visual appearance and factors such as marring, gloss change, and color transfer. 5. Plastic Spoon Mar Resistance. A 7 mil drawdown is prepared on a black vinyl chart and cured for 7 days. The back of a plastic spoon is run across the panel by hand with a consistent, even force for 30 cycles. The excess residue is wiped off the panel upon completion. The test is evaluated by visual appearance and factors such as scratching and gloss change. 6. Nail Scratch Mar Resistance. A 7 mil drawdown is prepared on a black vinyl chart and cured for 7 days. The edge of the tester’s nails is run across the panel with a consistent, even force for 30 cycles. The excess residue is wiped off the panel upon completion. The test is evaluated by visual appearance and factors such as scratching and gloss change. [0089] Table 9. Film appearance and abrasive burnish test results by gloss measurement in white color flat paint formula. [0090] Resins 1A-C were found to have a much lower gloss change than Resin 1, which indicated that the addition of siloxane products showed a significant mar and burnish improvement. Relatively, the film appearance and burnish performance of Resin 1A was found to be better compared to 1B and 1C. Because of this, the Silmer® EP Di-50 was used in Resin 2 and 3, when studying the film defects referenced in Table 4, to produce Tables 10 and 11. A comparison between the different incorporation methods of the siloxane in order to achieve a usable polymer composition to obtain a defect-free film is shown below. [0091] Table 10. Film appearance and burnish test results by gloss measurement in white color flat paint formula. [0092] Table 11. Mechanical burnish and mar testing for white color flat paint formula. Visual score ranking 1-5, 5 being best. [0093] White flat formulas are helpful for tests such as denim burnish and black rubber stopper burnish, where color transfer to the paint can more easily be observed visually during evaluation. Based on the above results, Resin 3 appeared to have the best balance between burnish resistance and resin film appearance. This pre-emulsion incorporation method was determined to be optimal for this invention. [0094] Deep color paints typically show poor burnish and mar resistance due to the contrast between the white scratching and the deep coloration. Given the above results in the white base paint formulas, the resins were then tested in deep color semi-gloss paint formulas. Testing was completed only with the pre-emulsion incorporation latex synthesis method. The other samples were omitted from testing due to less favorable results and surface defects. [0095] Table 12. Film appearance and burnish test results by gloss measurement in a deep color semi-gloss paint formula. [0096] Table 13. Mechanical burnish and mar testing for deep color semi-gloss paint formula. Visual score ranking 1-5, 5 being best. [0097] The resin system made by adding siloxane into the monomer pre-emulsion showed the best film appearance among the various addition methods investigated. The burnish and mar performance, determined by gloss measurement, was superior for siloxane addition into the pre- emulsion. Visual evaluation from mechanical burnish and mar testing, by means of color transfer, scuffing, and scratching, demonstrated that the addition of siloxane into the monomer pre-emulsion is the most effective method of incorporating siloxane. [0098] By the combination of the above effects, the resulting latex with siloxane is easily processable, clean, demonstrates self-defoaming capabilities, and improved burnish and mar resistance in final paint films for both white flat and semi-gloss deep paint formulations. [0099] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.
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