WO2017160310A1 - Bpa free sprayable epoxy resin - Google Patents
Bpa free sprayable epoxy resin Download PDFInfo
- Publication number
- WO2017160310A1 WO2017160310A1 PCT/US2016/023131 US2016023131W WO2017160310A1 WO 2017160310 A1 WO2017160310 A1 WO 2017160310A1 US 2016023131 W US2016023131 W US 2016023131W WO 2017160310 A1 WO2017160310 A1 WO 2017160310A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- resin
- bisphenol
- coating
- self
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention generally relates to a BPA free epoxy resin that is suitable for spray application. More specifically, the present invention relates to a BPA free epoxy resin material that is particularly spray application in a manner that allows a high coating build while also maintaining a viscosity characteristic that prevents sagging of the coating to facilitate single coat application.
- epoxy based protective coatings are well known in the art and due to their exceptional durability and structural properties epoxy based protective coatings have gained commercial acceptance as protective and decorative coatings for use on a wide variety of materials.
- epoxy based protective coatings represent one of the most widely used methods of corrosion control. They are used to provide long term protection of steel, concrete, aluminum and other structures under a broad range of corrosive conditions, extending from atmospheric exposure to full immersion in highly corrosive environments. Further, epoxy coatings are readily available and are easily applied by a variety of methods including spraying, rolling and brushing.
- the epoxy includes a first base resin matrix formed from a bisphenol material such as bisphenol A (BPA) and at least a second catalyst or hardener, although other components such as a pigment agent or an aggregate component may also be added. While the two parts remain separate, they remain in liquid form. After the two parts are mixed together, they begin a curing process that is typically triggered by exposure to heat, humidity or a ultra-violet light source, whereby the mixed material quickly begins to solidify. As a result, it is necessary to mix only a sufficient amount of compound such that it can be worked effectively before set up occurs. Accordingly, the use and application of these compounds is a tedious, slow and expensive proposition.
- BPA bisphenol A
- the preferred BPA material based on its viscosity and build properties has fallen greatly out of favor because of the possibility that the material will leach from the coatings.
- a coating composition for use on the inside of water distribution lines, storage tanks, tunnels and the like must be approved for direct food contact.
- the coating should be free of any material which might migrate into the materials transmitted in the distribution system.
- the coating should have enough flexibility for the structure to undergo natural expansion and contraction without damaging the coating.
- such a material must be able to be spray applied in a single coat high build pass without sagging.
- the present invention relates to a composition and method for a spray applied BPA free two-part, self-setting composition adapted for delivering the components of the composition at a temperature that promotes their spray application at a proper viscosity as well as inducing a self-setting reaction.
- a self-setting BPA free epoxy coating compound is adapted for curing in place once applied.
- the self-curing compound includes a multi-part compound which, upon a mixing of the parts, chemically reacts and cures.
- a spray-applied BPA free two-part, self-setting composition that exhibits desired properties such as a high build non-sag coating. Further, there is an object of the present invention to provide a spray-applied BPA free two-part, self-setting composition and is particularly adapted for delivering the components of the composition at a temperature that promotes their spray application as well as a self-setting reaction.
- compositions and methods for a spray applied BPAfree two- part, self-setting composition adapted for delivering the components of the composition at a temperature that promotes their spray application at a proper viscosity as well as inducing a self-setting reaction.
- a self-setting BPAfree epoxy coating compound is adapted for curing in place once applied.
- the self-curing compound includes a multi-part compound which, upon a mixing of the parts, chemically reacts and cures.
- Epoxy technology and methods of curing and reacting with amine-based hardeners have continued to evolve since the first epoxies were developed in the 1930s.
- the possible reactions combined with wide-ranging formulation additives have resulted in a myriad of products and a wide range of environmental factors that must be considered when choosing a protective coating system.
- Bisphenol A is a reaction product of phenol and acetone. Bisphenol A is reacted with epichlorohydrin to form diglycidylether bisphenol A resin or DGEBA. The resultant epoxy resin is a liquid with a honey-like consistency. DGEBA is most often used in solvent-free coatings and flooring systems. The molecular weight of the formulation is increased by adding more bisphenol A to liquid DGEBA to form semi-solid or solid resins. These resins are cut in solvent to allow their use as maintenance primers for steel or as corrosion-resistant films. Bisphenol A however is problematic in that it has been shown to leach significant pyproducts into the transported material.
- Bisphenol F is similar to bisphenol A except phenol is reacted with formaldehyde rather than acetone. The resultant phenolic chemical does not have the two methyl groups that are present between the ring structures in bisphenol A resins. Bisphenol F is reacted with epichlorohydrin to form diglycidylether bisphenol F (DGEBF) resins. Because of the missing methyl groups, the viscosity of bisphenol F resins are typically 1/3 lower than the bisphenol A resins. Further the crosslinking is higher and as a result bisphenol F does not exhibit significant leaching and is therefore considered safe for food contact. However the lower viscosity typically results in a low functionality for spray application and heat and chemical resistance.
- DGEBF diglycidylether bisphenol F
- the present invention provides a spray applied coating formed using a bisphenol F resin that is formulated and mixed in such a manner that it allows spray application in high build coating while also exhibiting low sag.
- the base resin is preferably a Diglycidyl Ether of Bisphenol F resin. More preferably the resin is a low viscosity, liquid epoxy resin manufactured from epichlorohydrin and Bisphenol-F.
- the blended resin will exhibit improved crystallization resistance properties when compared to the neat, liquid, Bisphenol-A.
- an air release agent is preferably employed to prevent foaming during mixing and application of the epoxy coating. This enhances application and provides a coating that is free from blisters and pinholes.
- an air release agent in the nature of a polysiloxane polymer blend is employed.
- a thixotropic agent such as a fumed silica. More preferably a thixotropic agent is employed in the form of a treated fumed silica such as a fumed silica treated with a dimethyl silicone fluid that replaces the surface hydroxyl groups with a polydimethyl-siloxane polymer rendering the silica hydrophobic.
- the coating material preferably includes a pigment such as a ⁇ 02 to make application and verification of coating integrity easier.
- the resin comprises between 80% and 99% bisphenol F resin, between 0.05% and 0.02% air release agent, between 2% and 6% thixotropic agent and between 1 % and 4% pigment all by weight.
- the resin comprises between 90% and 95% bisphenol F resin, between 0.02% and 0.03% air release agent, between 3% and 5% thixotropic agent and between 2% and 3% pigment all by weight.
- the hardener component is preferably a cycloaliphatic amine.
- the hardener preferably does not contain phenol or benzyl alcohol. This facilitates a solvent free coating that is safe for food grade coatings.
- an air release agent is preferably employed to prevent foaming during mixing and application of the epoxy coating. This enhances application and provides a coating that is free from blisters and pinholes.
- an air release agent in the nature of a polysiloxane polymer blend is employed.
- a thixotropic agent such as a fumed silica. More preferably a thixotropic agent is employed in the form of a treated fumed silica such as a fumed silica treated with a dimethyl silicone fluid that replaces the surface hydroxyl groups with a polydimethyl-siloxane polymer rendering the silica hydrophobic.
- the hardener comprises between 80% and 99% cycloaliphatic amine, between 0.05% and 0.02% air release agent and between 2% and 6% thixotropic agent all by weight.
- the hardener comprises between 94% and 96% cycloaliphatic amine, between 0.04% and 0.02% air release agent and between 2% and 3% thixotropic agent all by weight.
- the base resin and hardener components are fully blended separate and apart from one another.
- the two components are then maintained separated until ready for direct application to the surface.
- the materials were mixed in small batches for application and then the mixed batches were brush or roller applied.
- the two components were mixed and then thinned or diluted with a solvent to a point where their viscosity allowed spray application.
- the difficulty in such cases is that the working time for the material is quite short once mixed requiring constant rebatching and, if spraying, cleaning of the spray equipment. Plus the addition of significant solvents makes spray application in closed environments dangerous to the worker making the application.
- the viscosity required for spray application results in a coating that is too thin to apply as a high build coating.
- the base resin and hardener components are both very viscous and therefore difficult to pump. It has been found that the portions are easier to pump, and therefore easier to deliver to the spray device, if they are heated in a closed environment within the storage containers, and maintained in such a state all the way to the spray tip. This also facilitates more volumetrically-controlled delivery of each of the two portions of the compound to the spray device.
- both the base resin and hardener in anticipation of application ne heated in a system generally includes means for heating the contents of the containers that hold the two components, for example by using temperature-controlled heaters.
- Recirculating pumps may be used in the containers to ensure mixing and uniform heating of the two portions.
- the heated hose may be heated by including an electrical resistance heating element for the hose and then using a temperature controlled power supply for the electrical resistance heating element to maintain an elevated compound temperature in the heated hose.
- the hoses may also be heated with steam.
- the hoses that carry the liquids from the containers to the mixing assembly should be insulated or possibly heated themselves as necessary to maintain the portions at an elevated temperature so they flow better, and for volume control at the spray gun.
- the heated resin and hardener is mixed immediately prior to spray application in the sprayer itself.
- the containers holding the resin and hardener components are maintained at an elevated temperature.
- the components are maintained at about 170 degrees Fahrenheit to 220 degrees Fahrenheit. More preferably the components are maintained at about 180 degrees Fahrenheit to 190 degrees Fahrenheit.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16894762.0A EP3430068B1 (en) | 2016-03-18 | 2016-03-18 | Bpa free sprayable epoxy resin |
AU2016397680A AU2016397680B2 (en) | 2016-03-18 | 2016-03-18 | BPA free sprayable epoxy resin |
CA3015977A CA3015977C (en) | 2016-03-18 | 2016-03-18 | Bpa free sprayable epoxy resin |
JP2018546607A JP6788682B2 (en) | 2016-03-18 | 2016-03-18 | BPA-free sprayable epoxy resin |
KR1020187028261A KR20180114950A (en) | 2016-03-18 | 2016-03-18 | BPA-free sprayable epoxy resin |
PCT/US2016/023131 WO2017160310A1 (en) | 2016-03-18 | 2016-03-18 | Bpa free sprayable epoxy resin |
ES16894762T ES2941236T3 (en) | 2016-03-18 | 2016-03-18 | BPA-free epoxy resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2016/023131 WO2017160310A1 (en) | 2016-03-18 | 2016-03-18 | Bpa free sprayable epoxy resin |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017160310A1 true WO2017160310A1 (en) | 2017-09-21 |
Family
ID=59852033
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2016/023131 WO2017160310A1 (en) | 2016-03-18 | 2016-03-18 | Bpa free sprayable epoxy resin |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP3430068B1 (en) |
JP (1) | JP6788682B2 (en) |
KR (1) | KR20180114950A (en) |
AU (1) | AU2016397680B2 (en) |
CA (1) | CA3015977C (en) |
ES (1) | ES2941236T3 (en) |
WO (1) | WO2017160310A1 (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080197526A1 (en) | 2007-02-16 | 2008-08-21 | Asjad Shafi | Process for Preparing Composites Using Epoxy Resin Formulations |
US20110218270A1 (en) * | 2010-03-02 | 2011-09-08 | Basf Se | Use of linear triethylentetramine as curing agent for epoxy resins |
US20120328811A1 (en) * | 2011-06-24 | 2012-12-27 | Air Products And Chemicals, Inc. | Epoxy Resin Compositions |
US20130225788A1 (en) * | 2012-02-27 | 2013-08-29 | Cytec Technology Corp. | Curable resin composition and short-cure method |
US20140001029A1 (en) * | 2012-06-27 | 2014-01-02 | Samsung Corning Precision Materials Co., Ltd. | Method Of Manufacturing Thermochromic Window |
WO2014078218A1 (en) * | 2012-11-13 | 2014-05-22 | Dow Global Technologies Llc | Epoxy resin system containing polyethylene tetramines and triethylene diamine catalyst for resin transfer molding processes |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0525834A (en) * | 1991-07-24 | 1993-02-02 | Sumitomo Metal Ind Ltd | Method and apparatus for coating steel sheetpile with printer |
JP3454437B2 (en) * | 1992-10-02 | 2003-10-06 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | One-part epoxy resin adhesive composition with low viscosity and no solvent |
JPH0859962A (en) * | 1994-08-24 | 1996-03-05 | Three Bond Co Ltd | Lining composition for inner surface of pipe and treating of inner surface of pipe using the same |
JP2005187683A (en) * | 2003-12-26 | 2005-07-14 | Mitsui Kagaku Sanshi Kk | Primer for resin coating film |
US7694894B2 (en) * | 2005-04-19 | 2010-04-13 | Warren Environmental, Inc. | Method and system for preheating epoxy coatings for spray application |
JP2007182508A (en) * | 2006-01-07 | 2007-07-19 | Aica Kogyo Co Ltd | Base conditioner and coating film structure |
KR101919307B1 (en) * | 2011-06-08 | 2018-11-16 | 헌츠만 어드밴스드 머티리얼스 아메리카스 엘엘씨 | Curing agents providing a low ratio of thin-film cure time to gel time |
JP5913762B1 (en) * | 2016-02-12 | 2016-04-27 | 日本ペイントマリン株式会社 | Anticorrosion paint composition, paint film, ship and marine structure |
-
2016
- 2016-03-18 WO PCT/US2016/023131 patent/WO2017160310A1/en active Application Filing
- 2016-03-18 CA CA3015977A patent/CA3015977C/en active Active
- 2016-03-18 AU AU2016397680A patent/AU2016397680B2/en active Active
- 2016-03-18 JP JP2018546607A patent/JP6788682B2/en active Active
- 2016-03-18 KR KR1020187028261A patent/KR20180114950A/en not_active Application Discontinuation
- 2016-03-18 EP EP16894762.0A patent/EP3430068B1/en active Active
- 2016-03-18 ES ES16894762T patent/ES2941236T3/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080197526A1 (en) | 2007-02-16 | 2008-08-21 | Asjad Shafi | Process for Preparing Composites Using Epoxy Resin Formulations |
US20110218270A1 (en) * | 2010-03-02 | 2011-09-08 | Basf Se | Use of linear triethylentetramine as curing agent for epoxy resins |
US20120328811A1 (en) * | 2011-06-24 | 2012-12-27 | Air Products And Chemicals, Inc. | Epoxy Resin Compositions |
US20130225788A1 (en) * | 2012-02-27 | 2013-08-29 | Cytec Technology Corp. | Curable resin composition and short-cure method |
US20140001029A1 (en) * | 2012-06-27 | 2014-01-02 | Samsung Corning Precision Materials Co., Ltd. | Method Of Manufacturing Thermochromic Window |
WO2014078218A1 (en) * | 2012-11-13 | 2014-05-22 | Dow Global Technologies Llc | Epoxy resin system containing polyethylene tetramines and triethylene diamine catalyst for resin transfer molding processes |
Non-Patent Citations (1)
Title |
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See also references of EP3430068A4 |
Also Published As
Publication number | Publication date |
---|---|
EP3430068A4 (en) | 2019-10-16 |
AU2016397680A1 (en) | 2018-09-13 |
JP6788682B2 (en) | 2020-11-25 |
JP2019510106A (en) | 2019-04-11 |
CA3015977C (en) | 2021-03-30 |
EP3430068A1 (en) | 2019-01-23 |
EP3430068B1 (en) | 2023-01-04 |
AU2016397680B2 (en) | 2018-11-29 |
ES2941236T3 (en) | 2023-05-19 |
CA3015977A1 (en) | 2017-09-21 |
KR20180114950A (en) | 2018-10-19 |
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