coating

Abstract

Coating provided. [Solution] A coating composition, preferably a solvent-free composition, comprising (i) a binder; (ii) optionally a curing agent; (iii) hollow inorganic spherical filler particles; and (iv) hollow organic spherical filler particles, wherein the volume ratio of the inorganic spherical filler particles to the organic spherical filler particles is at least 1.1:1, preferably 1.1:1.0 to 10.0:1.0.

Description

Technical Field

[0001] Introduction The present invention relates to a coating composition that provides thermal insulation. The composition includes a binder, optionally a curing agent, hollow inorganic spherical filler particles, hollow organic spherical filler particles, and optionally a thickener. The present invention further relates to a method of preparing the coating composition and a container containing the composition. In addition, the present invention relates to a method of providing a coating, preferably a barrier coating, on a surface (e.g., a metal surface), and a coating on a surface formed from the composition of the present invention.

Background Art

[0002] Background Coatings that provide insulation are used in a wide range of applications. For example, in the oil and gas industry where equipment is often in contact with high-temperature liquids and gases, barrier coatings are used on metal pipes, tanks, and fittings. The coating is required to have a low thermal conductivity so that sufficient insulation is provided. Typical coatings used today are a combination of mineral wool, glass wool, and calcium silicate, which are usually covered with an aluminum sheet to protect from water and humidity.

[0003] Generally, the higher the temperature of the metal surface to which the coating is applied, the thicker the barrier coating needs to be to achieve the required heat reduction over its thickness. However, the greater the thickness of the barrier coating, the greater the tendency for the coating to crack, especially when exposed to temperature changes (e.g., a rapid increase or decrease in temperature). The occurrence of cracks in the coating also tends to cause peeling or flaking (sometimes referred to as "flaking") of the coating from the metal surface. Furthermore, as soon as cracks occur, there is a risk of water and salt penetrating under the coating, creating a poor environment at the metal surface. This is a well-known problem in the oil and gas industry and is often referred to as corrosion under insulation (CUI).

[0004] Furthermore, relatively thick barrier coatings are time consuming to apply, especially when the surface area to be coated is large (e.g., the entire surface of a length of pipe or a tank). This is because it is usually necessary to apply a first layer of coating, allow it to dry and harden, then apply a second layer of coating, and so on. Doing this is necessary to avoid sagging of the coating, i.e., the coating running before it has dried and hardened. The thicker the layer of coating, the greater the chance that it will sag and the greater the degree of sagging that occurs. Sagging is particularly problematic when coating non-horizontal surfaces, such as vertical surfaces, resulting in an unsightly, uneven coating.

[0005] Thus, the barrier coating: -Heat-resistant; · Resistant to peeling at high temperatures; · Resistant to cracking even during temperature changes; ·Resistant to smears; · Can be applied to large surface areas, e.g. sprayable; - It is required to be resistant to water absorption, which can cause corrosion. Summary of the Invention

[0006] Summary of the Invention In a first aspect, the present invention provides a method for producing a method for producing a liquid crystal display comprising: (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles A coating composition comprising: A coating composition is provided, wherein the volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is at least 1.1:1.

[0007] Viewed from a further aspect, the present invention provides a method for producing a method for manufacturing a semiconductor device comprising: (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles The present invention also provides a method for preparing a composition as defined above, comprising mixing

[0008] Viewed from a further aspect, the present invention provides a method for producing a method for manufacturing a device comprising: (i) a first container containing a binder, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; (ii) a second container containing a curing agent, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; A kit for preparing a composition as defined above, comprising: A kit is provided, wherein each of the hollow inorganic spherical filler particles and the hollow organic spherical filler particles are present in at least one of the containers.

[0009] Viewed from a further aspect, the present invention provides a method for producing a method for manufacturing a semiconductor device comprising: (i) a binder; (ii) a hardener; (iii) hollow inorganic spherical filler particles; (iv) hollow organic spherical filler particles; and (v) Thickener The present invention provides a coating composition comprising:

[0010] Viewed from a further aspect, the present invention provides a method for producing a method for manufacturing a semiconductor device comprising: (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; (iv) hollow organic spherical filler particles; and (v) Thickener The present invention also provides a method for preparing a composition as defined above, comprising mixing

[0011] Viewed from a further aspect, the present invention provides a method for producing a method for manufacturing a semiconductor device comprising: (i) a first container containing a binder, optionally hollow inorganic spherical filler particles, optionally hollow organic spherical filler particles, and optionally a thickening agent; (ii) a second container containing a hardener, optionally hollow inorganic spherical filler particles, optionally hollow organic spherical filler particles, and optionally a thickener; A kit for preparing a composition as defined above, comprising: The kit is provided, wherein each of the hollow inorganic spherical filler particles, the hollow organic spherical filler particles, and the thickening agent is present in at least one of the containers.

[0012] Viewed from a further aspect, the present invention provides a container containing the composition described above.

[0013] Viewed from a further aspect, the present invention provides a method of providing a coating on a surface, said method comprising the steps of: (i) applying the composition described above; and (ii) curing the composition to form a coating on the surface. The present invention provides a method comprising:

[0014] Viewed from a further aspect, the present invention provides a coating on a surface, preferably a metal surface, said coating being formed from a composition as hereinbefore described. A preferred coating is a barrier or barrier coating.

[0015] Viewed from a further aspect, the present invention provides the use of a composition as described hereinbefore for forming a coating, preferably a barrier coating, on at least one surface of an article.

[0016] Viewed from a further aspect, the present invention provides a method for forming a barrier coating on at least one surface of an article, preferably a metal surface, comprising: (i) a binder; (ii) a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles The present invention provides the use of a composition comprising:

[0017] Viewed from a further aspect, the present invention provides a coating on a surface, preferably a metal surface, said coating being barrier-resistant and having a thickness of at least 2 mm, said coating comprising: (i) a binder; (ii) a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles The present invention provides a coating comprising:

[0018] definition The term "coating composition" as used in this disclosure refers to a composition that, when applied to a surface, forms a film or coating thereon.

[0019] The term "binder" as used in this disclosure refers to a polymer that forms a continuous film on a substrate surface when applied. The other components of the composition are dispersed throughout the binder. The term "organic binder" refers to a binder that contains carbon.

[0020] The term "hybrid binder" as used in this disclosure refers to a polymer formed with monomers from at least two binder classes, for example, epoxy and acrylic.

[0021] The term "epoxy-based" as used in this disclosure refers to polymers or oligomers that contain epoxy groups and / or modified epoxy groups. The term epoxy-based binder includes binders that have a traditional epoxy backbone, but in which the epoxy end groups are modified with, for example, acrylic or methacrylic acid functional groups that can be cured with the same curing agents as the epoxy groups. In many cases, epoxy resins contain at least some epoxy groups. The term epoxy is used interchangeably with epoxide.

[0022] The term "solid epoxy resin" as used in this disclosure refers to a polymer that is solid at 25° C. and 1 atmosphere.

[0023] The term "liquid epoxy resin" as used in this disclosure refers to a polymer that is liquid at 25° C. and 1 atmosphere.

[0024] As used in this disclosure, the term "epoxy" refers to a three atom cyclic ether.

[0025] The term "epoxy binder system" as used in this disclosure refers to a combination of one or more epoxy resins, and one or more curing agents, and optionally reactive epoxy diluents, adhesion promoters, and accelerators.

[0026] The phrase "epoxy equivalent weight" or "EEW" as used in this disclosure refers to the number of epoxide equivalents in 1 kg of resin. It is measured by ASTM D-1652.

[0027] The phrase "polysiloxane-based binder" as used in this disclosure refers to binders that contain -Si-O- repeat units. The term polysiloxane-based encompasses binders that have a traditional -Si-O- backbone, but in which the end groups have been modified. Polysiloxane binders can be organic or inorganic, although organopolysiloxane binders are preferred. In organopolysiloxane binders, the organic groups are present in the side chains and / or in the end groups.

[0028] The term "curable polysiloxane binder" as used in this disclosure refers to a polysiloxane-based binder that contains functional groups that allow crosslinking reactions to occur between polysiloxane-based binder molecules or through a crosslinker.

[0029] The term "polyurethane-based binder" as used in this disclosure refers to binders having as the main component one or more di- or poly-isocyanate components and a hydroxy-functional component containing two or more hydroxyl groups (two-component systems), or binders having as the main component one or more isocyanate prepolymers (typically one-component systems). The reaction (curing) of the isocyanate component(s) and the hydroxy-functional component(s) results in the formation of urethane functional groups.

[0030] The term "hardener" as used in this disclosure refers to a compound that when mixed with a binder, such as an epoxy-based binder, produces a cured or hardened coating by the formation of crosslinks within the polymer. Hardeners are sometimes referred to as hardeners.

[0031] As used in this disclosure, the terms "cure accelerator" and "accelerator" are used interchangeably and refer to compounds that increase the rate of the curing reaction that cures or hardens a coating.

[0032] The term "filler" as used in this disclosure refers to compounds that increase the volume or bulk of the coating composition. They are substantially insoluble in the coating composition and disperse therein. When filler particle sizes are referred to in this disclosure, they are the particle sizes as they are added to the composition.

[0033] As used in this disclosure, the term "hollow" when used in reference to organic or inorganic spherical filler particles refers to particles that have a void, cavity or empty space in the center that is occupied by gas, typically air.

[0034] As used in this disclosure, the term "spherical" when used in reference to organic or inorganic filler particles includes substantially spherical particles and spherical particles that are identical in size in each of the x, y, and z dimensions, ±1.2 μm, more preferably ±0.6 μm.

[0035] The term "average diameter" as used in this disclosure refers to the Z-average diameter size as determined by ISO 22412:2017 using a Malvern Mastersizer 2000 when the particle size is greater than 5 μm.

[0036] As used in this disclosure, the term "wt. %" (wt. %) when used with respect to individual components of the composition, such as thickeners, reactive diluents, etc., refers to the actual weight of the component, i.e., the weight not including any volatile components present, unless otherwise specified.

[0037] As used herein, the term "% by weight", when used in reference to a coating composition, unless otherwise specified, refers to weight based on the total weight of the composition, i.e., weight based on the total weight of the composition including non-volatile and volatile components.

[0038] The term "volatile organic compounds" as used in this disclosure refers to compounds that have a boiling point at 101.3 kPa of ≦250° C. This is the definition given in EU Directive 2004 / 42 / CE.

[0039] As used in this disclosure, the term "solvent-free" refers to a composition containing less than 10 g / L VOCs.

[0040] As used in this disclosure, the term "adhesion promoter" refers to a compound that improves the adhesion of a layer of a coating to a target substrate (eg, a metal substrate and / or another layer of a coating).

[0041] As used in this disclosure, the term "organosilane" refers to a compound that contains at least one Si-C bond.

[0042] The term "anti-settling agent" as used in this disclosure refers to a compound that improves the consistency uniformity of the coating composition during storage. Generally, anti-settling agents are thixotropic.

[0043] The term "thickener" as used in this disclosure refers to a compound that increases the viscosity of a coating composition. Thickeners are sometimes referred to as rheology modifiers.

[0044] The term "molecular weight" as used in this disclosure, unless otherwise specified, refers to weight average molecular weight (Mw), which is determined by Gel Permeation Chromatography.

[0045] As used in this disclosure, the term "density," when used in reference to hollow spherical filler particles, refers to the density determined by gas pycnometer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] Detailed Description of the Invention The present invention relates to (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; and (iv) hollow organic spherical filler particles; A coating composition comprising: The volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is at least 1.1:1.

[0047] Preferably, the coating composition of the present invention does not contain a solvent. Particularly preferably, the composition contains 0 to 10 g / L of VOC, more preferably 0 to 5 g / L of VOC, and even more preferably 0 to 2.5 g / L of VOC.

[0048] Optionally, the coating composition of the present invention further comprises: (v) a thickener; (vi) an adhesion promoter; (vii) a reactive diluent; and / or (viii) an additive.

[0049] The coating composition of the present invention provides a coating with a high level of thermal barrier, which means that the thickness of the coating required to achieve sufficient barrier is minimized. Advantageously, the coating formed by the coating composition of the present invention has both crack resistance and excellent adhesion to the underlying surface, such as a metal surface, such as a primed metal surface, even during exposure to high temperatures (e.g., 150°C) and thermal shock (e.g., directly from 150 to -20°C) and temperature cycling (e.g., between -20 and 60°C). Thus, the coatings formed by the coating composition of the present invention are less prone to peel or flake off from the underlying surface to which they are applied than conventional coatings. In combination, the improved crack resistance and improved adhesion of the coating of the present invention means that the coating more effectively protects the underlying substrate (e.g., metal substrate) from corrosion.

[0050] Advantageously, the coating compositions of the present invention further have a high level of sag resistance, which is highly beneficial since it means that thicker layers of the coating can be applied in one step, meaning that thicker coatings can be prepared in a relatively small number of steps, which is particularly useful when coating large, non-horizontal surfaces, such as tank walls.

[0051] binder The coating composition of the present invention comprises a binder. The type of binder present will depend primarily on the environment in which the coating will ultimately reside, particularly the temperature and corrosiveness of the environment. Preferably, the binder is an organic binder.

[0052] Examples of suitable binders that may be present in the coating composition of the present invention include epoxy-based, preferably epoxy, acrylic-based, alkyd-based, phenolic-based, silicone, polysiloxane-based, polyurethane-based, polyurea-based, polyaspartic acid-based, and hybrids and mixtures thereof. Preferably, the binder is selected from epoxy-based (e.g., epoxy), polysiloxane-based (e.g., polysiloxane), polyurethane-based (e.g., polyurethane), polyurea-based, and hybrids and mixtures thereof.

[0053] Preferably, the binder present in the coating composition is an organic binder or a polysiloxane-based binder. More preferably, the binder is an organic binder. Even more preferably, the binder is an organic binder selected from epoxy-based, more preferably epoxy, polysiloxane-based, polyurethane, and hybrids and mixtures thereof.

[0054] The total amount of binder present in the coating composition of the present invention is preferably 10 to 70 mass %, more preferably 15 to 60 mass %, even more preferably 15 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total mass of the coating composition.

[0055] Epoxy Binder In a preferred coating composition of the present invention, the organic binder is epoxy-based, preferably epoxy. Optionally, the epoxy-based binder is modified with fatty acids, polypropylene oxide and / or polyethylene oxide.

[0056] The epoxy binder, for example, may be a liquid epoxy binder or a solid epoxy binder, or a combination thereof. However, preferably, the epoxy binder is a liquid epoxy binder. When the epoxy binder is liquid, its viscosity is preferably 1000-20000mPa, more preferably 1500-15000mPas, even more preferably 1500-10000mPas, and even more preferably 2000-6500mPas.

[0057] The epoxy equivalent weight (EEW) of the preferred epoxy binder, e.g., epoxy binder, present in the coating composition of the present invention is 150-2000 g / eq, more preferably 155-1500 g / eq, even more preferably 160-1000 g / eq, and even more preferably 160-300 g / eq. The level of EEW is important to achieve an optimal mix ratio of epoxy binder and hardener (e.g., 1:1-4:1, e.g., 3:1, volume solids). It is well known that low Mw binders (often associated with low EEW) have lower viscosity and therefore formulations require less solvent. This is beneficial to achieve low VOC content or solvent-free compositions.

[0058] A preferred epoxy-based liquid binder has an epoxy equivalent weight (EEW) of 156 to 1000. A more preferred epoxy-based liquid binder has an EEW of less than 300, more preferably 156 to 300, even more preferably 156 to 250. A preferred epoxy-based solid binder has an epoxy equivalent weight (EEW) of 300 to 1000, more preferably 350 to 750, even more preferably 400 to 700, and particularly preferably 500 to 670.

[0059] Preferred epoxy binders contain more than one epoxy group per molecule. Such epoxy groups may be in the internal or terminal positions of the epoxy binder or of cyclic structures incorporated in the epoxy binder. Preferably, the epoxy binder contains at least two epoxy groups so that a crosslinked network can be formed.

[0060] Preferably, the coating composition of the present invention comprises one or more epoxy-based binders selected from aromatic epoxy-based binders, aliphatic epoxy-based binders, and cycloaliphatic epoxy-based binders.

[0061] Representative examples of aliphatic and cycloaliphatic epoxy binders suitable for use in the compositions of the present invention include hydrogenated bisphenol A, hydrogenated bisphenol A novolac, and dicyclopentadiene-based binders, glycidyl ethers (e.g., polyglycidyl ethers of polyhydric alcohols), epoxy-functional acrylic resins, and any hybrids or mixtures thereof. Modified, particularly acrylic or methacrylic acid modified, hydrogenated bisphenol A, hydrogenated bisphenol A novolac, dicyclopentadiene-based binders, glycidyl ethers (e.g., polyglycidyl ethers of polyhydric alcohols) are also preferred.

[0062] Preferably, the coating composition of the present invention comprises an aromatic epoxy-based binder, such as an aromatic epoxy binder derived from a combination of a compound containing at least one epoxide functional group and an aromatic co-reactant containing at least two hydroxyl groups.

[0063] Representative examples of aromatic epoxy binders suitable for use in the compositions of the present invention include bisphenol-type epoxy binders such as bisphenol A, bisphenol F, and bisphenol S, resorcinol diglycidyl ether (RDGE), novolac-type epoxy binders such as phenol novolac-type binders (bisphenol A novolac, bisphenol S novolac), and cresol novolac-type binders, and any hybrids or mixtures thereof. Modified, particularly acrylic acid or methacrylic acid modified, bisphenol A, bisphenol F, and bisphenol S, resorcinol diglycidyl ether (RDGE), novolac-type epoxy binders such as phenol novolac-type binders (bisphenol A novolac, bisphenol S novolac), and cresol novolac-type binders are also preferred.

[0064] Preferred examples of epoxy-based binders used in the compositions of the present invention are bisphenol A-based binders, 4,4'-isopropylidenediphenol-epichlorohydrin binders, bisphenol F-based binders, novolac-based binders, and hybrids and mixtures thereof. Particularly preferred epoxy-based binders are bisphenol A-based binders, bisphenol F-based binders, and hybrids and mixtures thereof. In some compositions, the binder is preferably a bisphenol A epoxy binder. In other compositions, the binder is preferably a bisphenol F epoxy binder. In still other compositions, the binder is preferably a mixture of bisphenol A epoxy binder and bisphenol F epoxy binder.

[0065] Bisphenol A epoxy-based binders are known to those skilled in the art and have the following general structure: [ka]

[0066] Particularly preferred coating compositions of the present invention include one or more bisphenol F epoxy-based binders. Optionally, a combination of two or more bisphenol F binders may be used. It has been found that the bisphenol F epoxy-based binder reduces the viscosity of the coating composition relative to the coating composition containing the more common bisphenol A epoxy-based binder. This allows the preparation of high solids, solvent-free coating compositions, thereby reducing VOCs.

[0067] A preferred bisphenol F epoxy binder has an EEW of 100 to 350. More preferably, the EEW is 300 or less, for example, 100 to 300, more preferably 150 to 250. A preferred bisphenol F epoxy binder is liquid. The viscosity of the bisphenol F epoxy binder is preferably 1000 to 10000 mPas, more preferably 2000 to 5000 mPas.

[0068] A preferred bisphenol F (4',4'-methylene bisphenol) epoxy-based binder is derived from a combination of bisphenol F and epichlorohydrin. The use of a difunctional epoxy-based bisphenol F binder is particularly preferred.

[0069] The solids content of the epoxy-based binder is preferably more than 70% by weight, preferably more than 80% by weight, preferably more than 90% by weight, most preferably more than 99% by weight. Particularly preferably, the epoxy-based binder is solvent-free.

[0070] Epoxy-based binders suitable for use in the coating compositions of the present invention are commercially available. Examples of commercially available epoxy-based binders suitable for the coating compositions include the following: Bisphenol A epoxy binders: Epikote 828, Epikote 1004, Epikote 1001 X 75, and Epikote 1009 from Hexion. Araldite GY250, Araldite GZ7071X75BD, and Araldite GZ7071X75CH from Huntsman Advanced Materials. DER664-20 and DER684-EK40 from Dow Chemicals; Bisphenol F epoxy binders: Epikote 862 from Hexion, YDF-170 from Kukdo, GY285 from Huntsman, DER354 from Dow, BFE-170 from CCP, or KF8100 from Kolon; and Bisphenol A & Bisphenol F Mixtures: DER352 from Dow Chemicals, and DEN438-X 80, Epikote 235 from Hexion.

[0071] The coating composition of the present invention may contain one or more epoxy-based binders. When both liquid and solid epoxy-based binders are present in the coating composition, it is preferred that the liquid epoxy-based binder is in excess of the solid epoxy-based binder.

[0072] The total amount of epoxy-based binders (i.e. liquid and solid) present in the coating composition of the present invention is preferably 10-60% by weight, more preferably 15-70% by weight, even more preferably 15-50% by weight, and even more preferably 20-40% by weight, based on the total weight of the coating composition.

[0073] Polysiloxane Binder The polysiloxane-based binder present in the coating composition of the present invention can be any curable polysiloxane-based binder. Polysiloxane-based binders are particularly useful in coatings used to insulate articles, such as tanks or pipes, at very high temperatures, such as temperatures above 100° C.

[0074] The polysiloxane-based binder is preferably an organopolysiloxane containing terminal and / or pendant curing reactive functional groups. A minimum of two curing reactive functional groups per molecule is preferred. Examples of curing reactive functional groups are silanol, alkoxy, acetoxy, enoxy, ketoxime, alcohol, amine, epoxy, and / or isocyanate. The preferred polysiloxane-based binder contains a curing reactive functional group selected from a silanol, alkoxy, or acetoxy group. The curing reaction is typically a condensation curing reaction. The polysiloxane-based binder optionally contains more than one type of curing reactive group, and may be cured, for example, via both condensation curing and amine / epoxy curing.

[0075] The polysiloxane-based binder present in the coating composition of the present invention preferably comprises at least 30% by weight of polysiloxane moieties, preferably more than 50% by weight of polysiloxane moieties, even more preferably more than 70% by weight of polysiloxane moieties, such as 99.99% by weight of polysiloxane moieties, or more. Optionally, the polysiloxane-based binder is a pure polysiloxane.

[0076] The polysiloxane moiety is defined as a repeating unit containing the motif -Si-O-, based on the total weight of the polysiloxane-based binder. The weight percent of the polysiloxane moiety can be determined based on the stoichiometric weight ratio of the starting materials in the synthesis of the polysiloxane. Alternatively, the polysiloxane content can be determined using analytical techniques such as IR or NMR. Information regarding the weight percent of the polysiloxane moiety in commercially available polysiloxane-based binders can be readily obtained from the suppliers.

[0077] It is understood that the polysiloxane-based binder may consist of a single repeating sequence of siloxane units or may be interrupted by non-siloxane moieties, such as organic moieties, which may include, for example, alkylenes, arylenes, poly(alkylene oxides), amides, thioethers, or combinations thereof, preferably, the organic moieties may include, for example, alkylenes, arylenes, poly(alkylene oxides), amides, or combinations thereof.

[0078] In one preferred coating composition of the present invention, the polysiloxane-based binder contains amine functional groups at terminal or pendant positions.

[0079] The polysiloxane-based binder may consist of only one type of polysiloxane or may be a mixture of different polysiloxanes.

[0080] In one preferred coating composition, the polysiloxane-based binder is a branched polysiloxane-based binder.

[0081] A preferred polysiloxane-based binder present in the coating composition of the present invention is represented by the following formula (D1): [ka] During the ceremony, Each R 1 is a hydroxyl group, C 1~6 Alkoxy group, C 1~6 Hydroxyl group, C 1~6 Epoxy-containing group, C 1~6 Amine group, C 1~10 Alkyl, C 6~10 Aryl, C 7~10 Alkyl aryl 、 or O-Si(R 5 ) 3-z (R 6 ) z are independently selected from Each R 2 is C 1~10 Alkyl, C 6~10Aryl, C 7~10 alkylaryl, or poly(alkylene oxide) and / or R 1 C substituted with a group according to 1~6 independently selected from alkyl; Each R 3 and R 4 is C 1~10 Alkyl, C 6~10 Aryl, C 7~10 C substituted with alkylaryl or poly(alkylene oxide) 1~6 independently selected from alkyl; Each R 5 are independently hydrolyzable groups, e.g., C 1~6 an alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group; Each R 6 is unsubstituted or substituted C 1~6 independently selected from alkyl groups; z is 0 or an integer of 1 to 2; x is an integer of at least 2; y is an integer of 0 or at least 1.

[0082] Preferably, R 1 is a hydroxyl group and O-Si(R 5 ) 3-z (R 6 ) z wherein R 5 is C 1~6 is an alkoxy group, R 6 is C 1~6 alkyl, and z is an integer of 0 or 1 to 2. More preferably, R 1 is a hydroxyl group and O-Si(R 5 ) 3-z (R 6 ) z wherein R 5 is C 1~3 is an alkoxy group, R 6 is C 1~3 alkyl, and z is an integer of 0 or 1-2.

[0083] Preferably, R 2is C 1~10 Alkyl group, C 6~10 Aryl, C 7~10 Alkylaryl, or O-Si(R 5 ) 3-z (R 6 ) z It is.

[0084] Preferably, R 3 is C 1~10 Alkyl group or C 6~10 More preferably, R 3 is C 1~4 Alkyl group or C 6 is an aryl group, and even more preferably C 1~2 Alkyl group or C 6 It is preferably an aryl group, and even more preferably a methyl group or a phenyl group.

[0085] Preferably, R 4 is C 1~10 Alkyl group or C 6~10 More preferably, R 3 is C 1~4 Alkyl group or C 6 is an aryl group, and even more preferably C 1~2 Alkyl group or C 6 It is preferably an aryl group, and even more preferably a methyl group or a phenyl group.

[0086] In one preferred coating composition, the polysiloxane binder of the present invention is a branched polysiloxane containing methyl, phenyl and methoxy groups.

[0087] The weight average molecular weight of the polysiloxane binder present in the coating composition of the present invention is preferably 400 to 150,000 g / mol, more preferably 1000 to 120,000 g / mol, and even more preferably 5000 to 110,000 g / mol.

[0088] Polysiloxane-based binders suitable for use in the coating compositions of the present invention are commercially available. Representative commercially available polysiloxane-based binders include REN 50 and REN 80 from Wacker, Silikophen P50X and Silikophen P80X from Evonik.

[0089] Preferred coating compositions of the present invention comprise 10 to 60 wt % polysiloxane-based binder, more preferably 15 to 70 wt % polysiloxane-based binder, and even more preferably 15 to 50 wt % polysiloxane-based binder, based on the total dry weight of the composition.

[0090] Polyurethane binder In preferred coating compositions of the present invention, the organic binder is polyurethane-based, preferably polyurethane.

[0091] One preferred polyurethane-based binder for use in the coating composition of the present invention comprises a) a polyisocyanate component, and b) a hydroxy-functional component containing at least two hydroxyl groups, where crosslinking results from the reaction between the polyisocyanate component a) and the hydroxyl-functional component b).

[0092] Suitable polyisocyanates for use as polyisocyanate component a) in the coating composition are well known in the art. Examples of suitable low molecular weight polyisocyanates having a molecular weight of 168 to 300 g / mol include: hexamethylene diisocyanate (HDI), 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,4-diisocyanato-1-methyl-benzene (toluene diisocyanate, TDI), 2,4-diisocyanato-1-methylbenzene, 1,4-diisocyanatocyclohexane, 1- ... isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane, 2,4- and / or 4,4'-diisocyanato-diphenylmethane, and mixtures of these isomers with their higher homologues, the higher homologues being obtainable in known manner by phosgenation of aniline / formaldehyde condensates, 2,4- and / or 2,6-diisocyanatotoluene, and any mixtures of these compounds.

[0093] In some preferred coating compositions of the present invention, the polyisocyanate component a) is selected from aliphatic polyisocyanates, such as hexamethylene diisocyanate (HDI), 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane, and 2,4- and / or 4,4'-diisocyanato-diphenylmethane.

[0094] In other preferred coating compositions of the invention, the polyisocyanate component a) is selected from aromatic polyisocyanates, such as 2,4-diisocyanato-1-methyl-benzene (toluene diisocyanate, TDI), 2,4-diisocyanato-1-methyl-benzene, and mixtures of these isomers and their higher homologues, which are obtained in known manner by phosgenation of aniline / formaldehyde condensates, 2,4- and / or 2,6-diisocyanatotoluene, and any mixtures of these compounds.

[0095] In preferred coating compositions of the invention, the polyisocyanate component a) is, as is conventional in the art, a derivative of the aforementioned monomeric polyisocyanates. These derivatives include polyisocyanates containing biuret groups. Examples of particularly preferred derivatives include N,N',N"-tris-(6-isocyanatohexyl)-biuret and mixtures thereof with its higher homologues, and N,N',N"-tris-(6-isocyanatohexyl)-isocyanurate and mixtures thereof with its higher homologues containing more than one isocyanurate ring.

[0096] Examples of suitable commercially available polyisocyanates are: Desmodur N3900 (previously VP2410), e.g. Bayer (Germany), aliphatic polyisocyanate Desmodur N3600, e.g. Bayer (Germany), aliphatic polyisocyanate Desmodur N3800, e.g. Bayer (Germany), aliphatic polyisocyanate Tolonate HDT-LV2, e.g. Rhodia (France), aliphatic polyisocyanate Desmodur N3390, e.g. Bayer (Germany), aliphatic polyisocyanate Tolonate HDT90, e.g. Rhodia (France), aliphatic polyisocyanate Basonat HI 190 B / S, e.g. BASF (Germany), aliphatic polyisocyanate Desmodur N75, e.g. Bayer (Germany), aliphatic polyisocyanate Bayhydur VP LS 2319, e.g. Bayer (Germany), aliphatic polyisocyanate Tolonate IDT 70B, e.g. Rhodia (France), aliphatic polyisocyanate Desmodur H, e.g. Bayer (Germany) Basonat HB 175 MP / X BASF-Germany, aliphatic polyisocyanate.

[0097] Examples of suitable commercially available aromatic polyisocyanate resins are: Desmodur L67 BA(Bayer Material Science) Desmodur E21(Bayer Material Science) Desmodur VL(Bayer Material Science) Voratron EC 112 (Dow Chemicals) Desmodur E23(Bayer Material Science) Desmodur E 1660(Bayer Material Science) Suprasec 2495 (Huntsman Advanced Materials).

[0098] Also preferred for use as polyisocyanate component a) are isocyanate group-containing prepolymers and semi-prepolymers based on the abovementioned monomeric polyisocyanates and organic polyhydroxyl compounds. These prepolymers and semi-prepolymers usually have an isocyanate content of 0.5 to 30% by weight, preferably 1 to 20% by weight, and are prepared in known manner by reaction of the abovementioned starting materials in an NCO / OH equivalent ratio of 1.05:1 to 10:1, preferably 1.1:1 to 3:1, optionally followed by removal by distillation of any unreacted volatile starting polyisocyanates still present.

[0099] The prepolymers and semi-prepolymers can be prepared from polyhydroxyl compounds having a molecular weight of 62 to 299 g / mol. Examples include ethylene glycol, propylene glycol, trimethylolpropane, 1,6-dihydroxyhexane, low molecular weight hydroxyl-containing esters of these polyols with dicarboxylic acids of the type exemplified below, low molecular weight ethoxylation and / or propoxylation products of these polyols, and mixtures of the aforementioned polyhydric alcohols, modified or unmodified.

[0100] Preferably, the prepolymers and semi-prepolymers are prepared from relatively high molecular weight polyhydroxyl compounds having at least two hydroxyl groups per molecule, more preferably having a hydroxyl group content of 0.5 to 17% by weight, preferably 1 to 5% by weight.

[0101] Examples of commercially available polyester polyols include: Desmophen 651 MPA, e.g. Bayer (Germany) Desmophen VP LS 2089, e.g. Bayer Material Science (Germany).

[0102] Polyether polyols, which can be obtained by alkoxylation of suitable starter molecules in a known manner, are also suitable for preparing isocyanate group-containing prepolymers and semi-prepolymers. Examples of suitable starter molecules for polyether polyols include the above-mentioned monomeric polyols, water, and any mixtures thereof. Ethylene oxide and / or polylene oxide are particularly suitable alkylene oxides for the alkoxylation reaction. These alkylene oxides can be introduced into the alkoxylation reaction in any order or as a mixture.

[0103] Examples of commercially available polyether polyols include: Desmophen 1380 BT 03 / 2008 (previously Desmophen 550 U), e.g. Bayer Material Science (Germany) Voranol CP 450 Polyol, e.g. Dow Chemicals (Germany).

[0104] Hydroxyl-containing polycarbonates, which can be prepared by reaction of the above-mentioned monomeric diols with phosgene, and diaryl carbonates, such as diphenyl carbonate, are also suitable for preparing the prepolymers and semi-prepolymers.

[0105] Preferably, component b) is based wholly or partly on organic polyhydroxyl compounds, including both the low molecular weight polyhydroxyl compounds described hereinabove for the preparation of the prepolymers and semi-prepolymers suitable for use as polyisocyanate component a), and the relatively high molecular weight polyhydroxyl compounds.

[0106] Particularly preferred hydroxyl-functional isocyanate-reactive compounds which can be used as component b) are hydroxyl-functional polyacrylates known for use in polyurethane coatings. These compounds are hydroxyl-containing copolymers of olefinically unsaturated compounds having a number average molecular weight (Mn) of 800 to 50,000, preferably 1000 to 20,000, more preferably 5000 to 10,000, determined by vapor pressure or membrane osmometry, and a hydroxyl group content of 0.1 to 12% by weight, preferably 1 to 10% by weight, most preferably 2 to 6% by weight. The copolymers are based on olefinic monomers containing hydroxyl groups and on olefinic monomers not containing hydroxyl groups. Examples of suitable monomers include vinyl and vinylidene monomers such as styrene, α-methylstyrene, o- and p-chlorostyrene, o-, m- and p-methylstyrene, p-tert-butylstyrene; acrylic acid; (meth)acrylonitrile; acrylic acids and methacrylonitriles of alcohols containing 1 to 8 carbon atoms, such as ethyl acrylate, methyl acrylate, n- and isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate. These include acrylate esters; diesters of fumaric, itaconic or maleic acid having 4 to 8 carbon atoms in the alcohol component; (meth)acrylic acid amides; vinyl esters of alkane monocarboxylic acids having 2 to 5 carbon atoms, such as vinyl acetate or vinyl propionate; and hydroxyalkyl esters of acrylic or methacrylic acid having 2 to 4 carbon atoms in the hydroxyalkyl group, such as 2-hydroxyethyl-, 2,hydroxypropyl-, 4-hydroxybutyl-acrylate and methacrylate, as well as trimethylolpropane-mono- or pentaerythrityl mono-acrylate or methacrylate. Mixtures of the above-mentioned monomers can also be used to prepare the hydroxy-functional polyacrylates. Mixtures of the polyhydroxyl compounds described above can also be used as component b).

[0107] In preferred polyurethane-based binders, components a) and b) are used in amounts sufficient to provide an equivalent ratio of isocyanate groups to isocyanate-reactive (hydroxyl) groups of 0.8:1 to 20:1, preferably 0.8:1 to 2:1, more preferably 0.8:1 to 1.5:1, even more preferably 0.8:1 to 1.2:1, and most preferably about 1:1. The hydroxyl-functional compound b) is preferably present in an amount such that there are a maximum of 20 hydroxyl groups. Preferably, the equivalent ratio of hydroxyl groups to secondary amino groups is 10:1 to 1:10.

[0108] Examples of suitable commercially available hydroxyl-functional (isocyanate-reactive) resins include: Synocure 878 N 60, e.g. Arkem (Spain), a hydroxyl-functional acrylic resin in aromatic hydrocarbons Synthalat A 0 77, e.g. Synthopol Chemie (Germany) Synthalat A 045, e.g. Synthopol Chemie (Germany) Synthalat A 088 MS, e.g. Synthopol Chemie (Germany) Synthalat A 141 HS 05, e.g. Synthopol Chemie (Germany) Synthalat A 060, e.g. Synthopol Chemie (Germany) Desmophen A XP 2412, e.g. Bayer Material Science (Germany) Synthalat A-TS 1603, e.g. Synthopol Chemie (Germany) Acrylamac 332-2629, e.g. Momentive (Germany).

[0109] Polyurea Binder In some preferred coating compositions of the present invention, the organic binder is a polyurea-based binder, preferably a polyurea. The polyurea-based binder comprises a di- or poly-isocyanate component and an amine-functional component that contains at least two amine groups.

[0110] Suitable polyisocyanates for use in the coating compositions are well known in the art. Examples of suitable polyisocyanates are as described above for the polyurethane-based binders.

[0111] The amine groups in the amine-functional component are preferably primary or secondary amine groups. More preferably, the amine groups are secondary amine groups.

[0112] Particularly preferably, the amine groups have been pre-reacted with, for example, esters of maleic and fumaric acid to produce polyaspartic acid ester derivatives. Preferred polyaspartic acid ester derivatives are represented by the formula: [ka] During the ceremony, X represents an organic group which is inert towards isocyanate groups at temperatures up to 100°C; Each R 1 and R 2 are independently selected from organic groups that are inert towards isocyanate groups at temperatures up to 100°C; Each R 3 and R 4 are independently selected from hydrogen and organic groups that are inert towards isocyanate groups at temperatures up to 100° C.; n is an integer of at least two.

[0113] Examples of suitable amine-functional components include ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,2,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminoundecane, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4 and / or 2,6-hexahydrotoluylenediamine, 2,4'- and / or 4,4'-diamino-dicyclohexylmethane, and 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane. Aromatic polyamines such as 2,4- and / or 2,6-diaminotoluene, and 2,4'- and / or 4,4'-diaminophenylmethane are also suitable. Polyether polyamines can also be used.

[0114] Hardener The coating composition of the present invention optionally comprises a curing agent. The coating composition preferably comprises a curing agent when the binder is selected from epoxy-based, preferably epoxy, phenolic, silicone, polysiloxane-based, polyurethane-based, polyurea-based, polyaspartic acid-based, and hybrids and mixtures thereof. When the binder is an acrylic or alkyd, the curing agent is optionally present.

[0115] When present, the curing agent reacts with the binder, e.g., an epoxy-based binder, during curing to form a coating, e.g., a film coating. Thus, the curing agent facilitates providing a coating composition having an acceptable curing time. In a preferred coating composition of the present invention, the curing agent cures the binder at a temperature ranging from -5 to 50°C, more preferably from 0 to 40°C. Preferably, the curing agent cures at ambient temperature. The ambient temperature of the environment varies, e.g., depending on the geographic location, and may be -5 to 50°C. An advantage of the coating composition of the present invention is that it is curable in this range, i.e., from -5 to 50°C. Unlike many known coating compositions, it is not necessary to cure it in an oven.

[0116] Conventional curing agents may be used in the coating compositions of the present invention.

[0117] The total amount of the binder and one or more curing agents in the coating composition of the present invention is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, and even more preferably 40 to 60 mass %, based on the total mass of the coating composition. The total amount of the one or more curing agents in the coating composition of the present invention is preferably 10 to 40 mass %, and even more preferably 15 to 30 mass %, based on the total mass of the coating composition.

[0118] Hardener for epoxy binders To obtain a crosslinked network with an epoxy-based binder, the curing agent must contain at least two "reactive" hydrogen atoms. The term "reactive" refers to the hydrogen atoms that can be transferred from the nucleophile to the oxygen atom of the epoxide during a ring-opening reaction. The curing agent typically contains at least two curing reactive functional groups. Preferably, the curing agent contains at least two reactive hydrogen atoms attached to nitrogen.

[0119] Representative examples of suitable classes of curing agents that can be used with epoxy-based binders include thiol curing agents, polythiol curing agents, amine curing agents, polyamine curing agents, and / or amino-functional polymeric curing agents. Alternatively, the curing agent may comprise at least one amino-functional polysiloxane. The coating composition of the present invention may comprise a mixture of curing agents.

[0120] An example of a suitable polythiol curing agent includes pentaerythritol tetramercaptopropionate. An example of a suitable commercially available polythiol curing agent is GABEPRO® GPM800 from Gabriel performance materials.

[0121] Preferred coating compositions of the present invention include an amine curing agent, a polyamine curing agent, or an amino-functional polymeric curing agent, or a mixture thereof. More preferably, the coating composition includes at least one amine-functional curing agent.

[0122] Preferably, the curing agent contains at least two amine groups. The amine groups may be primary or secondary.

[0123] Suitable amine, polyamine, and amino-functional polymer curing agents are selected from aliphatic amines and polyamines (e.g., cycloaliphatic amines and polyamines), polyamido amines, polyamide amines, polyoxyalkylene amines (e.g., polyoxyalkylenediamines), alkylene amines (e.g., alkylenediamines), aralkyl amines, aromatic amines, Mannich bases (e.g., those commercially sold as "phenalkamines"), amino-functional silicones or silanes, and their epoxy adducts, and their derivatives. The adducts can be prepared by reaction of the amines with suitable reactive compounds, such as epoxy binders, epoxy-functional reactive diluents, acrylates, maleates, fumarates, methacrylates, or with electrophilic vinyl compounds, such as acrylonitrile. Preferred amine, polyamine, and amino-functional polymer curing agents are selected from aliphatic amines and polyamines (e.g., cycloaliphatic amines and polyamines), polyamido amines, polyoxyalkylene amines (e.g., polyoxyalkylenediamines), alkylene amines (e.g., alkylenediamines), aralkyl amines, aromatic amines, Mannich bases (e.g., those commercially sold as "phenalkamines"), amino-functional silicones or silanes, and their epoxy adducts, and their derivatives. The adducts can be prepared by reaction of the amines with suitable reactive compounds, such as epoxy binders, epoxy-functional reactive diluents, acrylates, maleates, fumarates, methacrylates, or with electrophilic vinyl compounds, such as acrylonitrile.

[0124] Examples of suitable commercially available amine-functional curing agents include: Sunmide CX-105X, Ancamine 2609, Ancamine 2695, Ancamine 2712M, Ancamine 2738, Ancamine 260A, Ancamide 500, Ancamide 506, Ancamine 2386, Ancamine 2759, Ancamine 2760, Ancamine 1618, Ancamine 2165, Ancamine 2280, Ancamine 2432, Ancamine 2519, Ancamine 2802, Ancamine 2609w, Ancamine 2806 from Evonik; Epikure 3090, Epikure 3140, and Epikure 3115-X-70 from Hexion; Mannich base AP1077 from Admark Polycoats; MXDA and Gaskamine 240 from Mitsubishi Gas Chemical Company, Inc.; and Aradur 42 BD and Aradur 943 CH from Huntsman Advanced Materials.

[0125] Particularly preferably, the curing agent is a cyclic amine functional curing agent.

[0126] In one preferred coating composition of the present invention that includes an epoxy-based binder, the hardener is a Mannich base (phenalkamine) hardener. Phenalkamine is derived from cardanol, a major component of cashew nut shell liquid. Phenalkamine contains an aliphatic or cycloaliphatic polyamine substituent attached to an aromatic ring. Suitable commercially available Mannich base (phenalkamine) hardeners are available from Cardolite. Examples include Cardolite NC 541, Cardolite Lite 2001, and Cardolite Lite 2002.

[0127] In another preferred coating composition of the invention comprising an epoxy-based binder, the hardener is an aliphatic and / or cycloaliphatic polyamine, such as the Ancamine hardener from Evonik. Cycloaliphatic polyamine hardeners are particularly preferred. Specific examples of cycloaliphatic polyamine hardeners include 1,4-cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine), 2,2'-dimethyl-4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, bis(aminomethyl)cyclohexane, isophoronediamine, menthene diamine (MDA), 2,5-di(4-aminocyclohexylamine), ...1,4-cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine), 1,4-cyclohexanediamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexylamine, diaminodicyclohexyl Examples of such amines include 4-(p-aminobenzyl)cyclohexylamine, 4-(p-aminobenzyl)cyclohexylamine, 2,4'-bis(4"-aminocyclohexyl)-2',4-methylenedianiline, 4-[(4-aminocyclohexyl)methyl]-[4-[(4-aminocyclohexyl)methyl]cyclohexaneXyl]-cyclohexylamine, 2,4-di(4-aminocyclohexylmethyl)aniline, and 2,5-di(4-aminocyclohexylmethyl)aniline.

[0128] Mixtures of two or more curing agents can also be used, such as mixtures of cycloaliphatic and aliphatic curing agents, mixtures of two or more cycloaliphatic curing agents, mixtures of aromatic and cycloaliphatic curing agents, mixtures of aromatic and aliphatic curing agents, and the like.

[0129] The curing agent may be supplied neat or in a solvent. However, preferably, the curing agent is solvent-free. The main parameter of the curing agent is its viscosity. Preferably, the curing agent has a viscosity of less than 1000 mPas, more preferably less than 700 mPas. Such a viscosity facilitates the incorporation of a higher amount of hollow sphere filler, thereby improving the heat barrier.

[0130] It is common in the art to refer to the equivalent weight of a hardener in terms of "active hydrogen equivalents." The number of "active hydrogen equivalents" for one or more hardeners is the sum of the contributions from each of the one or more hardeners. The contribution to active hydrogen equivalents from each of the one or more hardeners is defined as grams of hardener divided by the active hydrogen equivalent of the hardener, and the active hydrogen equivalent of the hardener is determined as follows: grams of hardener equivalent to 1 mole of active hydrogen. For adducts with epoxy binders, the contributions of the reactants prior to the adduct are used to determine the number of "active hydrogen equivalents" in the finished epoxy binder system.

[0131] It is also common to indicate the number of "epoxy equivalents" of an epoxy binder. The "epoxy equivalent" is the sum of the contributions from each of one or more epoxy binders and any other epoxy-containing components such as silanes or reactive diluents. The contribution to the epoxy equivalent from each of one or more epoxy binders is defined as grams of epoxy binder divided by the epoxy equivalent of the epoxy binder, and the epoxy equivalent of the epoxy binder is determined as follows: grams of epoxy resin equivalent to 1 mole of epoxy groups. For adducts with epoxy binders, the contribution of the reactants prior to the adduct is used to determine the number of "epoxy equivalents" of the epoxy binder system.

[0132] In a preferred coating composition of the present invention, the ratio of hydrogen equivalent of the total hardener to epoxy equivalent of the total epoxy-based binder system of the present invention is in the range of 50:100 to 120:100.More preferred epoxy-based binder systems have a ratio of hydrogen equivalent of the hardener to epoxy equivalent of the epoxy resin in the range of 60:100 to 130:100, such as 80:100 to 120:100, for example 90:100 to 110:100.

[0133] It should be appreciated that the hardener is stored separately from the binder, e.g., epoxy-based binder, and mixed only immediately prior to application to the surface. The mixing ratio of the binder, e.g., epoxy-based binder, and hardener is governed by the relative amounts of epoxy and active hydrogen present. Preferably, the mixing ratio of binder to hardener by solid volume is 1:1 to 10:1, more preferably 5:1 to 2:1.

[0134] The total amount of the binder, e.g., an epoxy-based binder, and one or more curing agents is preferably 20-80% by mass, more preferably 30-70% by mass, and even more preferably 40-60% by mass, based on the total mass of the coating composition. The total amount of the one or more curing agents in the coating composition of the present invention is preferably 10-40% by mass, and even more preferably 15-30% by mass, based on the total mass of the coating composition.

[0135] Hardener for polysiloxane binders As described above, the polysiloxane-based binder that may be present in the coating composition of the present invention is curable and contains a curing reactive functional group such as silanol, carbinol, carboxyl, ester, hydride, alkenyl, vinyl ether, allyl ether, alkoxysilane, ketoxime, amine, epoxy, isocyanate, and / or alkoxy group. Preferably, the polysiloxane-based binder contains at least two curing reactive functional groups. Optionally, the polysiloxane-based binder contains more than one type of curing reactive functional group. Preferably, the polysiloxane-based binder contains one type of curing reactive functional group. The appropriate crosslinker and / or curing agent is selected according to the curing reactive functional groups present in the polysiloxane-based binder.

[0136] In preferred polysiloxane-based binders, the curing reactive functional groups are silanols, carbinols, alkoxysilanes, isocyanates, amines, and / or epoxies. In more preferred polysiloxane-based binders, the curing reactive functional groups are silanols, amines, and / or alkoxysilanes.

[0137] It may be necessary to add a crosslinking agent to obtain the desired crosslink density. When the curing reactive functional group is a silanol, the preferred crosslinking agent is an organosilicon compound represented by the general formula shown below, its partial hydrolysis condensation product, or a mixture of the two: R d -Si-K 4-d During the ceremony, Each R is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms, or a C substituted with a poly(alkylene oxide). 1~6 independently selected from alkyl; Each K is independently selected from hydrolyzable groups such as alkoxy groups; d is 0, 1 or 2, more preferably 0 or 1.

[0138] Preferred crosslinkers of this type include tetraethoxysilane, vinyltris(methylethyloximo)silane, methyltris(methylethyloximo)silane, vinyltrimethoxysilane, methyltrimethoxysilane, and vinyltriisopropenoxysilane, and their hydrolytic condensates.

[0139] When the curable reactive functional groups are di- or tri-alkoxy, a separate crosslinker is usually not necessary.

[0140] The crosslinker is preferably present in an amount of 0 to 10% by weight of the total dry weight of the coating composition. Suitable crosslinkers are commercially available, for example Silcate TES-40 WN from Wacker, and Dynasylan A from Evonik.

[0141] When the curing reactive functional group is amine, epoxy or isocyanate, the curing agent is preferably amine, sulfur or epoxy functional.

[0142] The curing agent may be, for example, a dual curing agent containing both an amine / sulfur / epoxy / isocyanate and an alkoxysilane. A preferred dual curing agent is represented by the following general formula: [ka] During the ceremony, LL is independently selected from unsubstituted or substituted monovalent hydrocarbon radicals of 1 to 6 carbon atoms; Each M is independently selected from a hydrolyzable group, such as an alkoxy group; a is 0, 1 or 2, preferably 0 or 1; b is an integer from 1 to 6; Fn is an amine, epoxy, glycidyl ether, isocyanate or sulfur group.

[0143] Preferred examples of such dual curing agents include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane. One particularly preferred curing agent is 3-aminopropyltriethoxysilane, e.g. Dynasylan AMEO from Evonik.

[0144] This type of dual curing agent can be used as the sole curing agent or can be used to end-capping the polysiloxane binder so that the end groups of the polysiloxane binder are modified prior to the curing reaction. For example, the polysiloxane binder and the curing agent can be mixed immediately prior to application of the coating to the article, for example within one hour prior to coating, or the polysiloxane binder can be provided in a curable form but kept dry to prevent premature curing. In some compositions, the curing agent / end-capping agent is preferably provided separately to the remainder of the coating composition to prevent the coating from curing before it is applied to the object.

[0145] Hardener for polyurethane and polyurea binders Catalysts are optionally used with polyurethane and polyurea binders to accelerate the curing reaction. Examples of suitable catalysts include tetramethylbutanediamine (TMBDA), N-alkylmorpholine, triethylamine (TEA), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), pentamethyldiethylene-triamine (PMDETA), zinc octoate, dioctyltin dilaurate, dibutyltin dilaurate, and dibutyltin oxide, particularly dioctyltin dilaurate, dibutyltin dilaurate, and dibutyltin oxide.

[0146] Accelerator The coating composition of the present invention optionally further comprises a curing accelerator. In some preferred coating compositions, the curing accelerator is not present. In such compositions, the curing agent is used without the use of a separate catalyst to accelerate the crosslinking process. In other preferred coating compositions, the curing accelerator is used to increase the speed of the curing reaction to form a coating, such as a film coating.

[0147] Any conventional cure accelerator may be present in the coating composition of the present invention.For example, the cure accelerator may be selected from imidazoles, anhydrides, polyamides, aliphatic amines, epoxy resin-amine adducts, phenols, and tertiary amines.Imidazoles, such as 2-methylimidazole, are preferred cure accelerators.

[0148] The total amount of cure accelerators present in the coating composition of the present invention is preferably 0 to 5 wt %, more preferably 0.1 to 2 wt %, even more preferably 0.1 to 1 wt %, based on the total weight of the coating composition.

[0149] Accelerators for epoxy binders When the binder is epoxy-based (e.g., an epoxy binder), the cure accelerator can be any cure accelerator known for epoxy-based coating systems. Examples include tertiary amines, (meth)acrylic esters, imidazoles, organic acids, phenols, and organic phosphines.

[0150] Examples of suitable tertiary amines are triethanolamine, dialkylaminoethanol, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diaza-bicyclo[5.4.0]undec-7-ene, and 2,4,6-tris(dimethylaminomethyl)phenol. One particularly preferred accelerator is 2,4,6-tris(dimethylaminomethyl)phenol, such as Ancamine K54 from Evonik.

[0151] Examples of suitable imidazoles are 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole.

[0152] Examples of suitable organic acids are benzoic acid derivatives, such as salicylic acid.

[0153] Examples of suitable organophosphines are tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.

[0154] Examples of suitable phenols are nonylphenol and alkylphenols such as Novares LS500.

[0155] Particularly preferred cure accelerators, especially for use with epoxy-based binders, are (meth)acrylic acid esters. (Meth)acrylic acid ester accelerators are preferably aliphatic (meth)acrylates that contain at least two (meth)acrylate functional groups linked by an organic linker. Such multiesters may be diesters, triesters or tetraesters.

[0156] The molecular weight of the (meth)acrylic ester is preferably less than 1,000.

[0157] Preferably, the (meth)acrylic acid ester is a (meth)acrylate ester of a polyol, such as a diol or triol, or a sugar-based polyol, such as a sugar alcohol. It is not necessary that all OH groups in the polyol are accompanied by a (meth)acrylate ester group, but preferably there are at least two ester functional groups in the (meth)acrylic acid ester. Suitable polyols for functionalization include alkylene diols (e.g., hexanediol, pentanediol), sugars (e.g., monosaccharides or disaccharides), or polyols (especially sugar alcohols), such as erythritol, sorbitol, maltitol, and mannitol.

[0158] Particularly preferred (meth)acrylic esters for use as cure accelerators are of formula (I): [ka] During the ceremony, each R is H or Me; each n is 2 to 5; L represents the residue of a polyol, a sugar, or a sugar alcohol, where at least two OH groups in the polyol carrier are derivatized as shown in formula (I).

[0159] Preferably, L consists only of C, H and O atoms. Preferably, the molecular weight of L is less than 1000 g / mol.

[0160] An example of a commercially available (meth)acrylic acid ester is M-Cure 400 from Sartomer.

[0161] Accelerators for polysiloxane binders When the binder is polysiloxane-based, the curing accelerator preferably comprises a catalyst.Representative examples of catalysts that can be used include transition metal compounds, metal salts and organometallic complexes of various metals such as tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium, germanium, titanium, boron, lithium, potassium, bismuth, and zirconium.The salts are preferably salts of long-chain carboxylic acids and / or chelates, or organometallic salts.

[0162] Examples of suitable tin catalysts include, for example, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, or dioctyltin dilaurate. Examples of commercially available tin catalysts include BNT-CAT 400 and BNT-CAT 500 from BNT Chemicals, FASCAT 4202 from PMC Organometallix, and Metatin Katalysator 702 from DOW.

[0163] Examples of suitable zinc catalysts are zinc 2-ethylhexanoate, zinc naphthenate, and zinc stearate. Commercially available examples of zinc catalysts include K-KAT XK-672 and K-KAT670 from King Industries, and Borchi Kat 22 from Borchers.

[0164] Examples of suitable bismuth catalysts are organobismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate, and bismuth neodecanoate. Examples of commercially available organobismuth catalysts are Borchi Kat 24 and Borchi Kat 315 from Borchers, K-KAT XK-651 from King Industries, Reaxis C739E50 from Reaxis, and TIB KAT716 from TIB Chemicals.

[0165] Examples of suitable titanium catalysts are organotitanium catalysts such as titanium naphthenate, tetrabutyl titanate, tetrakis(2-ethylhexyl)titanate, triethanolamine titanate, tetra(isopropenyloxy)-titanate, titanium tetrabutanolate, titanium tetrapropanolate, titanium tetraisopropanolate, and chelated titanates such as diisopropyl bis(acetylacetonyl)titanate, diisopropyl bis(ethylacetoacetonyl)titanate, and diisopropoxytitanium bis(ethylacetoacetate). Examples of suitable commercially available titanium catalysts are Tyzor IBAY from Dorf Ketal, and TIB KAT 517 from TIB Chemicals.

[0166] Other suitable catalysts are iron catalysts such as iron stearate and iron 2-ethylhexanoate, lead catalysts such as lead octoate and lead 2-ethyloctoate, cobalt catalysts such as cobalt-2-ethylhexanoate and cobalt naphthenate, manganese catalysts such as manganese 2-ethylhexanoate, and zirconium catalysts such as zirconium naphthenate, tetrabutyl zirconate, tetrakis(2-ethylhexyl)zirconate, triethanolamine zirconate, tetra(isopropenyloxy)-zirconate, zirconium tetrabutanolate, zirconium tetrapropanolate, and zirconium tetraisopropanoate.

[0167] Further suitable catalysts are zirconate esters.

[0168] The catalyst may be an organic compound such as triethylamine, guanidine, amidine, cyclic amines, tetramethylethylenediamine, 1,4-ethylenepiperazine, and pentamethyldiethylenetriamine. Further examples include aminosilanes such as 3-aminopropyltriethoxysilane, and N,N-dibutylaminomethyl-triethoxysilane.

[0169] In a preferred embodiment, the catalyst is a tin, titanium, bismuth, guanidine, and / or amidine catalyst, more preferably a titanium, guanidine, and / or amidine catalyst.

[0170] Preferably, the catalyst is present in the coating composition of the present invention in an amount of from 0.01 to 5% by weight, more preferably from 0.05 to 4% by weight, based on the total dry weight of the coating composition.

[0171] Reactive Diluents The coating composition of the present invention preferably further comprises a reactive diluent, which may be used alone or in combination, for example, in a mixture of two or more reactive diluents.

[0172] Preferably, the viscosity of the reactive diluent is <100 cP, preferably <50 cP, more preferably <30 cP, even more preferably <20 cP.

[0173] Preferably, the epoxy equivalent weight (EEW) of the reactive diluent is 50-500, more preferably 100-400, and even more preferably 100-300.

[0174] The preferred reactive diluents used in the coating compositions of the present invention are formed from modified epoxy compounds. Examples of suitable reactive diluents include: phenyl glycidyl ether, C 1~16 Alkyl glycidyl ether, neodecanoic acid C8~10 Alkyl glycidyl esters (i.e., R 1 R 2 R 3 C-COO-Gly, where R 1 , R 2 , and R 3 is C 8~10 alkyl group, and Gly is a glycidyl group), olefin epoxides, CH 3 -(CH 2 ) n -Gly (wherein n is 11 to 13, and Gly is a glycidyl group), 1,4-butanediol diglycidyl ether (i.e., Gly-O-(CH 2 ) 4 -O-Gly), 1,6-hexanediol diglycidyl ether (i.e., Gly-O-(CH 2 ) 6 -O-Gly), neopentyl glycol diglycidyl ether (i.e., Gly-O-CH 2 -C(CH 3 ) 2 -CH 2 -O-Gly), trimethylolpropane triglycidyl ether (i.e., CH 3- CH 2 -C(CH 2 -O-Gly) 3 ), C 1~20 -Alkyl phenyl glycidyl ether (preferably C 1~5 Alkyl phenyl glycidyl ethers, (e.g., methyl phenyl glycidyl ether, ethyl phenyl glycidyl ether, propyl phenyl glycidyl ether, and para-tertiary butyl phenyl glycidyl ether (p-TBPGE)), and reaction products of epichlorohydrin with oil obtained from cashew nut shells.

[0175] Particularly preferred reactive diluents are 1~16 Alkyl glycidyl ether, more preferably C 10~14 It is an alkyl glycidyl ether.

[0176] Another preferred reactive diluent is the reaction product of epichlorohydrin with oil obtained from cashew nut shells. An example of a commercially available reactive diluent of this type is Cardolite NC-513 from Cardolite.

[0177] Another preferred class of reactive diluents is aliphatic reactive diluents. Aliphatic reactive diluents are preferably formed from the reaction of a compound containing at least one aliphatic epoxide functional group with an aliphatic alcohol or a polyol such as 1,6-hexanediol diglycidyl ether or 1,4-butanediol diglycidyl ether. Aliphatic glycidyl ethers with chain lengths of 8 to 14 are also preferred. Aliphatic reactive diluents can contribute to the flexibility of the coating film.

[0178] The coating composition of the present invention preferably comprises 0-30 wt. %, more preferably 10-25 wt. %, even more preferably 10-20 wt. % of a reactive diluent, based on the total weight of the coating composition. The presence of the reactive diluent in the coating composition of the present invention reduces the viscosity of the coating composition and facilitates the preparation of high solids, solvent-free coating compositions.

[0179] The total amount of the binder, e.g., epoxy-based binder, one or more curing agents, accelerator, and reactive diluent is preferably 20-80% by weight, more preferably 30-70% by weight, and even more preferably 40-60% by weight, based on the total weight of the coating composition.

[0180] Hollow inorganic spherical filler particles The coating composition of the present invention comprises hollow inorganic spherical filler particles.Suitable hollow inorganic spherical filler particles are commercially available.Commercially available examples of hollow inorganic spherical filler particles include Fillite Cenosphere, Poraver (foam glass), Thermospheres, Omega spheres, and Hollolite (e.g., available from 3M, Trelleborg, Potters, SMC minerals).

[0181] Hollow inorganic spherical particles are an important component of the coating composition. These particles contribute to the heat insulation provided by the coatings prepared with the coating composition and to the coating crack resistance even during exposure to high temperatures (e.g., 150°C), thermal shock (e.g., directly from 150 to -20°C), and temperature cycling between -20°C and 60°C.

[0182] The inorganic spherical filler particles are hollow. This means that the particle has a void or cavity in its center. This void or empty space is filled with a gas, preferably air. This provides the barrier properties of the coating. The preferred inorganic spherical filler particles used in the present invention are substantially hollow. Thus, preferably, the volume of the void or cavity is at least 70% by volume, more preferably at least 80% by volume, of the total volume of the particle. Preferably, the hollow inorganic spherical filler particles have a density as low as practicable, for example, the density of the hollow inorganic spherical filler particles is between 0.1 and 1 gcm, for example as specified on the technical specifications provided by the supplier. -3 , more preferably 0.2 to 0.8 gcm -3 , and even more preferably 0.25 to 0.5 gcm -3 This reflects the fact that the particles are hollow rather than solid. Less dense particles are advantageous because they have thinner walls, which improves heat rejection.

[0183] Preferably, the hollow inorganic spherical filler particles present in the coating composition of the present invention have a crush strength of at least 3000 psi, as determined, for example, by Nitrogen Isostatic Crash Strength test. This is beneficial because it means that the filler particles do not break during processing, and therefore maintain their ability to provide insulation in the final coating. It is also advantageous that the filler particles do not change shape and / or size during processing, so they can be densely packed and achieve high structure in the final coating formed.

[0184] The hollow inorganic spherical filler particles present in the coating composition of the present invention comprise, and more preferably consist of, glass, ceramic or metal oxide. More preferably, the hollow inorganic spherical filler particles present in the coating composition of the present invention comprise, and even more preferably consist of, glass. This is because glass particles provide a good balance of crush strength, hardness and conductivity. Optionally, the hollow inorganic spherical filler particles present in the coating composition of the present invention may be surface treated. Some examples of surface treatments include treatments to modify the hydrophobicity of the surface, treatments to improve compatibility with binders, and / or treatments to facilitate chemical incorporation into binders.

[0185] The hollow inorganic filler particles present in the coating composition of the present invention are substantially spherical, more preferably spherical. This is advantageous because it allows the filler particles to be more densely packed in the coating composition of the present invention. Preferably, the hollow inorganic filler particles have a Z-average diameter of 1 to 100 μm, more preferably 1 to 80 μm, even more preferably 10 to 50 μm, as determined by ISO 22412:2017 using a Malvern Mastersizer 2000. These particle sizes are preferred because they ensure that the coating has suitable barrier properties and achieve high packing efficiency in the coating.

[0186] Preferred coating compositions of the present invention comprise 30-60% by volume, more preferably 30-55% by volume, and even more preferably 40-55% by volume of hollow inorganic spherical filler particles, based on the total volume of the composition.

[0187] Preferred coating compositions of the present invention comprise 10-40% by weight, more preferably 15-35% by weight, even more preferably 20-30% by weight of hollow inorganic spherical filler particles, based on the total weight of the composition.

[0188] Hollow organic spherical filler particles The coating composition of the present invention comprises hollow organic spherical filler particles. The hollow organic spherical filler particles present in the coating composition of the present invention can be prepared by conventional polymerization processes, such as emulsion polymerization, seed-growth polymerization, and suspension polymerization. The polymerization can be a one-stage process or a multi-stage process. Alternatively, suitable hollow organic spherical filler particles are commercially available. Examples of commercially available hollow organic spherical filler particles include Dualite (from Chase), Sunsheres (from Dow), and Expancel (from Nouryon).

[0189] The hollow organic spherical particles are important components of the coating composition because they contribute to the thermal insulation provided by coatings prepared with the coating composition, as well as to the crack resistance and adhesion, i.e., resistance to peeling, of the coating.

[0190] The organic spherical filler particles are hollow, meaning that the particle has a void or cavity in its center. This void or empty space is filled with gas, preferably air, C 1~8The organic spherical filler particles preferably have a void or cavity volume of at least 70% by volume, more preferably at least 80% by volume, of the total volume of the particle. Preferably, the hollow organic spherical filler particles have a density as low as practicable, e.g., the density of the hollow organic spherical filler particles is between 0.005 and 0.9 g cm, e.g., as specified on the technical specification provided by the supplier. -3 , more preferably 0.01 to 0.5 gcm -3 , and even more preferably 0.015 to 0.2 gcm -3 This reflects the fact that the particles are hollow rather than solid.

[0191] The hollow organic spherical filler particles present in the coating composition of the present invention comprise, and more preferably consist of, poly(meth)acrylates, polystyrenes, polyacrylamides, polyurethanes, polysiloxanes, polyolefins (e.g., polyethylene, polypropylene, polytetrafluoroethylene), polyacrylonitriles, nylons, poly(vinyl esters), vinylidenes, polyacetates, poly(esters), or copolymers thereof. It has been found that hollow organic spherical filler particles comprising these polymers produce coatings with high thermal insulation and good crack resistance even at high temperatures.

[0192] The hollow organic filler particles present in the coating composition of the present invention are substantially spherical, more preferably spherical. This is advantageous because it allows the filler particles to be more densely packed in the coating composition of the present invention. Preferably, the hollow organic filler particles have a Z-average diameter of 10 to 150 μm, more preferably 10 to 120 μm, even more preferably 15 to 120 μm, as determined by ISO 22412:2017 using a Malvern Mastersizer 2000. These particle sizes are preferred to ensure that the coating has appropriate barrier properties and to achieve high packing efficiency in the coating.

[0193] A preferred coating composition of the present invention contains 5 to 20% by volume, more preferably 10 to 20% by volume, even more preferably 10 to 15% by volume of hollow organic spherical filler particles based on the total volume of the composition.

[0194] A preferred coating composition of the present invention contains 0.25 to 1.75% by mass, more preferably 0.25 to 1% by mass, even more preferably 0.3 to 0.7% by mass of hollow organic spherical filler particles based on the total mass of the composition.

[0195] In a preferred coating composition of the present invention, the average diameter of the hollow organic spherical filler particles is larger than the average diameter of the hollow inorganic spherical filler particles. Preferably, the average diameter of the hollow organic spherical filler particles is 1 to 5 times larger, more preferably 2 to 4 times larger, than the average diameter of the hollow inorganic spherical filler particles. This combination of hollow filler particles has been found to provide a coating having a high level of heat insulation, as well as peel resistance and crack resistance.

[0196] In a preferred coating composition of the present invention, the volume ratio of the hollow inorganic spherical filler particles to the hollow organic spherical particles is 1.1:1.0 to 10.0:1.0, preferably 5 . 1:1.0 to 1.2:1.0, more preferably 4 . 1:1.0 to 1.2:1.0, even more preferably 3.8:1 It has been found that this ratio, where the volumetric amount of hollow inorganic spherical filler particles is greater than the volumetric amount of hollow organic spherical filler particles, provides the most desirable balance of crack resistance and peel resistance while maintaining adequate heat insulation and hardness.

[0197] In a more preferred coating composition of the present invention, the weight ratio of the hollow inorganic spherical filler particles to the hollow organic spherical particles is at least 50:2.5, preferably from 50:2.5 to 50:0.25.

[0198] A preferred coating composition of the present invention comprises a combined amount of hollow inorganic spherical filler particles and hollow organic spherical filler particles of 50-80 volume %, more preferably 60-70 volume %, based on the total volume of the composition, such that the hollow spherical filler particles make up a significant amount of the total volume of the composition and provide its important thermal barrier properties.

[0199] A more preferred coating composition of the present invention comprises a combined amount of hollow inorganic spherical filler particles and hollow organic spherical filler particles of 10 to 40% by mass, more preferably 15 to 30% by mass, based on the total mass of the composition.

[0200] Thickener The coating composition of the present invention further comprises a thickener. Optionally, a mixture of at least two or three thickeners may be present. The presence of a thickener in the coating composition of the present invention advantageously improves the storage stability, application properties of the composition, and sagging resistance of the composition.

[0201] Thus, another coating composition of the present invention comprises: (i) a binder; (ii) a hardener; (iii) hollow inorganic spherical filler particles; (iv) hollow organic spherical filler particles; and (v) Thickener Includes.

[0202] Preferred coating compositions of the present invention include a solvent-free thickener, which is beneficial for reducing the VOC content of the composition and increasing its solids content.

[0203] A wide variety of conventional thickeners can be used in the coating composition of the present invention. For example, fumed silica can be used as a thickener. However, the preferred coating composition of the present invention includes an oligomeric thickener. Without wishing to be bound by theory, it is believed that these thickeners increase the viscosity at low shear rates by building an interacting network of crystalline fibers, thereby improving the sagging resistance of the composition. This is particularly beneficial when the coating composition of the present invention is applied to a non-horizontal (e.g., vertical) surface. Optionally, the coating composition of the present invention includes fumed silica and at least one (e.g., one) oligomeric thickener.

[0204] Examples of suitable oligomeric thickeners include polyhydroxycarboxylic acid amides, polyhydroxycarboxylic acid esters, modified ureas, metal sulfonates, acrylated oligoamines, polyacrylic acids, modified urethanes, micronized amide waxes, micronized amide modified castor waxes, micronized castor oil derived waxes, pre-activated amide waxes dispersed in (meth)acrylate monomers, or polyamides. A preferred coating composition of the present invention comprises an oligomeric thickener selected from micronized amide waxes, micronized amide modified castor waxes, micronized castor oil derived waxes, pre-activated amide waxes dispersed in (meth)acrylate monomers. Particularly preferred thickeners are amide waxes.

[0205] The oligomeric thickeners used in the coating compositions of the present invention are commercially available, for example, micronized amide waxes available from Arkema under the trade name Crayvallac.

[0206] The amount of thickener, preferably oligomeric thickener, present in the coating composition of the present invention is preferably 0-5% by weight, more preferably 0.25-3.0% by weight, even more preferably 0.5-3.0% by weight, even more preferably 0.5-2.0% by weight, based on the total weight of the coating composition.

[0207] Adhesion promoter The coating composition of the present invention preferably further comprises an adhesion promoter, more preferably an organosilane adhesion promoter. Such adhesion promoters are well known in the art.

[0208] Silanes, especially organosilanes, are believed to improve the drying characteristics of the coating composition, especially at low temperatures. Additionally, they are believed to improve flexibility, adhesion to the substrate, and anti-corrosion performance.

[0209] Preferably, the silane contains an epoxy group. Preferably, the Mw of the silane is less than 400 g / mol.

[0210] Preferred silanes for use in the coating compositions of the present invention have the general formula (II) or (III): (II) YR (4-z) Six z (III) YR (3-y) R 1 Six y During the ceremony, z is an integer from 1 to 3; y is an integer from 1 to 2; R is a hydrocarbyl group having 1 to 12 C atoms, which optionally contains an ether or amino linker; R 1 is a hydrocarbyl group having 1 to 12 C atoms; Y is a functional group attached to R that can react with a binder, e.g., an epoxy-based binder, and / or a hardener; Each X independently represents a halogen group or an alkoxy group.

[0211] In preferred compounds of formula (II) and (III), Y is an isocyanate, epoxy, amino, hydroxy, carboxy, acrylate, or methacrylate group. The Y group may be attached to any part of the chain R. When Y represents an epoxy group, it will be understood that R has at least two carbon atoms, allowing the formation of an epoxide ring system.

[0212] In further preferred compounds of formula (II) and (III), Y is an amino group or an epoxy group. The amino group is preferably NH 2 Preferably, Y is an epoxy group. When the Y group is an amino group capable of reacting with an epoxy-based binder, the silane is preferably provided separately from the epoxy-based binder together with the hardener. Generally, in the kit of the present invention, the silane should not react with any of the components of the kit in which the silane is present.

[0213] In the preferred compounds of formula (II) or (III), R is a hydrocarbyl group, preferably having up to 12 carbon atoms. By hydrocarbyl is meant a group containing only C and H atoms. It may contain an alkylene chain or a combination of an alkylene chain and a ring, such as a phenyl or cyclohexyl ring. The term "optionally containing an ether or amino linker" refers to a group in which the carbon chain is interrupted by an -O- or -NH- group in the chain, for example, [3-(2,3-epoxypropoxy)propyl]trimethoxysilane:H 2 COCHCH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 This means that silanes such as

[0214] It is preferred that the group Y is not attached to a carbon atom which is attached to such a linker -O-, or -NH-.

[0215] R is preferably an unsubstituted (obviously other than Y) unbranched alkyl chain having 2 to 8 C atoms.

[0216] In preferred compounds of formula (II) and (III), X is C 1~6 It is an alkoxy group, such as an alkoxy group, particularly preferably a methoxy or ethoxy group. It is also particularly preferred when two or three alkoxy groups are present. Thus, in the compound of formula (II), z is preferably 2 or 3, particularly 3. In the compound of formula (III), y is preferably 2.

[0217] In preferred compounds of formula (III), R 1 is preferably C 1~4 Alkyl, for example methyl.

[0218] Particularly preferred silanes present in the coating composition of the present invention are of formula (IV): (IV) Y'-R'( 4-z’ )SiX' z’ During the ceremony, z' is an integer from 2 to 3; R' is an unsubstituted unbranched alkyl chain having 2 to 8 C atoms, optionally containing an ether or amino linker; Y' is an amino or epoxy functional group attached to the R' group; X' represents an alkoxy group.

[0219] Examples of suitable silanes for use in the coating compositions of the present invention include products manufactured by Degussa of Rheinfelden and sold under the trade name Dynasylan® D, Silquest® silane manufactured by OSi Specialties, and GENOSIL® silane manufactured by Wacker.

[0220] Specific examples include methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane (Dynasylan MTMO or 3201; Silquest A-189), 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A-187), tris(3-trimethoxysilylpropyl)isocyanurate (Silquest Y-11597), γ-mercaptopropyltrimethoxysilane (Silquest A-189), β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Silquest A-186), γ-isocyanatopropyltrimethoxysilane (Silquest A-Link35, Genosil GF40), (methacryloxymethyl)trimethoxysilane (Genosil XL 33), (isocyanatomethyl)trimethoxysilane (Genosil XL 43), aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest AI 110), aminopropyltriethoxysilane (Dynasylan AMEO) or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Dynasylan DAMO, Silquest AI 120) or N-(2-aminoethyl)-3-aminopropyltriethoxysilane, triaminofunctional trimethoxysilane (Silquest A-1130), bis(γ-trimethoxysilylpropyl)amine (Silquest AI 170), N-ethyl-γ-aminoisobutyltrimethoxysilane (Silquest A-Link15), N-phenyl-γ-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino-3,3-dimethylbutyltrimethoxysilane (Silquest YI 1637), (N-cyclohexylaminomethyl)triethoxysilane (Genosil XL 926), (N-phenylaminomethyl)trimethoxysilane (Genosil XL 973), Deolink Epoxy TE and Deolink Amino TE (DOG Deutsche Oelfabrik), and mixtures thereof.

[0221] Other preferred silanes include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(aminoethyl)-aminopropyltrimethoxysilane (H 2 NCH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ), 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, (H 2 NCH 2 CH 2 NHCH 2 CH 2 CH 2 SiCH 3 (OCH 3 ) 2 ), [3-(2,3-epoxypropoxy)propyl]triethoxysilane (H 2 COCHCH 2 OCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , [3-(2,3-epoxypropoxy)propyl]trimethoxysilane (H 2 COCHCH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) are mentioned.

[0222] 3-glycidoxypropyltrimethoxysilane is particularly preferred. Mixtures of silanes can also be used.

[0223] The amount of adhesion promoter, preferably organosilane adhesion promoter, present in the coating composition of the present invention is preferably 0-15% by weight, more preferably 0.1-10% by weight, even more preferably 0.5-5% by weight, even more preferably 0.5-3% by weight, based on the total weight of the coating composition. In preferred compositions of the present invention, the total amount of organosilanes present therein is preferably 0-15% by weight, more preferably 0.1-10% by weight, even more preferably 0.5-5% by weight, even more preferably 0.5-3% by weight, based on the total weight of the coating composition.

[0224] Additives The coating composition of the present invention optionally contains various additives. Examples of additives that are optionally present in the composition of the present invention include co-binders, hydrocarbon resins, anti-settling agents, fillers, amino alcohols, color pigments, drying agents, dispersants, and surface modifiers. Examples of compounds that are preferably absent from the composition (e.g., present at less than 0.1% by weight, preferably less than 0.05% by weight) include alkaline earth metal hydroxides, aluminum group hydroxides, and phosphorus-containing compounds.

[0225] The additional additives are preferably present in an amount of 0 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.1 to 5% by weight, and especially preferably 0.5 to 5% by weight, based on the total weight of the coating composition.

[0226] The coating composition of the present invention optionally comprises a co-binder. Examples of suitable co-binders include saturated polyester resins, polyvinyl acetate, polyvinyl butyrate, copolymers of vinyl acetate, vinyl isobutyl ether, copolymers of vinyl chloride and vinyl isobutyl ether, styrene copolymers such as styrene / butadiene copolymers, acrylic resins, hydroxy-acrylate copolymers, fatty acids, and cyclized rubbers.

[0227] The coating composition of the present invention preferably contains 0 to 10% by weight of a co-binder, based on the total weight of the composition.

[0228] The coating composition of the present invention optionally includes a hydrocarbon resin. A variety of hydrocarbon resins are suitable for inclusion in the coating composition. Preferably, the hydrocarbon resin is a petroleum resin.

[0229] Examples of petroleum resins suitable for the present invention include C 2 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 2 9 Aromatic petroleum resins obtained by polymerization of fractions (for example styrene derivatives such as alpha-methylstyrene, o, m, p-cresol, indene, methylindene, cumene, naphthalene or vinyltoluene), C 1,3-pentadiene or isoprene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene or cyclopentene, 5 and aliphatic petroleum resins obtained by polymerization of the C 9 Fraction and C 5 Copolymer-based petroleum resins obtained by copolymerization of fractions such as cyclopentadiene or 1,3-pentadiene. 5 Aliphatic petroleum resins in which the conjugated diene portion of the fraction is cyclically polymerized, resins obtained by hydrogenating aromatic petroleum resins, and alicyclic petroleum resins obtained by polymerization of dicyclopentadiene can also be used in the present invention. 9 Mixtures of diaryl and triaryl compounds resulting from the reaction of blends may also be utilized.

[0230] The coating composition of the present invention preferably contains 0 to 10% by weight of the hydrocarbon resin, based on the total weight of the composition.

[0231] composition A preferred coating composition of the present invention comprises (i) a binder, preferably an epoxy-based binder; (ii) a hardener; (iii) Hollow inorganic (e.g., glass) spherical filler particles; and (iv) Hollow organic spherical filler particles; comprising, the volume ratio of the inorganic spherical filler particles to the organic spherical filler particles being at least 1.1:1.

[0232] A more preferred coating composition of the present invention is (i) An epoxy binder; (ii) A curing agent; (iii) An accelerator; (iv) A reactive diluent; (v) Hollow inorganic spherical filler particles, preferably hollow glass spherical filler particles; (vi) Hollow organic spherical filler particles; (vii) Optionally an adhesion promoter; and (viii) Optionally a thickener comprising, the volume ratio of the inorganic spherical filler particles to the organic spherical filler particles being at least 1.1:1.

[0233] A more preferred coating composition of the present invention is (i) 15 - 50% by mass, preferably 20 - 40% by mass of an epoxy binder; (ii) 10 - 40% by mass, preferably 15 - 30% by mass of a curing agent; (iii) 15 - 35% by mass, preferably 20 - 30% by mass of hollow inorganic (e.g., glass) spherical filler particles; and (iv) 0.25 - 1.0% by mass, preferably 0.3 - 0.7% by mass of hollow organic spherical filler particles; comprising, the volume ratio of the inorganic spherical filler particles to the organic spherical filler particles being at least 1.1:1.

[0234] A particularly preferred coating composition of the present invention is (i) 15 - 50% by mass, preferably 20 - 40% by mass of an epoxy binder; (ii) 10 - 40% by mass, preferably 15 - 30% by mass of a curing agent; (iii) 15 to 35% by weight, preferably 20 to 30% by weight, of hollow inorganic (e.g. glass) spherical filler particles; (iv) 0.25 to 1.0 mass %, preferably 0.3 to 0.7 mass %, of hollow organic spherical filler particles; (v) 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of an adhesion promoter; and (vi) 0.25 to 3 mass %, preferably 0.5 to 2 mass %, of a thickener Includes.

[0235] In such compositions, the volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is preferably at least 1.1:1.

[0236] The solids content of the preferred coating compositions of the present invention is at least 98% by weight, more preferably at least 99% by weight. Particularly preferred is a solids content of the coating composition of the present invention of 100% by weight, which means that the coating composition is substantially free of VOCs.

[0237] The preferred coating composition of the present invention is sprayable. Particularly preferred coating compositions of the present invention are thixotropic. Thus, the coating composition flows when shear is applied with a spray device, but does not flow when applied to a surface. This minimizes the amount of sagging that occurs, even when a thick layer of the coating composition is applied.

[0238] Preferred coating compositions of the present invention provide coatings having a thermal conductivity of less than 0.15 W / mK, more preferably between 0 and 0.12 W / mK.

[0239] Preferred coating compositions of the present invention provide coatings that have a heat loss of at least 5° C. / mm, more preferably at least 7° C. / mm, more preferably 9° C. / mm or greater.

[0240] Preferred coating compositions of the present invention provide coatings that are curable at ambient temperatures. Particularly preferred coating compositions provide coatings that are curable at temperatures below 100° C., more preferably below 50° C., and even more preferably below 40° C., each at 50% RH. Preferably, the coating compositions provide coatings over a relatively wide temperature range over which the coating can be cured (e.g., a range spanning at least 80° C., more preferably a range spanning at least 100° C. (e.g., 80-150° C.)).

[0241] Preferred coating compositions of the present invention provide coatings having a sag resistance of at least 1.5 mm, more preferably at least 2 mm, more preferably at least 2.5 mm, as determined, for example, by the methods described in the Examples. Particularly preferred coating compositions provide coatings having a sag resistance of at least 5 mm, more preferably at least 10 mm.

[0242] Preferred coating compositions of the present invention provide coatings that are resistant to peeling at 150° C. when the DFT is at least 5 mm, preferably at least 10 mm.

[0243] Preferred coating compositions of the invention provide coatings that are resistant to cracking during temperature changes from -20°C to 60°C, for example as determined by the method described in the Examples, when the DFT is at least 5mm, preferably at least 10mm.

[0244] Particularly preferred coating compositions of the present invention provide coatings having one or more of the following: a thermal conductivity of less than 0.15 W / mK, more preferably 0 to 0.12 W / mK; a thermal reduction of at least 5°C / mm, more preferably at least 7°C / mm; It is curable at temperatures below 100°C, preferably below 50°C, at 50% RH; a sag resistance of at least 1.5 mm, more preferably at least 2.0 mm, as determined by the method described in the Examples; Resistance to peeling at 150°C at a dry thickness of at least 5mm, preferably at least 10mm; and / or Resistance to cracking during a temperature change from -20°C to 60°C (determined, for example, by the method described in the Examples) at a dry thickness of at least 5mm, preferably at least 10mm.

[0245] Containers and kits The present invention further relates to a container containing the coating composition described above. Suitable containers include cardboard boxes lined with plastic bags, and plastic bags (so-called "big bags").

[0246] Alternatively, the coating composition of the present invention can be provided in the form of a kit. In the kit, the hardener is preferably present in a separate container from the binder. Thus, the kit comprises: (iii) a first container containing a binder, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; (iv) a second container containing a curing agent, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles. Including, The hollow inorganic spherical filler particles and the hollow organic spherical filler particles are each present in at least one of the containers, and the volume ratio of the inorganic spherical filler particles to the organic spherical filler particles is at least 1.1:1.

[0247] In a preferred kit of the present invention, the hollow inorganic spherical filler particles are present in one container (e.g., the first container) and the hollow organic spherical filler particles are present in another container (e.g., the second container). Alternatively, the hollow inorganic spherical filler particles and the hollow organic spherical filler particles can be present in both the first and second containers. A preferred kit further comprises an accelerator, particularly preferably in the second container. A preferred kit further comprises a reactive diluent, particularly preferably in the first container. A preferred kit further comprises an adhesion promoter, particularly preferably in the first container.

[0248] Particularly preferred kits of the invention further comprise a thickening agent. The thickening agent may be present in the first container, the second container, or both containers. In particularly preferred kits, the thickening agent is present in both containers.

[0249] manufacturing The present invention further provides a method for preparing the coating composition described above, comprising the steps of: (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles The method relates to a method comprising mixing

[0250] In a preferred method of the invention, the binder is premixed with a certain percentage of each of the hollow spherical filler particles, and separately, the hardener is premixed with the remaining percentage of each of the hollow spherical filler particles, and the two resulting mixtures are then mixed together.

[0251] If present, the reactive diluent is preferably premixed with the binder.If present, the adhesion promoter is preferably premixed with the binder.If present, the accelerator is preferably premixed with the curing agent.

[0252] If present, the thickening agent is preferably premixed with each of the binder and hardener.

[0253] Any conventional mixing equipment can be used.

[0254] Surface Application The present invention further relates to a method of coating a surface, said method comprising the steps of: (i) applying the composition described above; and (ii) curing the composition to form a coating on the surface. Includes.

[0255] Optionally, the surface is pretreated before application of the coating composition of the present invention. Optionally, the surface is coated with one or more primer compositions before application of the coating composition of the present invention. Thus, the coating composition of the present invention may be part of a coating system. In a preferred coating system, one or more primers are applied to the surface, and then the coating composition is applied to the primer layer. Examples of suitable primers include poly(urethane)-based and epoxy-based primers. Epoxy-based primers are particularly preferred.

[0256] The temperature of the surface to which the composition is applied is preferably in the range of −10 to 180° C., more preferably in the range of −5 to 150° C., even more preferably in the range of 0 to 10° C., and 10 to 50° C. An advantage of the coating compositions of the present invention is that they can be applied to both hot and cold surfaces.

[0257] The coating composition of the present invention can be applied to the substrate by any conventional coating method, such as spraying, rolling, dipping, etc. Preferably, the coating composition is applied by spraying, more preferably by airless spraying. Airless spraying can be carried out, for example, using a two-component airless spray pump. Preheating of the product up to 70°C and / or pressures such as 3-6 bar may be required. The coating composition may also be applied manually, for example with a trowel.

[0258] Spraying is preferred because it allows large surface areas to be coated uniformly. In addition, spraying can be used to coat non-horizontal surfaces. Preferably, the substrate is metal, especially steel. The present invention further relates to a coating comprising the coating composition described above. Optionally, the coating is applied in multiple steps, in which a first layer of the coating is applied, dried and cured, and then a subsequent layer of the coating is applied. Preferably, the number of application steps is minimized. An advantage of the coating composition of the present invention is that it has a high sagging resistance, and therefore a relatively thick layer of the coating can be applied in one step. Preferably, the layer of the coating applied in one step is 0.2 to 20 mm, more preferably 0.5 to 10 mm.

[0259] The coating composition of the present invention can be used to form a single layer coating or a multi-layer coating (i.e., a coating system). In the case of a multi-layer coating, the coating composition of the present invention is preferably used to form a second layer on a substrate, such as a metal pipe, on top of a primer layer. Preferably, a topcoat is applied. Examples of suitable topcoat layers are layers comprising poly(urethane)-based resins, acrylic resins, silicone resins, or mixtures thereof. However, the coating composition of the present invention can also be used as a primer layer.

[0260] hardening Preferably, the coating of the present invention is cured. Thus, when the substrate is coated with the coating composition of the present invention, the coating is preferably cured. Preferably, the coating of the present invention can be cured at ambient temperature. Thus, preferably the coating of the present invention does not require heating to cause curing. This means that the coating of the present invention can be cured over a wide temperature range, for example, from a relatively low temperature to a relatively high temperature (e.g., a hot surface). Particularly preferably, the coating of the present invention cures without external heating in the temperature range of -5 to 50°C. Preferably, the curing time (i.e., the time to achieve surface dryness by the thumb test) is 0.5 to 10 hours, more preferably 1 to 5 hours.

[0261] Coatings and Articles The present invention further relates to a coating composition as described above or a substrate coated with the coating as described above. The coating composition of the present invention can be applied to any substrate. Representative examples of substrates include metal substrates (steel, galvanized steel, aluminum, copper), glass, ceramics, and polymeric materials (e.g., plastics). Preferred substrates are metal substrates. More preferably, the substrate is carbon steel. The coating of the present invention provides a heat-insulating coating to such substrates. Thus, the types of metal substrates preferably coated with the coating of the present invention are those in contact with high-temperature substances or low-temperature substances. Examples of metal substrates include tanks, line pipes, bends and fittings, valves, pumps, manifolds, coils, and tracers. Particularly preferred substrates are metal tanks or metal pipes, e.g., metal tanks and pipes for oil and gas recovery. Preferably, the diameter of the metal tank is 5 m or more.

[0262] The substrate may be partially or completely coated with the coating composition or coating of the present invention. However, preferably, the entire substrate is coated with the coating composition or coating of the present invention. In the case of a tank or pipe, preferably the external wall is coated with the coating composition of the present invention.

[0263] Preferably, the coating has a total dry thickness of 2 to 150 mm, more preferably 5 to 100 mm, even more preferably 8 to 80 mm. Preferably, the coating is barrier. Preferably, the coating provides insulation to the metal surface in the temperature range of -196 to 450°C, more preferably -196 to 250°C. Thus, a preferred coating of the present invention is on a metal surface, said coating being barrier and having a thickness of at least 2 mm, the coating comprising: (i) a binder; (ii) a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles.

[0264] Preferably, the coating is a thermal barrier coating. Preferred binders, hardeners, filler particles, and other components present in the coating are as described above.

[0265] Preferred coatings of the present invention have a thermal conductivity of less than 0.15 W / mK, more preferably between 0 and 0.12 W / mK.

[0266] Preferred coatings of the present invention have a thermal reduction of at least 5° C. / mm, more preferably at least 7° C. / mm, and even more preferably 9° C. / mm or greater.

[0267] Preferred coatings of the invention are curable at ambient temperature. Particularly preferred coatings are curable at temperatures below 100° C., more preferably below 50° C., even more preferably below 40° C., each at 50% RH. Preferably, the coatings have a relatively wide temperature range over which they can be cured, for example a range spanning at least 80° C., more preferably a range spanning at least 100° C. (e.g. 80-150° C.).

[0268] Preferred coatings of the present invention have a sag resistance of at least 1.5 mm, more preferably at least 2.0 mm, as determined, for example, by the method described in the Examples.

[0269] Preferred coatings of the invention are resistant to peeling at 150° C. when the DFT is at least 5 mm, preferably at least 10 mm.

[0270] Preferred coatings of the invention are resistant to cracking during a temperature change from -20°C to 60°C, for example as determined by the method described in the examples, when the DFT is at least 5mm, preferably at least 10mm.

[0271] Particularly preferred coatings of the present invention have one or more of the following: a thermal conductivity of less than 0.15 W / mK, more preferably 0 to 0.12 W / mK; a thermal reduction of at least 5°C / mm, more preferably at least 7°C / mm; It is curable at temperatures below 100°C, preferably below 50°C, at 50% RH; a sagging resistance of at least 1.5 mm, more preferably at least 2.0 mm, e.g., as determined by the method described in the Examples; Resistance to peeling at 150°C at a dry thickness of at least 5mm, preferably at least 10mm; and / or Resistance to cracking during a temperature change from -20°C to 60°C (determined, for example, by the method described in the Examples) at a dry thickness of at least 5mm, preferably at least 10mm.

[0272] Viewed from another aspect, the present invention provides a coating having one or more of the following: a thermal conductivity of less than 0.15 W / mK, more preferably 0 to 0.12 W / mK; a thermal reduction of at least 5°C / mm, more preferably at least 7°C / mm; It is curable at temperatures below 100°C, preferably below 50°C, at 50% RH; a sagging resistance of at least 1.5 mm, more preferably at least 2.0 mm, e.g., as determined by the method described in the Examples; Resistance to peeling at 150°C at a dry thickness of at least 5mm, preferably at least 10mm; and / or Resistance to cracking during a temperature change from -20°C to 60°C (determined, for example, by the method described in the Examples) at a dry thickness of at least 5mm, preferably at least 10mm.

[0273] use The present invention further provides the use of a composition as described hereinbefore for forming a coating, preferably a barrier coating, on at least one surface of an article, preferably the surface being a metal surface as described hereinbefore.

[0274] The invention will now be described with reference to the following non-limiting examples. EXAMPLES

[0275] example material The compounds and polymers used in the examples were all commercially available and are summarized in the table below.

[0276] [Table 1]

[0277] Preparation of the coating composition The components of the coating composition were mixed in the proportions described in the following table. The components of the composition are given in the table as mass % without parentheses and volume % with parentheses.

[0278] All of the liquid portion of Component A was mixed in a dissolver. Then, the appropriate one or more fillers were added to the measured amount of the premixed liquid phase and sealed in a container. This was then homogenized in a Speedmixer operating at 1800 rpm for 90 seconds. The same procedure was followed for Component B, and then Components A and B were transferred to the same container and subjected to the Speedmixer at 1800 rpm for 90 seconds.

[0279] The solids content was calculated based on the information provided by the supplier regarding the solids content of the product.

[0280] The VOC was less than 0.5 g / L. The coating composition was essentially solvent-free.

[0281] Preparation of test samples For the thermal conductivity test, the mixed liquid coating was poured into a circular silicone mold (60 mm in diameter) to depths of 10 mm and 20 mm and then left to cure (24 hours at 22°C, 5 days at 60°C, 24 hours at 22°C).

[0282] For the heat reduction test, a steel plate (3 mm thick, carbon steel, Sa 2 1 / 2) was placed in an appropriate silicone mold and coated with the mixed liquid coating. The (wet and dry) thickness of the coating was 12 mm.

[0283] Coating of T-bars (carbon steel, Sa 2 1 / 2, 1 cm thick, LxWxH 10x11x14 cm) was performed by placing the T-bars on a 3D printed mold with a spacing of 15 mm on all sides. The premixed compositions to be tested were poured into the molds and cured (24 h at 22°C, 5 days at 60°C, 24 h at 22°C).

[0284] For the sagging tests, steel plates were placed in suitable silicone moulds and coated with the mixed liquid coating. The coating thickness (wet and dry) was varied from 1 mm to 15 mm.

[0285] All molds were removed prior to testing.

[0286] spray The coating compositions in the following spray examples were sprayed using the following equipment and conditions:

[0287] Components A and B were heated to 65°C in two separate pressurized storage tanks (4.5 bar (65 psi)). Two airless feed pumps (ram assisted feed plate) were used. Metering pumps were additionally used to ensure the correct volumetric ratio of each component was delivered (metering pump pressure 200-320 bar (2900-4000 psi)). In-line heaters were used to ensure the temperatures of the components were in the correct range (in-line heater temperatures, component A 45°C, component B 35°C). The nozzle tip size was 27-35 (in / 1000) and the nozzle temperature was 50°C-60°C. The coating composition was sprayed at a wet film thickness of up to 75 mm without coating sagging.

[0288] [Table 2]

[0289] Test Method Coating thickness was measured using a ruler or calipers. Thermal conductivity (W / mK) was tested with a FOX50 instrument from TA Instruments according to ASTM C518 and / or C177. The heat loss (°C / mm) was measured by comparing the temperature of the steel surface (below the coating) with the temperature above the coating surface by a separate thermocouple. Heating was performed by placing the coated steel on a hot plate set at 180-210°C. The coated steel was monitored and it was reported whether any peeling of the coating occurred. Temperature change test - cycle: Coated T-bars were subjected to the following thermal cycle: 3 hours at 60°C, 2 hours with a temperature drop of 40°C / h, 3 hours at -20°C, 1 hour with a temperature rise of 40°C / h, 2 hours at 20°C, 1 hour with a temperature rise of 40°C / h, repeating the cycle. Samples were monitored and visually inspected. If cracks were observed, the test was stopped. If no cracks were observed, the samples were tested for 1 month. Thermal shock testing was performed by placing the coated T-bars in an oven set at 150°C for 16 hours and then transferring the samples directly to a climate chamber set at -20°C where they were left for 2 hours. The T-bars were visually inspected and any cracks were reported. If cracks were observed, the result was reported as "poor". · Sagging resistance was tested by placing a steel plate in the bottom of a silicone mold to allow for various coating thicknesses. The mold was filled with the composition to be tested and immediately positioned vertically. A spatula was used to draw a horizontal line down to the exposed steel. The test samples were then cured for 16 hours at 23°C and 50% RH. The samples were visually inspected to determine coating sagging. The highest coating thickness at which no sagging was observed was reported unless otherwise specified. The density of the coating was calculated based on the density of each component in relation to its mass / volume percentage in the coating.

[0290] The test results are also given in the table below, where CE means comparative example.

[0291] [Table 3-1] [Table 3-2]

[0292] The coatings of the present invention (Examples 1 and 2) exhibit a desirable balance of properties. The coating compositions are sprayable and dry in an acceptable time at room temperature. The coatings exhibit desirable low levels of thermal conductivity and high levels of heat reduction, and do not degrade during temperature change testing, i.e., do not peel or crack when the temperature changes, whether the temperature change is rapid or gradual. In contrast, comparative coatings (CE1 and CE2) that do not contain a mixture of hollow glass spherical filler particles and hollow organic filler particles did not peel or crack during the tests performed.

[0293] Similarly, the inventive coatings (Examples 1 and 2) performed better than a comparative coating (CE3) that contains a mixture of hollow glass spherical filler particles and hollow organic filler particles, but with a lower volume ratio of glass filler particles to organic filler particles of 0.71:1 (Cf. Examples 1 and 2, 3.6:1 and 1.8:1, respectively). As discussed above, Examples 1 and 2 produced coatings that did not degrade during temperature change cycling, i.e., did not peel or crack when the temperature changed during thermal shock experiments, while the coating of CE3 failed in the same experiments.

[0294] Another important property of a coating composition, especially one that is applied to a non-horizontal surface, is its ability to resist sagging. Thicker coatings tend to sag more than thinner coatings. However, to achieve thermal insulation, it is often necessary to build up a relatively thick coating, e.g., 10-15 mm, and the fewer coats required to achieve the desired thickness, the better. Various coating compositions have been tested for sagging resistance.

[0295] Coating compositions similar to Examples 1-3 and CE1-3, here Examples 1-1, 2-1, 3-1, CE1-1, CE2-1 and CE3-1, were prepared by additionally including a thickener. The results of sagging tests on the resulting compositions are shown below in Table 2. The coating compositions of the present invention exhibit strong resistance to sagging, which is advantageous as it means that the coating can be applied in a relatively thick layer.

[0296] Additional coating compositions 4-8 and CE4-6 were prepared and tested. The results are shown below in Table 3. The results show that the coating compositions of the present invention provide desirable low levels of thermal conductivity and resistance to sagging.

[0297] [Table 4-1] [Table 4-2]

[0298] [Table 5-1] [Table 5-2]

[0299] The results in Table 3 show that the coating compositions of the present invention can resist sagging. For example, when the coating composition of Example 5 was applied at a thickness of >10 mm, no sagging was observed when it was placed vertically. This is highly advantageous as it means that the coating can be applied in relatively few thick coats. In contrast, CE4, which does not contain a thickener, CE5, which does not contain a thickener and hollow organic filler particles, and CE6, which does not contain a thickener and hollow inorganic filler particles, sag much more significantly.

[0300] Among the different thickeners tested, the results show that the amide wax provided the coating composition with the highest level of sagging resistance (Example 5, cf. Examples 6, 7 and 8). The present disclosure also includes the following: [Aspect 1] (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles A coating composition, preferably a solvent-free composition, comprising: A coating composition, wherein the volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is at least 1.1:1, preferably 1.1:1.0 to 10.0:1.0. [Aspect 2] 2. The composition of claim 1, wherein the binder is selected from epoxy based, preferably epoxy, acrylic, alkyd, phenolic, silicone, polysiloxane, polyurethane, polyurea, polyaspartic, and hybrids and mixtures thereof, preferably the binder is epoxy based, in particular epoxy. [Aspect 3] 3. The composition of any one of the preceding claims, wherein the curing agent is an aliphatic or alicyclic amine or polyamine. [Aspect 4] A composition according to any one of Aspects 1 to 3 above, wherein the hollow inorganic spherical filler particles comprise, and preferably consist of, glass. [Aspect 5] Aspect 5. The composition of any one of aspects 1 to 4, wherein the hollow inorganic spherical filler particles have an average diameter of 10 to 100 microns. [Aspect 6] Aspect 6. The composition of any one of aspects 1 to 5, wherein the hollow organic spherical filler particles have an average diameter of 10 to 120 microns. [Aspect 7] Aspect 7. The composition of any one of aspects 1 to 6, wherein the hollow organic spherical filler particles have an average diameter greater than the average diameter of the hollow inorganic spherical filler particles. [Aspect 8] The composition according to any one of the above aspects 1 to 7, wherein the volume ratio of the hollow inorganic spherical filler particles to the hollow organic spherical particles is 1.1:1.0 to 10.0:1.0, preferably 5:1:1.0 to 1.2:1.0. [Aspect 9] 9. The composition according to any one of the above aspects 1-8, further comprising a thickener, preferably an amide wax thickener. [Aspect 10] The composition of any one of the above embodiments 1-9, further comprising an organosilane adhesion promoter. [Aspect 11] (i) a binder; (ii) optionally a hardener; (iii) hollow inorganic spherical filler particles; and (iv) Hollow organic spherical filler particles A method for preparing a composition according to any one of the above aspects 1 to 10, comprising mixing: [Aspect 12] (i) a first container containing a binder, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; (ii) a second container containing a curing agent, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; A kit for preparing the composition according to any one of the above aspects 1 to 10, comprising: said hollow inorganic spherical filler particles and said hollow organic spherical filler particles are each present in at least one of said containers, and the volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is at least 1.1:1. [Aspect 13] 1. A method for providing a coating on a surface, preferably a metal surface, said method comprising: (i) applying a composition according to any one of the above aspects 1 to 10; and (ii) curing the composition to form a coating on the surface. A method comprising: [Aspect 14] 11. A coating on a surface, preferably a metal surface, said coating being formed from a composition according to any one of aspects 1-10 above. [Aspect 15] Use of a composition according to any one of the above embodiments 1 to 10 for forming a coating, preferably a barrier coating, on at least one surface of an article (e.g. a metal surface).

Claims

1. (i) a binder; (ii) optionally a curing agent; (iii) hollow inorganic spherical filler particles; (iv) hollow organic spherical filler particles; and (v) Thickener A coating composition comprising: A coating composition, wherein the volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is at least 1.1:

1.

2. The composition of claim 1, which does not contain a solvent.

3. 3. The composition of claim 1 or 2, wherein the binder is selected from epoxy, acrylic, alkyd, phenolic, silicone, polysiloxane, polyurethane, polyurea, polyaspartic, and hybrids and mixtures thereof.

4. The composition described in claim 3, wherein the binder is epoxy-based.

5. The composition of claim 4, wherein the binder is an epoxy.

6. The composition of any one of claims 1 to 5, wherein the curing agent is an aliphatic or cycloaliphatic amine or polyamine.

7. The composition of any one of claims 1 to 6, wherein the hollow inorganic spherical filler particles comprise glass.

8. The composition of claim 7, wherein the hollow inorganic spherical filler particles are made of glass.

9. The composition of any one of claims 1 to 8, wherein the hollow inorganic spherical filler particles have an average diameter of from 10 to 100 microns.

10. The composition of any one of claims 1 to 9, wherein the hollow organic spherical filler particles have an average diameter of 10 to 120 microns.

11. The composition according to any one of claims 1 to 10, wherein the average diameter of the hollow organic spherical filler particles is greater than the average diameter of the hollow inorganic spherical filler particles.

12. The composition according to any one of claims 1 to 11, wherein the volume ratio of the hollow inorganic spherical filler particles to the hollow organic spherical particles is from 1.1:1.0 to 10.0:1.

0.

13. The composition of claim 1, wherein the thickener is an amide wax thickener.

14. The composition of any one of claims 1 to 13, further comprising an organosilane adhesion promoter.

15. (i) a binder; (ii) optionally a curing agent; (iii) hollow inorganic spherical filler particles; (iv) hollow organic spherical filler particles; and (v) Thickener A method for preparing a composition according to any one of claims 1 to 14, comprising mixing

16. (i) a first container containing a binder, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; (ii) a second container containing a curing agent, optionally hollow inorganic spherical filler particles, and optionally hollow organic spherical filler particles; A kit for preparing a composition according to any one of claims 1 to 14, comprising: a thickening agent is present in the first container and / or the second container; said hollow inorganic spherical filler particles and said hollow organic spherical filler particles are each present in at least one of said containers, and a volume ratio of said inorganic spherical filler particles to said organic spherical filler particles is at least 1.1:

1.

17. 1. A method of providing a coating on a surface, the method comprising: (i) applying a composition according to any one of claims 1 to 14; and (ii) curing the composition to form a coating on the surface. A method comprising:

18. A coating on a surface, said coating being formed from the composition of any one of claims 1 to 14.

19. Use of a composition according to any one of claims 1 to 14 for forming a coating on at least one surface of an article.

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