WO2019023838A1 - GLACIOPHOBIC COATINGS - Google Patents

GLACIOPHOBIC COATINGS Download PDF

Info

Publication number
WO2019023838A1
WO2019023838A1 PCT/CN2017/095146 CN2017095146W WO2019023838A1 WO 2019023838 A1 WO2019023838 A1 WO 2019023838A1 CN 2017095146 W CN2017095146 W CN 2017095146W WO 2019023838 A1 WO2019023838 A1 WO 2019023838A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicone fluid
coating composition
weight
article
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/095146
Other languages
French (fr)
Inventor
Yu Chen
Xiaomei Song
Guodong SHEN
Hongyu Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Dow Silicones Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC, Dow Silicones Corp filed Critical Dow Global Technologies LLC
Priority to CN201780093461.XA priority Critical patent/CN110945093A/en
Priority to KR1020207004105A priority patent/KR20200035409A/en
Priority to EP17920510.9A priority patent/EP3662029A4/en
Priority to US16/634,831 priority patent/US20200157380A1/en
Priority to PCT/CN2017/095146 priority patent/WO2019023838A1/en
Priority to TW107125918A priority patent/TW201910445A/en
Publication of WO2019023838A1 publication Critical patent/WO2019023838A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups

Definitions

  • the present invention relates generally to a coating composition which provides a coating with a very low adhesion to ice.
  • the coating composition comprises methylpolysiloxane resin and a lubricant package comprising two kind of different siloxane fluids.
  • Icing ice build-up on an article
  • problems for many applications including rotors and blades of wind turbines, power lines, telecommunications, transportations, air crafts and housewares such as refrigerators, freezer box and ice tray.
  • Such ice build-up may be removed by heating, by applying chemicals that reduce the melting point of ice, by applying a mechanical force or by occluding air to break the bonding between ice and the surface of an article.
  • An alternative method to prevent ice build-up on an article is to protect the surface of the article with a coating that has a very low ice adhesion strength (i.e. ice barely adheres to the coating) .
  • Such coating is called as “ice-phobic coating” .
  • Some prior art references disclose an ice-phobic coating on the surface of articles, for example, US2015/0361319A, WO2016/176350A, WO2015/119943A, US9,388,325B and US2010/0326699.
  • the present invention provides a coating composition which shows very low adhesion to ice.
  • One aspect of the invention relates to a coating composition
  • a coating composition comprising:
  • Me is a methyl group
  • R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n is a number from 100 to 300
  • the viscosity of the first silicone fluid is 10,000 centistokes or more
  • Me is a methyl group
  • R 3 is an alkyl group having 1 to 3 carbon atoms
  • m is a number from 10 to 40
  • the viscosity of the second silicone fluid is from 100 to 2,000 centistokes
  • weight ratio of the first silicone fluid over the second silicone fluid ( (B-1) / (B-2) ) is from 0.6 to 2.8.
  • the invention relates to a coating film formed from the coating composition disclosed above.
  • the invention relates to an article having a film at least a part of the surface of the article, wherein the film is formed from the coating composition disclosed above.
  • the invention relates to a method for forming a film at least a part of the surface of an article, comprising the steps of:
  • the coating composition of this invention comprises (A) methylpolysiloxane resin, (B) a lubricant package comprising two kind of different siloxane fluids, (C) a catalyst and (D) a solvent.
  • Methylpolysiloxane resin used in the coating composition is a main component of the coating composition and becomes a matrix resin after the composition is cured.
  • the methylpolysiloxane resin has an average unit formula disclosed below.
  • Me is a methyl group. Both a and b are positive numbers and refer to molar ratio. The sum of a and b is 1. (O 1/2 R 1 ) is a remained reactive group.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of R 1 include hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and tert-butyl group.
  • C is a positive number and less than 2.
  • R 1 is an alkyl group
  • (O 1/2 R 1 ) is an alkoxy group. Such alkoxy group can be hydrolyzed to hydroxyl group, and become a reactive group.
  • at least 0.1 %of R 1 is a hydrogen atom.
  • at least 1 %of R 1 is a hydrogen atom.
  • R 1 is an alkyl group
  • 10 %or less of R 1 is a hydrogen atom.
  • 5 %or less of R 1 is a hydrogen atom.
  • Such methylpolysiloxane resin is commercially available from WACKER Chemie AG.
  • the amount of methylpolysiloxane resin in the coating composition is 50 to 95 weight %, preferably from 60 to 90 weight %, more preferably from 70 to 85 weight %based on the weight of the coating composition.
  • the lubricant package used in the coating composition comprises two kind of different siloxane fluids.
  • the first one is a high viscous reactive silicone fluid while the second one is a low viscous non-reactive silicone fluid.
  • the first silicone fluid is a reactive silicone fluid and is defined as the following Formula (1) .
  • Me is a methyl group.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of R 2 include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a sec-propyl group, n-butyl group and a tert-butyl group.
  • R 2 is a hydrogen atom or a methyl group.
  • At least one of R 2 is a hydrogen atom.
  • at least one of each end of the Formula (1) are hydrogen atoms.
  • n is a number from 100 to 300, preferably from 200 to 300.
  • the viscosity of the first silicone fluid is 10,000 centistokes or more. Preferably, the viscosity of the first silicone fluid is 15,000 centistokes or more.
  • the first silicone fluid can react with the methylpolysiloxane resin during curing step and form a crosslink network in a coating.
  • the first silicone fluid since the first silicone fluid has a straight and quite long chain, the first silicone fluid works as a lubricant because of its chain flexibility, thus it contributes good ice-phobic property of the coating.
  • the second silicone fluid is a non-reactive silicone fluid and is defined as the following Formula (2) .
  • Me is a methyl group.
  • R 3 is an alkyl group having 1 to 3 carbon atoms. Examples of R 3 include a methyl group, an ethyl group, a n-propyl group and a sec-propyl group. Preferably, R 3 is a methyl group.
  • m is a number from 10 to 40, preferably from 10 to 20.
  • the viscosity of the second silicone fluid is from 100 to 2,000 centistokes, preferably from 100 to 1000 centistokes.
  • the low viscous non-reactive fluid can be mixed in a coating composition and locates in a domain of the crosslinked network formed by the methylpolysiloxane resin and the first silicone fluid after curing step. If a high viscous non-reactive silicone fluid is used instead of the low viscous non-reactive fluid, the high viscous non-reactive silicone fluid cannot be well dispersed in the coating composition thus it cannot locate discretely in the domain disclosed above. So an obtained coating from the composition does not have a sufficient ice-phobic property.
  • the total amount of the silicone fluids (i.e. a sum of the first silicone fluid and the second silicone fluid) is from 10 to 50 weight %, preferably from 15 to 40 weight %, more preferably from 15 to 30 weight %based on the weight of the coating composition.
  • the weight ratio of the first silicone fluid over the second silicone fluid ( (B-1) / (B-2)) is from 0.6 to 2.8, preferably from 0.8 to 2.0, more preferably from 1.0 to 1.5.
  • Catalyst used in the coating composition of the invention is a catalyst for condensation of hydroxyl groups, and form a crosslink structure of methylpolysiloxane resins as well as the first silicone fluid.
  • Any known catalyst can be used. Examples of such catalyst include, but are not limited to, zirconium compound such as zirconium octoate and zirconium acetate, titanium compound such as tetrabutyl titanate, zinc compound such as zinc octoate and zinc acetate and tin compound such as dibutyltin dilaurate.
  • the amount of catalyst in the coating composition should be sufficient to crosslink silicone matrix resin, but typically is from 0.1 to 4 weight %, preferably from 0.2 to 3 weight %, more preferably from 0.5 to 2 weight %based on the weight of the coating composition.
  • the coating composition of the invention comprises a solvent.
  • solvent include, but are not limited to, alcohols, esters, ethers, ketones, ether-alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons and volatile silicones. Silicone fluid with quite low viscosity can be also used as a solvent.
  • the amount of solvent in the coating composition is from 50 to 90 weight %, preferably from 60 to 80 weight %, more preferably from 60 to 70 weight %based on the weight of the coating composition.
  • the coating composition of the invention can optionally include filler in addition to silicone powder.
  • filler include, but are not limited to, silica, borate nitride, zinc oxide, aluminum oxide and titanium dioxide.
  • the particle size of the filler is, preferably from 10 to 300 nanometers, more preferably from 20 to 50 nanometers.
  • the amount is from 10 to 50 weight %, preferably from 20 to 30 weight %based on the weight of the coating composition.
  • the coating composition of the invention can include other ingredients such as rheology modifier, wetting agent and dispersers these are known to those skilled in the art.
  • the present invention also relates to a method for forming a coating film on the surface of an article.
  • the coating film is formed at least a part of the surface of an article by the following method which comprises two steps.
  • the first step is (a) contacting at least a part of the surface of the article with the coating composition disclosed above.
  • Any article can be used. Examples of such article include, but are not limited to, rotors and blades of wind turbines, power lines, telecommunications, transportations, air crafts and housewares such as refrigerators, freezer box and ice tray. Any techniques can be used to contacting the surface of the article with the coating composition. Examples of such techniques include dipping, splaying, brushing, roll coating, spin coating and wire coating.
  • the second step is (b) heating the article to react the first silicone fluid with the methylpolysiloxane.
  • This step is also called as curing step.
  • One is a reaction between two or more methylpolysiloxane.
  • the hydroxyl groups in methlpolysiloxane condense together and release water.
  • the other is a reaction between the first silicone fluid and methylpolysiloxane, or a condensed methylpolysiloxane.
  • the cross-linking is normally occurred by heat under a catalyst.
  • the conditions such as temperature or heating time is vary and are known to those skilled in the art, but one example is from 180 to 270 degrees C for 0.5 to 2 hours.
  • the coating composition of the present invention can provide a hard coating with quite low adhesion to ice.
  • the hardness of the coating film is 2H or more by pencil hardness method.
  • the thickness of the coating film is preferably from 3 to 20 micrometers, more preferably from 5 to 15 micrometers.
  • Ice adhesion test was repeated for 25 cycles and record the result as 25 th cycle.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)

Abstract

A coating composition which provides a coating with a very low adhesion to ice is disclosed. The coating composition contains methylpolysiloxane resin and a lubricant package comprising two kinds of different siloxane fluids.

Description

ICE-PHOBIC COATINGS Field
The present invention relates generally to a coating composition which provides a coating with a very low adhesion to ice. The coating composition comprises methylpolysiloxane resin and a lubricant package comprising two kind of different siloxane fluids.
Introduction
Icing (ice build-up on an article) in a cold environment causes problems for many applications, including rotors and blades of wind turbines, power lines, telecommunications, transportations, air crafts and housewares such as refrigerators, freezer box and ice tray. Such ice build-up may be removed by heating, by applying chemicals that reduce the melting point of ice, by applying a mechanical force or by occluding air to break the bonding between ice and the surface of an article. However, all of these methods have limitations and disadvantages. An alternative method to prevent ice build-up on an article is to protect the surface of the article with a coating that has a very low ice adhesion strength (i.e. ice barely adheres to the coating) . Such coating is called as “ice-phobic coating” . Some prior art references disclose an ice-phobic coating on the surface of articles, for example, US2015/0361319A, WO2016/176350A, WO2015/119943A, US9,388,325B and US2010/0326699.
Summary
The present invention provides a coating composition which shows very low adhesion to ice.
One aspect of the invention relates to a coating composition comprising:
(A) 50 to 95 weight ％of methylpolysiloxane resin,
(B) 10 to 50 weight ％of silicone fluid mixture comprising a first silicone fluid and a
second silicone fluid represented by the following formulas,
(B-1) the first silicone fluid having the Formula (1)
R2O (Me2SiO) nMe2SiOR2 Formula (1)
wherein Me is a methyl group, R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is a number from 100 to 300, and the viscosity of the first silicone  fluid is 10,000 centistokes or more,
(B-2) the second silicone fluid having the Formula (2) :
R3 3Si (OSiMe2) mOSiR3 3   Formula (2)
wherein Me is a methyl group, R3 is an alkyl group having 1 to 3 carbon atoms, m is a number from 10 to 40, and the viscosity of the second silicone fluid is from 100 to 2,000 centistokes,
(C) 0.1 to 4 weight ％of a catalyst and
(D) 50 to90 weight ％of solvent,
wherein the weight ratio of the first silicone fluid over the second silicone fluid ( (B-1) / (B-2) ) is from 0.6 to 2.8.
In another aspect, the invention relates to a coating film formed from the coating composition disclosed above.
In yet another aspect, the invention relates to an article having a film at least a part of the surface of the article, wherein the film is formed from the coating composition disclosed above.
In yet further aspect, the invention relates to a method for forming a film at least a part of the surface of an article, comprising the steps of:
(a) contacting at least a part of the surface of the article with the coating composition disclosed above, and
(b) heating the article to react the first silicone fluid with the methylpolysiloxane.
Detailed Description
The coating composition of this invention comprises (A) methylpolysiloxane resin, (B) a lubricant package comprising two kind of different siloxane fluids, (C) a catalyst and (D) a solvent.
(A) Methylpolysiloxane resin
Methylpolysiloxane resin used in the coating composition is a main component of the coating composition and becomes a matrix resin after the composition is cured. The methylpolysiloxane resin has an average unit formula disclosed below.
(MeaSiO) a (MeSiO3/2) b (O1/2R1) c
In the formula, Me is a methyl group. Both a and b are positive numbers and refer to molar ratio. The sum of a and b is 1. (O1/2R1) is a remained reactive group. R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of R1 include hydrogen atom,  methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and tert-butyl group. C is a positive number and less than 2.
When R1 is an alkyl group, (O1/2R1) is an alkoxy group. Such alkoxy group can be hydrolyzed to hydroxyl group, and become a reactive group. In one embodiment, at least 0.1 ％of R1 is a hydrogen atom. Preferably, at least 1 ％of R1 is a hydrogen atom. When R1 is an alkyl group, 10 ％or less of R1 is a hydrogen atom. Preferably, 5 ％or less of R1 is a hydrogen atom.
Such methylpolysiloxane resin is commercially available from WACKER Chemie AG.
The amount of methylpolysiloxane resin in the coating composition is 50 to 95 weight ％, preferably from 60 to 90 weight ％, more preferably from 70 to 85 weight ％based on the weight of the coating composition.
(B) Lubricant package
The lubricant package used in the coating composition comprises two kind of different siloxane fluids. The first one is a high viscous reactive silicone fluid while the second one is a low viscous non-reactive silicone fluid.
(B-1) First silicone fluid
The first silicone fluid is a reactive silicone fluid and is defined as the following Formula (1) .
R2O (Me2SiO) nMe2SiOR2    Formula (1)
In the Formula (1) , Me is a methyl group. R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of R2 include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a sec-propyl group, n-butyl group and a tert-butyl group. Preferably, R2 is a hydrogen atom or a methyl group. At least one of R2 is a hydrogen atom. Preferably, at least one of each end of the Formula (1) , totally at least two of R2, are hydrogen atoms. n is a number from 100 to 300, preferably from 200 to 300.
The viscosity of the first silicone fluid is 10,000 centistokes or more. Preferably, the viscosity of the first silicone fluid is 15,000 centistokes or more.
Since at least one of R2 is a hydrogen atom, the first silicone fluid can react with the methylpolysiloxane resin during curing step and form a crosslink network in a coating. In addition, since the first silicone fluid has a straight and quite long chain, the first silicone fluid works as a lubricant because of its chain flexibility, thus it contributes good ice-phobic property of the coating.
(B-2) Second silicone fluid
The second silicone fluid is a non-reactive silicone fluid and is defined as the following Formula (2) .
R3 3Si (OSiMe2) mOSiR3 3     Formula (2)
In the Formula (2) , Me is a methyl group. R3 is an alkyl group having 1 to 3 carbon atoms. Examples of R3 include a methyl group, an ethyl group, a n-propyl group and a sec-propyl group. Preferably, R3 is a methyl group. m is a number from 10 to 40, preferably from 10 to 20.
The viscosity of the second silicone fluid is from 100 to 2,000 centistokes, preferably from 100 to 1000 centistokes.
The low viscous non-reactive fluid can be mixed in a coating composition and locates in a domain of the crosslinked network formed by the methylpolysiloxane resin and the first silicone fluid after curing step. If a high viscous non-reactive silicone fluid is used instead of the low viscous non-reactive fluid, the high viscous non-reactive silicone fluid cannot be well dispersed in the coating composition thus it cannot locate discretely in the domain disclosed above. So an obtained coating from the composition does not have a sufficient ice-phobic property.
The total amount of the silicone fluids (i.e. a sum of the first silicone fluid and the second silicone fluid) is from 10 to 50 weight ％, preferably from 15 to 40 weight ％, more preferably from 15 to 30 weight ％based on the weight of the coating composition.
The weight ratio of the first silicone fluid over the second silicone fluid ( (B-1) / (B-2)) is from 0.6 to 2.8, preferably from 0.8 to 2.0, more preferably from 1.0 to 1.5.
(C) Catalyst
Catalyst used in the coating composition of the invention is a catalyst for condensation of hydroxyl groups, and form a crosslink structure of methylpolysiloxane resins as well as the first silicone fluid. Any known catalyst can be used. Examples of such catalyst include, but are not limited to, zirconium compound such as zirconium octoate and zirconium acetate, titanium compound such as tetrabutyl titanate, zinc compound such as zinc octoate and zinc acetate and tin compound such as dibutyltin dilaurate.
The amount of catalyst in the coating composition should be sufficient to crosslink silicone matrix resin, but typically is from 0.1 to 4 weight ％, preferably from 0.2 to 3 weight ％, more preferably from 0.5 to 2 weight ％based on the weight of the coating composition.
(D) Solvent
The coating composition of the invention comprises a solvent. Examples of solvent include, but are not limited to, alcohols, esters, ethers, ketones, ether-alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons and volatile silicones. Silicone fluid with quite low viscosity can be also used as a solvent.
The amount of solvent in the coating composition is from 50 to 90 weight ％, preferably from 60 to 80 weight ％, more preferably from 60 to 70 weight ％based on the weight of the coating composition.
(E) Filler
The coating composition of the invention can optionally include filler in addition to silicone powder. Examples of such filler include, but are not limited to, silica, borate nitride, zinc oxide, aluminum oxide and titanium dioxide. The particle size of the filler is, preferably from 10 to 300 nanometers, more preferably from 20 to 50 nanometers. When the coating composition comprises such filler, the amount is from 10 to 50 weight ％, preferably from 20 to 30 weight ％based on the weight of the coating composition.
Other ingredients
The coating composition of the invention can include other ingredients such as rheology modifier, wetting agent and dispersers these are known to those skilled in the art.
Method for forming a coating
The present invention also relates to a method for forming a coating film on the surface of an article. The coating film is formed at least a part of the surface of an article by the following method which comprises two steps.
The first step is (a) contacting at least a part of the surface of the article with the coating composition disclosed above. Any article can be used. Examples of such article include, but are not limited to, rotors and blades of wind turbines, power lines, telecommunications, transportations, air crafts and housewares such as refrigerators, freezer box and ice tray. Any techniques can be used to contacting the surface of the article with the coating composition. Examples of such techniques include dipping, splaying, brushing, roll coating, spin coating and wire coating.
The second step is (b) heating the article to react the first silicone fluid with the methylpolysiloxane. This step is also called as curing step. Two reactions happen during the curing step. One is a reaction between two or more methylpolysiloxane. The hydroxyl groups in methlpolysiloxane condense together and release water. The other is a reaction between the first silicone fluid and methylpolysiloxane, or a condensed methylpolysiloxane. The cross-linking is normally occurred by heat under a catalyst. The conditions such as temperature or heating time is vary and are known to those skilled in the art, but one example is from 180 to 270 degrees C for 0.5 to 2 hours.
Coating film
The coating composition of the present invention can provide a hard coating with quite low adhesion to ice. The hardness of the coating film is 2H or more by pencil hardness method. The thickness of the coating film is preferably from 3 to 20 micrometers, more preferably from 5 to 15 micrometers.
Examples
The raw materials disclosed in Table 1 were used to prepare samples in Examples and Comparative Examples.
Table 1
Figure PCTCN2017095146-appb-000001
Examples 1 to 4 and Comparative Examples 1 to 7
The law materials listed in Tables 2 and 3 were homogeneously mixed by shaking for 30 minutes at room temperature. 0.6 ml of each solution was blade coated on aluminum panel and heated to cure the composition, at 200 degrees C for 1. Dry film thickness was analyzed by the film thickness gauge,
Figure PCTCN2017095146-appb-000002
FN2.2, made from PHYNIX GmbH&Co. KG. Pencil hardness were also evaluated.
Ice adhesion testing method:
Prepared plastic caps (diameter is 4.3 cm) and aluminum plates. The plastic cap is put on the aluminum plate, then the plate with the plastic cap was cooled to form ice on the surface of the aluminum plate under -20 degrees C for 24 hours. The plate with plastic cap was fixed by a clamp in environmental chamber set at -20 degrees C. The cap was pushed by a metal probe in parallel direction with the plate surface, with speed of 1mm/minutes. The maximum force (F. N) was recorded to isolate the cap from the surface of the plate. Then ice adhesion strength was calculated by the following equation: t＝F/1.45 (kPa)
The result are also added in Tables 2 and 3. Ice adhesion test was repeated for 25 cycles and record the result as 25th cycle.
Table 2
Figure PCTCN2017095146-appb-000003
Figure PCTCN2017095146-appb-000004
Table 3
Figure PCTCN2017095146-appb-000005

Claims (7)

  1. A coating composition comprising:
    (A) 50 to 95 weight ％of methylpolysiloxane resin,
    (B) 10 to 50 weight ％of silicone fluid mixture comprising a first silicone fluid and a second silicone fluid represented by the following formulas,
    (B-1) the first silicone fluid having the Formula (1)
    R2O (Me2SiO) nMe2SiOR2 Formula (1)
    wherein Me is a methyl group, R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is a number from 100 to 300, and the viscosity of the first silicone fluid is 10,000 centistokes or more,
    (B-2) the second silicone fluid having the Formula (2)
    R3 3Si (OSiMe2) mOSiR3 3 Formula (2)
    wherein Me is a methyl group, R3 is an alkyl group having 1 to 3 carbon atoms, m is a number from 10 to 40,
    wherein the viscosity of the second silicone fluid is from 100 to 2,000 centistokes,
    (C) 0.1 to 4 weight ％of a catalyst and
    (D) 50 to 90 weight ％of solvent,
    wherein the weight ratio of the first silicone fluid over the second silicone fluid ( (B-1) / (B-2) ) is from 0.6 to 2.8.
  2. The coating composition of claim 1, the catalyst is selected from zirconium octoate, zirconium acetate, zinc octoate, zinc acetate, tetrabutyl titanate and dibutyltin dilaurate.
  3. The coating composition of claim 1, further comprises (E) a filler.
  4. The coating composition of claim 3, wherein the particle size of the filler is from 10 to 300 micrometers.
  5. A coating film formed from the coating composition of claim 1.
  6. An article having a film at least a part of the surface of the article, wherein the film is formed from the coating composition of claim 1.
  7. A method for forming a film at least a part of the surface of an article, comprising the steps of:
    (a) contacting at least a part of the surface of the article with the coating composition of claim 1, and
    (b) heating the article to react the first silicone fluid with the methylpolysiloxane.
PCT/CN2017/095146 2017-07-31 2017-07-31 GLACIOPHOBIC COATINGS Ceased WO2019023838A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201780093461.XA CN110945093A (en) 2017-07-31 2017-07-31 Ice-phobic coating
KR1020207004105A KR20200035409A (en) 2017-07-31 2017-07-31 Ice-phobic coating
EP17920510.9A EP3662029A4 (en) 2017-07-31 2017-07-31 Ice-phobic coatings
US16/634,831 US20200157380A1 (en) 2017-07-31 2017-07-31 Ice-phobic coatings
PCT/CN2017/095146 WO2019023838A1 (en) 2017-07-31 2017-07-31 GLACIOPHOBIC COATINGS
TW107125918A TW201910445A (en) 2017-07-31 2018-07-26 Ice coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/095146 WO2019023838A1 (en) 2017-07-31 2017-07-31 GLACIOPHOBIC COATINGS

Publications (1)

Publication Number Publication Date
WO2019023838A1 true WO2019023838A1 (en) 2019-02-07

Family

ID=65233212

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/095146 Ceased WO2019023838A1 (en) 2017-07-31 2017-07-31 GLACIOPHOBIC COATINGS

Country Status (6)

Country Link
US (1) US20200157380A1 (en)
EP (1) EP3662029A4 (en)
KR (1) KR20200035409A (en)
CN (1) CN110945093A (en)
TW (1) TW201910445A (en)
WO (1) WO2019023838A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230167307A1 (en) * 2020-05-08 2023-06-01 Nitto Denko Corporation Coating material and laminate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188750A (en) * 1988-11-29 1993-02-23 Kansai Paint Company, Limited Anti-icing composition and method of preventing icing
CN1995251A (en) * 2006-12-27 2007-07-11 清华大学深圳研究生院 Paint for preventing covering ice for insulator and its preparation method
US7399738B1 (en) * 2007-08-03 2008-07-15 The Clorox Company Sprayable dry wash and wax composition comprising a silicone blend and acrylic-based polymer
WO2012135187A1 (en) * 2011-03-31 2012-10-04 The Armor All/Stp Products Company Compositions and methods for treating automotive surfaces
CN104530967A (en) * 2014-12-26 2015-04-22 湖北武大有机硅新材料股份有限公司 Reactive organosilicon waterproofing agent as well as preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000080354A (en) * 1998-09-03 2000-03-21 Ge Toshiba Silicones Co Ltd Rust and stain resistant protective coating composition
US6169066B1 (en) * 1998-11-17 2001-01-02 Ameron International Corporation Waterborne hydrophobic cleaning and coating composition
JP2002241695A (en) * 2000-12-15 2002-08-28 Dow Corning Toray Silicone Co Ltd Water repellent silicone coating composition
US20060281861A1 (en) * 2005-06-13 2006-12-14 Putnam John W Erosion resistant anti-icing coatings
US9688894B2 (en) * 2013-01-30 2017-06-27 University of Pittsburgh—of the Commonwealth System of Higher Education Compositions for prevention of ice build-up

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188750A (en) * 1988-11-29 1993-02-23 Kansai Paint Company, Limited Anti-icing composition and method of preventing icing
CN1995251A (en) * 2006-12-27 2007-07-11 清华大学深圳研究生院 Paint for preventing covering ice for insulator and its preparation method
US7399738B1 (en) * 2007-08-03 2008-07-15 The Clorox Company Sprayable dry wash and wax composition comprising a silicone blend and acrylic-based polymer
WO2012135187A1 (en) * 2011-03-31 2012-10-04 The Armor All/Stp Products Company Compositions and methods for treating automotive surfaces
CN104530967A (en) * 2014-12-26 2015-04-22 湖北武大有机硅新材料股份有限公司 Reactive organosilicon waterproofing agent as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3662029A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230167307A1 (en) * 2020-05-08 2023-06-01 Nitto Denko Corporation Coating material and laminate

Also Published As

Publication number Publication date
EP3662029A1 (en) 2020-06-10
CN110945093A (en) 2020-03-31
KR20200035409A (en) 2020-04-03
TW201910445A (en) 2019-03-16
EP3662029A4 (en) 2021-03-24
US20200157380A1 (en) 2020-05-21

Similar Documents

Publication Publication Date Title
CN106244093B (en) Room temperature vulcanization addition type organic silicon pouring sealant composition
TWI780221B (en) Thermally conductive ice-phobic coatings
JP5087620B2 (en) Siloxane-based lubricating composition that does not release hydrogen, method for producing the same, and use thereof
US20150361319A1 (en) Compositions for prevention of ice build-up
EP2828316A1 (en) Compositions of resin-linear organosiloxane block copolymers
WO2013154718A1 (en) Compositions comprising resin- linear organosiloxane block copolymers and organopolysiloxanes
JP7239836B2 (en) Film-forming composition
EP3662029A1 (en) Ice-phobic coatings
CN106753215B (en) Low stress thermally conductive silicone gel composition
EP3662028A1 (en) Ice-phobic coatings
JP2003165906A (en) Silicone gel composition and silicone gel
JP2025535928A (en) Silicone coating composition containing mica
JPS63258965A (en) Impact resistant silicone paint composition
KR102806590B1 (en) A one-component, post-curable, thermally conductive silicone with vertical stability and room temperature storage
CN111615542A (en) Crack-resistant polysiloxane dielectric planarization compositions, methods and films
WO2025166614A2 (en) Method of making curable thermally conductive composition
KR20250161525A (en) Polysiloxane mica blend
KR20250141157A (en) Polysiloxane mica blend
TW202603035A (en) Condensation-curing silicone resin compositions and grain-attach materials for optical semiconductor devices
Baritko et al. Fluorosiloxane elastomers and sealants on their basis
WO2019148341A1 (en) Polysiloxane resin composition
JP2014055227A (en) Surface treatment composition
JP2008208200A (en) Polysiloxane composition and method for producing cured polysiloxane

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17920510

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207004105

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2017920510

Country of ref document: EP

Effective date: 20200302