Peelable coating composition and its use

Abstract

A strippable coating composition that can be applied onto a substrate surface and then dried / cured to obtain a strippable coating. The composition comprises an aqueous vinyl (meth)acrylic copolymer emulsion binder in combination with a silicone polyether copolymer and one or more optional additives. The resulting strippable coating is designed to be water-resistant so as to temporarily protect articles and / or substrates during periods such as construction, storage or transportation, and continue to protect the substrate even after a certain period of time outdoors exposed to elements such as rain.

Description

Technical Field

[0001] The present disclosure relates to a peelable coating composition that dries / cures to obtain a peelable coating. The composition includes an aqueous vinyl (meth)acrylic copolymer emulsion binder in combination with a silicone polyether copolymer. The resulting peelable coating is designed to be water-resistant so that it can temporarily protect articles and / or substrates during periods such as construction, storage, or transportation, and continue to protect the substrate even after a certain period outdoors exposed to elements such as rain.

[0002] In recent years, as described in U.S. Pat. Nos. 8,440,759, 6,822,012, 6,620,890, and Chinese Patent No. 102,850,923, the demand for peelable coatings that can be applied to a wide range of substrates has been increasing. Peelable coatings, sometimes also called release coatings, are designed to adhere well enough to the substrate so that the coating does not spontaneously peel from the protected substrate surface while maintaining durability, and can be easily peeled from the substrate in any other way, if necessary and when needed, without cracking, tearing, or breaking the coating. Thus, a peelable coating is a temporary protective coating that can be removed by peeling it from the substrate surface after use. A peelable coating composition imparts appropriate physical properties to provide a peelable coating having excellent film properties such as light resistance and thermal stability to the substrate to which the peelable coating composition is applied, while also providing chemical and / or physical protection, and it is necessary to enable the coating to be peeled from the substrate in a continuous fairly large sheet after the use period.

[0003] It is designed to be a cost - effective and time - efficient means for protecting a wide range of substrate surfaces such as construction materials like metals, plastics, glass, and concrete during the periods of construction, storage, or transportation. Thus, in the case of construction applications, such a peelable coating can be used to protect glass such as facade glass and window glass during construction, as well as the frames and window sashes of metals, plastics, and / or shutters, and actually concrete articles, etc., and can be easily removed after construction is completed. Similarly, the peelable coating can be used to protect vehicles, machine parts, metal household items as well as other ferrous and non - ferrous articles, wooden articles, glass articles, rubber articles, and coated rubber articles during transportation or storage.

[0004] The peelable coating is used, for example, to protect the substrate surface from weathering caused by sunlight, wind, and rain, as well as scratches, stains, discoloration damage, and / or contamination by sand, dust, iron powder, salt, alkali, acid, soot, insect, and bird excrement, etc.

[0005] Many commercially available peelable coatings require the use of one or more release agents to prevent permanent adhesion of the film to the substrate and to enhance the peelability of the film from the substrate surface to which the film has been applied after the protection period is completed. Historically, release agents have often been based on materials containing fatty acids that tend to contaminate masonry and wood through undesirable reactions with metals, so the industry often prefers to avoid release agents. However, many peelable coatings are known not to function well after being weathered, such as after rain and then drying in sunlight. Such situations of coatings in outdoor situations can result in a significant loss of coating durability, and in some cases, the coating adheres too strongly to the substrate surface and cannot be removed by hand, resulting in the coating cracking or tearing when removed from the substrate.

[0006] This was a situation where a coating prepared from a peelable coating composition having one or more binders or film formers (hereinafter referred to as "binders") containing or consisting of an aqueous emulsion or aqueous dispersion was used.

[0007] As used herein, there is provided a peelable coating composition, which (a) an aqueous vinyl (meth) acrylic copolymer emulsion binder, and (b) a silicone polyether copolymer in an amount of 0.75 to 10 wt% of the peelable coating composition, selected from one or both of the following: (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 (OCH2CH2) n’ (OC3H6) m’ OR 1 [wherein: -R and R 1 may be the same or different and are each selected from H or an alkyl group, (C3H6O) is (CH2(CH3)CHO), (CH2CH2CH2O), ((CH3)CHCH2O) or a mixture thereof, (OC3H6) is (OCH2CH(CH3)), (OCH2CH2CH2), (OCH(CH3)CH2) or a mixture thereof, R 15 and R 16 may be the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n" and n' may be the same or different and are in the range of 3 to about 50], or (ii) (CH3)3SiO - ((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3 [wherein, R' = -R17 -(OCH2CH2) n’ (OC3H6) m’ is OR, wherein R, x, m', n' and (OC3H6) are the same as above, and R 17 is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100], and optionally (c) one or more additives selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, a plasticizer, a pigment and a colorant and / or a mixture thereof.

[0008] Also provided is a substrate coated with a temporary peelable coating which is a cured / dried product of the above peelable coating composition.

[0009] Also, a method of forming a peelable coating on a substrate, (I') an aqueous vinyl (meth) acrylic copolymer emulsion binder (a), together with that is, a silicone polyether copolymer (b) in an amount of 0.75 to 10 wt% of the peelable coating composition, selected from one or both of the following: (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 -(OCH2CH2) n’ (OC3H6) m’ OR 1 [wherein: - R and R 1 may be the same or different and are each selected from H or an alkyl group, (C3H6O) is (CH2(CH3)CHO), (CH2CH2CH2O), ((CH3)CHCH2O) or a mixture thereof, (OC3H6) is (OCH2CH(CH3)), (OCH2CH2CH2), (OCH(CH3)CH2) or a mixture thereof, R 15 and R16 is the same or different and is an alkylene group having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n'' and n' may be the same or different and are in the range of 3 to about 50], or (ii)(CH3)3SiO-((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3 [wherein, R' = -R 17 -(OCH2CH2) n’ (OC3H6) m’ OR, wherein, R, x, m', n' and (OC3H6) are the same as above, and R 17 is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100], and optionally combining with one or more additives (c) selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, a plasticizer, a pigment and a colorant and / or mixtures thereof for forming a peelable coating composition, (II') applying the peelable coating composition to the surface of a substrate, (III') drying the peelable coating composition applied in step (II') to form a peelable coating on the surface of the substrate. A method is also provided. The peelable coating obtained from this method is a temporary coating that protects the surface of the substrate to which the peelable coating composition is applied.

[0010] Also provided is a substrate coated with a peelable coating obtained according to or obtainable by the above process. The substrate coated with the peelable coating is thereby provided with a temporary coating that protects the surface of the substrate to which the peelable coating composition is applied. The peelable coating is removable from the substrate surface by peeling when necessary.

[0011] Also, the use of the silicone polyether copolymer (b) in the peelable coating composition in an amount of 0.75 to 10 wt% of the peelable coating composition, wherein the silicone polyether copolymer (b) is as follows: (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 -(OCH2CH2) n’ (OC3H6) m’ OR 1 [wherein: - R and R 1 may be the same or different and are each selected from H or an alkyl group, (C3H6O) is (CH2(CH3)CHO), (CH2CH2CH2O), ((CH3)CHCH2O) or a mixture thereof, (OC3H6) is (OCH2CH(CH3)), (OCH2CH2CH2), (OCH(CH3)CH2) or a mixture thereof, R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n" and n' may be the same or different and are in the range of 3 to about 50], or (ii) (CH3)3SiO - ((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3 [wherein, R' = -R 17 -(OCH2CH2) n’ (OC3H6) m’ OR, wherein, R, x, m', n' and (OC3H6) are the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100]] selected from one or both of them, and in another aspect, the peelable coating composition (a) an aqueous vinyl (meth)acrylic copolymer emulsion binder, and optionally (c) one or more additives selected from aqueous solvents, film-forming aids, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof, is also provided for use.

[0012] To avoid misunderstanding, the total wt% of all components in the composition is 100 wt%. The term "peelable" is intended to mean that the coating applied on the above substrate is peelable, i.e., removably or temporarily adhered to the substrate. Thus, the peelable coating adheres to the substrate but can be removed from the substrate by peeling the film when necessary or when required. The use of the term "(meth)" in (meth)acrylate used throughout this disclosure is intended to mean acrylate or methacrylate or mixtures thereof.

[0013] The peelable coating is a temporary coating provided to protect the substrate surface. It is designed to be water-resistant and functions as a protective coating on the substrate to which it is applied. It is designed to be removable from the substrate surface by peeling. The use of the term "water-resistant" is intended to mean that the peelable coating described herein can resist water penetration to such an extent that the peelability and adhesiveness of the peelable coating to the substrate are not significantly adversely affected after exposure to water in the form of rain or the like. It is intended to be used as a means of temporary protection for a period of up to one year, but may be used for long-term protection if desired.

[0014] The components of the peelable coating composition are described in more detail below.

[0015] Binder (a) The binder (a) in the above-described peelable coating composition is an aqueous vinyl (meth)acrylic copolymer emulsion.

[0016] aqueous vinyl (meth)acrylic copolymer emulsion The vinyl (meth)acrylic copolymer described in this specification may be a random, block or alternating copolymer or a mixture thereof. Standard vinyl (meth)acrylic copolymers are copolymers of vinyl acetate monomer and at least one (meth)acrylate monomer. Examples of the (meth)acrylate monomer include (meth)acrylic acid, C1-C 20 -alkyl esters of (meth)acrylic acid, or C1-C 10 -alkyl esters of (meth)acrylic acid or C1-C8-alkyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, and neopentyl (meth)acrylate or combinations thereof.

[0017] Vinyl (meth)acrylic copolymers can be prepared using two or more alkyl (meth)acrylates, and other organic monomers such as aryl (meth)acrylate monomers like phenyl (meth)acrylate and tolyl (meth)acrylate, aralkyl (meth)acrylate monomers like benzyl (meth)acrylate and phenethyl (meth)acrylate, cycloalkyl (meth)acrylate monomers like cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylamide; (meth)acrylonitrile; ureido-functional monomers such as hydroxyethyl ethylene urea methacrylate, cyclohexyl (meth)acrylate, methacylcyclohexyl acrylate, isobornyl methacrylate, isobornyl acrylate, and cycloalkyl (meth)acrylates such as dihydrodicyclopentadienyl acrylate, monomers having acetoacetate functional groups such as acetoacetoxyethyl methacrylate (AAEM), monomers having carbonyl-containing groups such as diacetoneacrylamide (DAAM), vinyl aromatic monomers including styrene and substituted styrenes such as α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, or mixtures thereof, α-olefins such as butadiene, ethylene, propylene, and 1-decene, vinyl esters such as vinyl acetate, vinyl butyrate, vinyl versatate and other vinyl esters, glycidyl (meth)acrylate; or combinations thereof may also be incorporated.

[0018] Vinyl (meth)acrylic copolymers may alternatively or additionally incorporate silicon-containing monomers such as vinyltrialkoxysilanes like vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(2-methoxyethoxy)silane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, and (meth)acryloxyalkyltrialkoxysilanes such as (meth)acryloxyethyltrimethoxysilane and (meth)acryloxypropyltrimethoxysilane, or combinations thereof.

[0019] The vinyl (meth)acrylic copolymer of the present specification can be prepared using any suitable combination of the above monomers and vinyl acetate polymers.

[0020] The vinyl (meth)acrylic copolymer can be prepared, for example, by emulsion polymerization that can be initiated / catalyzed by heat, redox (using a redox catalyst), photochemical, and electrochemical initiation. However, the polymerization process usually uses one or more conventional free radical initiators, such as peroxides, for example, hydrogen peroxide, sodium or potassium hydroperoxide, t-alkyl peroxides, t-alkyl hydroperoxides, such as dicumyl hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, etc., t-alkyl peresters where the t-alkyl group contains at least 5 carbon atoms, perboric acid and its salts, such as sodium perborate, etc., perphosphoric acid and its salts, ammonium persulfate and / or alkali, potassium permanganate, and ammonium salts or alkali metal salts of peroxydisulfuric acid to initiate / catalyze. Such initiators can be used in an amount in the range of 0.01 to 3.0 wt% (weight percent) based on the total weight of the monomers.

[0021] Any suitable weight-average molecular weight of the vinyl (meth)acrylic copolymer of the present specification may be in the range of 10,000 to 5,000,000 g / mol, for example, 10,000 to 1,000,000 g / mol, or alternatively 10,000 to 750,000 g / mol. As used herein, unless otherwise indicated, the term "molecular weight" with respect to the vinyl (meth)acrylic copolymer refers to the weight-average molecular weight measured by gel permeation chromatography (GPC) relative to a polystyrene (PS) standard substance. The vinyl (meth)acrylic copolymer may have any suitable glass transition temperature (Tg) in the range of -10 to 100 °C, for example, -10 to 75 °C, or -10 to 50 °C. As used herein, unless otherwise indicated, the terms "Tg" or "glass transition temperature" of the polymer refer to the Tg of the polymer calculated by using the Fox equation with respect to the aqueous vinyl (meth)acrylic copolymer emulsion and its components (T.G. Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956)).

[0022] The vinyl (meth)acrylic copolymer of the present specification can be made from any suitable combination of (meth)acrylate monomer and vinyl acetate monomer. Typically, at least 50 wt% of the monomer, or 60 to 90 wt% of the monomer, is vinyl acetate monomer. The remaining monomer is typically an alkyl (meth)acrylate monomer or a combination of an alkyl (meth)acrylate monomer and (meth)acrylic acid, an aromatic derivative of (meth)acrylic acid, (meth)acrylamide, acrylonitrile, etc. at a wt% ratio of 20:1 to 1:1, or 20:1 to 2.5:1, or 20:1 to 5.0:1.

[0023] Optionally, a mixture of vinyl (meth)acrylic copolymers may be present, and the copolymer (mixture) is an emulsion of a liquid in water and / or small polymer particles in water.

[0024] When vinyl (meth)acrylic copolymer particles are present, they can have an average particle size (diameter) in the range of 75 to 450 nm, or 100 to 375 nm, or 115 to 375 nm, or 150 to 300 nm. As used herein, unless otherwise indicated, the term "average particle size" means the particle size determined by light scattering (LS) using a BI-90 particle size analyzer (Brookhaven Instruments Corp., Holtsville, NY). Such aqueous vinyl (meth)acrylic copolymer emulsions are commercially available under the trade names POLYCO (trademark) emulsion or ROVACE (trademark) emulsion from manufacturers such as Dow Chemical Company.

[0025] The vinyl (meth)acrylic copolymer is present in the peelable coating composition in an amount of 70 wt% to 99.25 wt% of the peelable coating composition.

[0026] Silicone polyether copolymer (b) The silicone polyether copolymer (b) is present in the composition in an amount of 0.75 to 10 wt% of the peelable coating composition. This is selected from one or both of the following: (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 -(OCH2CH2) n’ (OC3H6) m’ OR 1 [wherein: - R and R 1 may be the same or different and are each selected from H or an alkyl group, (C3H6O) is (CH2(CH3)CHO), (CH2CH2CH2O), ((CH3)CHCH2O) or a mixture thereof, (OC3H6) is (OCH2CH(CH3)), (OCH2CH2CH2), (OCH(CH3)CH2) or a mixture thereof, R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n" and n' may be the same or different and are in the range of 3 to about 50], or (ii) (CH3)3SiO - ((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3 [wherein, R' = -R 17 -(OCH2CH2) n’ (OC3H6) m’ OR, wherein, R, x, m', n' and (OC3H6) are the same as above, and R 17 is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100].

[0027] Structurally, the (C3H6O) and (OC3H6) units are (CH2(CH3)CHO) and (OCH(CH3)CH2), (CH2CH2CH2O) and (OCH2CH2CH2), and ((CH3)CHCH2O) and (OCH2CH(CH3)) and are to be understood as being the same in the same way.

[0028] In one embodiment, the (C3H6O) and (OC3H6) units are each (CH2(CH3)CHO) and (OCH(CH3)CH2), respectively, which may alternatively be referred to as propylene oxide (PO) units, and the (CH2CH2O) and (OCH2CH2) units may alternatively be referred to as ethylene oxide (EO) units.

[0029] Option (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si - R 16(OCH2CH2) n’ (OC3H6) m’ OR 1 In the case of R and R 1 may be the same or different and are each selected from H or an alkyl group.

[0030] In the most preferred embodiment of alternative (i), (C3H6O) is (CH2(CH3)CHO) and (OC3H6) is (OCH(CH3)CH2).

[0031] In another embodiment of alternative (i), (C3H6O) is (CH2(CH3)CHO) and (OC3H6) is (OCH2CH(CH3).

[0032] In a further embodiment of alternative (i), (C3H6O) is (CH2CH2CH2O) and (OC3H6) is (OCH2CH2CH2).

[0033] R and R 1 If one or both of them are alkyl groups, the alkyl group may contain 1 to 12 carbons, or 1 to 10 carbons, or 1 to 6 carbons, or be methyl or ethyl. In one embodiment, at least one of R and R 1 is H or a methyl group, or both of R and R 1 are H or a methyl group. In one embodiment, both of R and R 1 are either H or a methyl group.

[0034] R 15 R 16 and R 17 are each an alkylene group having 2 to 6 carbons. The alkylene group may be linear or branched, preferably linear, for example -(CH2) k (wherein k is 2 to 6, or 2 to 5, or 2 to 4), or is a -(CH2)3- group.

[0035] The subscript x is from 2 to 500, or the subscript x is from 3 to 450, or the subscript x is from 4 to 400, or the subscript x is from 5 to 375.

[0036] The subscripts m and m' may be the same or different and are each selected from 0 to about 50, or one or both of the subscripts m and m' are from 0 to 45, or one or both of the subscripts m and m' are from 0 to 40. In one embodiment, both of the subscripts m and m' have the same value from 0 to 40.

[0037] The subscripts n'' and n' may be the same or different and are each selected from 3 to about 50, or each of the subscripts n'' and n' is from 3 to 40, or each of the subscripts n'' and n' is from 4 to 35, or each of the subscripts n'' and n' is from 5 to 30. In one embodiment, the subscripts n'' and n' are the same and are from 5 to 30.

[0038] In one embodiment regarding option (i) of the silicone polyether copolymer (b) (i.e., (b)(i)), both R and R 1 are hydrogen, each of m and m' is from 0 to 40, preferably m and m' are equal, each of the subscripts n'' and n' is from 5 to 30, preferably n'' and n' are equal, and x is from 5 to 375. In such an embodiment, preferably, R 15 and R 16 are the same and are -(CH2)3-.

[0039] When option (ii) is (CH3)3SiO - ((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3, wherein R' = -R 17 -(OCH2CH2) n’ (OC3H6) m’ OR, that is, wherein R' = -R 17 -(OCH2CH2)n’ (OCH(CH3)CH2) m’ is OR, or R’ = -R 17 -(OCH2CH2) n’ (OCH2CH(CH3) m’ is OR, or R’ = -R 17 -(OCH2CH2) n’ (OCH2CH2CH2) m’ is OR.

[0040] Preferably, in the case of option (ii), R’ = -R 17 -(OCH2CH2) n’ (OCH(CH3)CH2) m’ is OR, and wherein R, R 17 , x, m’, and n’ are the same as above, y is from 1 to about 100, or y is from 1 to 75, or y is from 1 to 50, or y is from 1 to 40, or y is from 1 to 30, or y is from 1 to 25. In one embodiment of (b)(ii), m’ is from 0 to 45, y is from 1 to 25, and n’ is from 4 to 35. In each of the above preferred embodiments, R 17 is -(CH2)3-.

[0041] Additive (c) The peelable coating composition may further comprise one or more additives (c). The additives (c) are all optional and can be selected from an aqueous solvent, a film-forming aid, an antifoaming agent (also called a foam inhibitor or a foam suppressant), a rheology modifier, a wetting agent, a plasticizer, a pigment and / or a colorant, and mixtures thereof, or can be selected from an aqueous solvent, a film-forming aid, an antifoaming agent (also called a foam inhibitor or a foam suppressant), a rheology modifier, a wetting agent, and mixtures thereof. In one embodiment, the peelable coating composition comprises at least one additive (c).

[0042] Aqueous solvent As described above, the binder (a), namely the aqueous vinyl (meth)acrylic copolymer emulsion, contains an aqueous liquid continuous phase. Optionally, additional aqueous solvent may be introduced into the strippable coating composition during its preparation, although this is usually not necessary. If introduced, this may again be water only, although it may additionally contain small amounts of other solvents, such as alcohols, such as methanol, ethanol, isopropanol, butanol and / or hexanol. The additional aqueous solvent, if present, is added in an amount of up to 10 wt% of the strippable coating composition, or up to 5.0 wt% of the strippable coating composition.

[0043] Film-forming aid Optionally, the peelable coating composition of the present specification may contain one or more film-forming aids to assist in the formation of a continuous peelable coating on the substrate surface. The "film-forming aid" in the present specification refers to a solvent with a slow evaporation rate that fuses polymer particles into a continuous film under ambient conditions. The presence of the film-forming aid(s) in the present specification helps prevent crack formation on the film surface when the peelable coating is formed on the substrate surface. The film-forming aid may include glycols, ester alcohols, and ethers, such as butoxydiglycol, butyl glycol, glycol ethyl ether, diethylene glycol ethyl ether, alkylene glycol ethers, such as ethylene glycol monomethyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl ether, propylene glycol n-butyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether ethylene glycol monomethyl ether acetate, 2-n-butoxyethanol, n-butyl ether, and any mixture of two or more thereof, and may include a partially hydrophobic organic solvent that is less volatile than water. Preferred film-forming aids include dipropylene glycol n-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, n-butyl ether, or a mixture thereof. The film-forming aid, if present, may be present in an amount of up to 12 wt% of the peelable coating composition, or up to 10 wt% of the peelable coating composition, or up to 7.5 wt% of the peelable coating composition, or up to 5.0 wt% of the peelable coating composition.

[0044] Defoaming agent The strippable coating composition may contain one or more defoaming agents. As used herein, "defoaming agent" refers to a chemical additive that reduces and prevents the formation of foam. The defoaming agent may be an ethylene oxide / propylene oxide-based defoaming agent, silicone polyether (SPE), polyoxyalkylene-substituted silicone, silicone alkanolamide, silicone ester, and silicone glycoside-containing silicone-based defoaming agent, mineral oil-based defoaming agent, alkyl polyacrylate, or a mixture thereof.

[0045] When present, the silicone polyether defoaming agent may have a rake-like structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto the siloxane main chain, or SPE may have an ABA block copolymer structure in which A in the ABA structure represents a polyether moiety and B represents a siloxane moiety. Suitable SPEs include DOWSIL (trademark) OFX-5329 Fluid manufactured by Dow Silicones Corporation (Midland, Michigan, USA). When SPE is used as the defoaming agent in this specification, typically it has a hydrophilic-lipophilic balance (HLB) of about 2 to 3. The defoaming agent may be an emulsion of a polyether siloxane copolymer combined with fumed silica such as TEGO (trademark) Airex 902 W supplied by Evonik. To avoid misunderstanding, the defoaming agent is different from component (b) in this specification.

[0046] When present, the defoaming agent can be incorporated into the composition in an amount of up to 2 wt% of the strippable coating composition, or up to 1.5 wt% of the strippable coating composition, or up to 1.0 wt% of the strippable coating composition, for example, in an amount in the range of 0.1 wt% to 1 wt% of the strippable coating composition.

[0047] Rheology modifier The peelable coating composition may include one or more rheology modifiers, sometimes referred to as thickeners. These may include one or more clay materials, acid derivatives, such as natural polymers having polysaccharide or amino acid building blocks (such as starch, modified starch, proteins, and denatured proteins), dimeric and trimeric fatty acids, and / or imidazolines. Alternatively, they may be polyvinyl alcohol (PVA), acid copolymers, urethane associative thickeners (UAT), polyether urea polyurethanes (PEUPU), polyether polyurethanes (PEPU), alkali swellable emulsions (ASE), such as hydrophobic modified alkali swellable emulsions (HASE) like sodium or ammonium neutralized acrylic acid polymers, hydrophobically modified acrylic acid copolymers, associative thickeners such as hydrophobically modified ethoxylated urethanes (HEUR), and cellulose thickeners such as methyl cellulose ether, hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydrophobically modified hydroxyethyl cellulose (HMHEC), styrene - maleic anhydride terpolymers (SMAT), sodium carboxymethyl cellulose (SCMC), sodium carboxymethyl 2 - hydroxyethyl cellulose, 2 - hydroxypropyl methyl cellulose, 2 - hydroxyethyl methyl cellulose, 2 - hydroxybutyl methyl cellulose, 2 - hydroxyethyl ethyl cellulose, and 2 - hydroxypropyl cellulose.

[0048] The ASE - rheology modifier is similar to the HASE rheology modifier in polymer structure but is a dispersion of an insoluble acrylic polymer in water that does not contain a hydrophobic group, i.e., has a high proportion of acid groups distributed throughout its polymer chain. When the acid groups are neutralized, the salts formed are "hydrated" and the salts swell in the aqueous solution or become completely water - soluble. As the concentration of the neutralized polymer in the aqueous formulation increases, the swollen polymer chains begin to overlap until they "entangle". This overlapping and entanglement increase the viscosity. Here too, the concentration of acid groups, the molecular weight and degree of cross - linking of the polymer are important in determining rheology and thickening efficiency. An example is ACRYSOL(™) ASE - 75 manufactured by Dow.

[0049] HASE polymers are commercially important as associative rheology modifiers of the associative rheology modifier type in waterborne paints and coatings. This is an aqueous dispersion of a water-insoluble acrylic polymer that can be made water-soluble by neutralizing the acid groups on the polymer chain, and also contains long-chain hydrophobic groups and may be called a "hydrophobic substance". Typically, this is an aqueous dispersion of the following copolymer: (i) acrylate or methacrylate monomers, such as methyl methacrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate), (ii) methacrylic acid, acrylic acid, or itaconic acid, and (iii) monomers containing long-chain hydrophobic groups such as ethylenically unsaturated polyethylene oxide (poly EO) macromonomers, such as alkylated ethoxylate monomers, preferably alkylated ethoxylate acrylates or methacrylates.

[0050] The alkylated chain may range from C10 to C25, or from C12 to C20.

[0051] For example, the following HASEs commercially available from The Dow Chemical Company: ACRYSOL™ DR-6600, ACRYSOL™ DR-5500, ACRYSOL™ RM-7, ACRYSOL™ TT-615, ACRYSOL™ DR-72, and ACRYSOL™ TT-935 contain polymerized units of ethyl acrylate and methacrylic acid monomers to which hydrophobic substances are attached. Other commercially available HASEs include ACRYSOL™ Primal HT-400, ACULYN™ 88, ACULYN™ 28, ACULYN™ 88, and Romax™ 7011 from The Dow Chemical Company, and RHEOTECH™ 4800 from Coatex.

[0052] Hydrophobically modified ethoxylated urethane (HEUR) associative rheology modifiers are widely used in aqueous coatings because of their desirable rheological and application properties. Hydrophobically modified alkylene oxide urethane polymers are polyethylene oxide, polypropylene oxide, or polybutylene oxide urethane polymers, preferably polyethylene oxide urethane polymers modified with a suitable hydrophobic substance, and can be prepared, for example, by reacting a diisocyanate, a water-soluble polyalkylene glycol, and a capping agent containing a hydrophobic substance. The isocyanate-terminated prepolymer is then end-capped with, for example, a hydrophobic alcohol or amine to introduce the hydrophobic substance. Commercially available HEURs include ACRYSOL™ RM-8W Rheology Modifier and ACRYSOL™ RM-5000 Rheology Modifier, both of which are available from The Dow Chemical Company.

[0053] Hydroxyethyl cellulose polymer (HEC) is a nonionic water-soluble polymer that can thicken, suspend, bind, emulsify, form films, stabilize, disperse, retain water, and provide a protective colloid effect. It dissolves easily in hot or cold water and can be used to prepare solutions with a wide range of viscosities. An example is Natrosol™ 250 HBR (a water-soluble nonionic hydroxyethyl cellulose surface-treated with glyoxal, manufactured by Ashland Specialty Chemical). Preferably, the rheology modifier(s), if present, is selected from HEC, HUER, or mixtures thereof.

[0054] The rheology modifier(s), when present in the peelable coating composition, may be present in an amount of up to 5 wt% of the peelable coating composition, or up to 4.0 wt% of the peelable coating composition, or in the range of 0.01 - 4 wt% of the peelable coating composition, or in the range of 0.05 wt% - 3 wt% of the peelable coating composition.

[0055] Wetting agent The peelable coating composition described above in this specification may further contain one or more wetting agents. "Wetting agent" as used herein refers to a chemical additive that reduces the surface tension of the coating composition and enables the peelable coating composition to spread more easily over the entire surface of the substrate or penetrate the surface of the substrate. The wetting agent may be a polycarboxylate, anionic, zwitterionic, or nonionic.

[0056] Examples of anionic wetting agents include, but are not limited to, alkali metal alkyl sulfates such as sodium lauryl sulfate, fatty alcohol ether sulfates (FAES), alkylphenol ether sulfates (APES), carboxylic acids, phosphoric acids, and sulfonic acids, and their salt derivatives, alkyl carboxylates, acyl lactylates; alkyl ether carboxylates; n-acyl sarcosinates; n-acyl glutamates; fatty acid-polypeptide condensates; alkali metal sulfosuccinates, sulfonated glycerol esters of fatty acids such as sulfonated monoglyceride of oleic acid; salts of monovalent sulfonated alcohol esters such as sodium oleyl isethionate; amides of aminosulfonic acids such as sodium salt of oleyl methyl tauride; sulfonated products of fatty acid nitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate; condensation products of naphthalene sulfonic acid with formaldehyde; sodium octahydroanthracene sulfonate; ether sulfates having an alkyl group of 8 or more carbon atoms; alkylaryl sulfonates having one or more alkyl groups of 8 or more carbon atoms. Sodium dodecylbenzenesulfonate, dioctyl sulfosuccinate, sodium polyoxyethylene lauryl ether sulfate, diphenyl sulfonate derivatives such as sodium dodecyldiphenyloxide disulfonate, sodium salt of tert-octylphenoxyethoxypoly(39)ethoxyethyl sulfate can be mentioned.

[0057] Examples of commercially available anionic wetting agents useful in this specification include, for example, POLYSTEP(TM) A4, A7, A11, A15, A15-30K, A16, A16-22, A18, A13, A17, B1, B3, B5, B11, B12, B19, B20, B22, B23, B24, B25, B27, B29, C-OP3S, ALPHA-STEP(TM) ML40, MC48, STEPANOL(TM) MG (all manufactured by STEPAN CO., Chicago, IL), HOSTAPUR(TM) SAS manufactured by HOECHST CELANESE, HAMPOSYL(TM) C30 and L30 manufactured by W.R. GRACE & CO., Lexington, MA. Examples of silicone polyether wetting agents include DOWSIL(TM) OFX-5329 Fluid manufactured by Dow Silicones Corporation (Midland, Michigan, USA), or BYK-346 commercially available from Byk-Chemie GmbH.

[0058] Examples of nonionic wetting agents include polyethoxylates such as ethoxylated alkyl polyethylene glycol ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene sorbitan esters, polyoxyalkylene esters, polyoxyalkylene alkyl phenyl ethers, ethoxylated amides, ethoxylated alcohols, ethoxylated esters, polysorbate esters, polyoxypropylene compounds such as propoxylated alcohols, ethoxylated / propoxylated block polymers and propoxylated esters, alkanolamides, amine oxides, fatty acid esters of polyhydric alcohols such as ethylene glycol esters, diethylene glycol esters, propylene glycol esters, glyceryl esters, polyglyceryl fatty acid esters, sorbitan esters, sucrose esters, and glucose esters. Examples of commercially available nonionic wetting agents include, for example, TERGITOL™ TMN-6, TERGITOL™ 15S40, TERGITOL™ 15S9, TERGITOL™ 15S12, TERGITOL™ 15S15, and TERGITOL™ 15S20 manufactured by The Dow Chemical Company (Midland, Michigan), and TRITON™ X405, BRIJ™ 30 and BRIJ™ 35 manufactured by Croda (UK), MAKON™ 10 manufactured by STEPAN COMPANY (Chicago, IL), and ETHOMID™ O / 17 manufactured by Akzo Nobel Surfactants (Chicago, IL).

[0059] The wetting agent may alternatively or additionally contain silicone polyether (SPE). The silicone polyether as a wetting agent may have a rake-like structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane main chain, or the SPE may have an ABA block copolymer structure in which A in the ABA structure represents a polyether moiety and B represents a siloxane moiety. Alternatively, the wetting agent may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. When SPE is used as the wetting agent herein, typically it has a hydrophilic-lipophilic balance (HLB) of about 7 to 9 as determined by the above method.

[0060] To avoid misunderstanding, the SPE utilized as a wetting agent is different from component (b) herein. A commercially available example of the SPE wetting agent is BYK-346 commercially available from Byk-Chemie GmbH.

[0061] When present, the wetting agent may be present in an amount of up to 5 wt% of the removable coating composition, or 0.01 wt% to 4 wt%, or 0.1 wt% to 3 wt% of the removable coating composition, based on the total weight of the removable coating composition.

[0062] Additive (c) may additionally contain a plasticizer and / or a pigment and a colorant.

[0063] Plasticizer Any suitable plasticizer, for example, phthalic acid esters such as di-n-octyl phthalate (DOP), diisononyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP) and diisodecyl phthalate (DIDP), citrate esters such as acetyl tributyl citrate (ATBC), adipic acid esters such as dioctyl adipate (DOA), di-2-ethylhexyl adipate (DEHA), diisononyl adipate (DINA), and di-isononyl-1,2-cyclohexanedicarboxylate, and mixtures thereof may be incorporated.

[0064] Pigments and colorants Examples of pigments include titanium dioxide, chromium oxide, bismuth vanadium oxide, iron oxide, and mixtures thereof.

[0065] Examples of colorants that may be utilized herein include pigments, vat dyes, reactive dyes, acid dyes, chrome dyes, disperse dyes, cationic dyes, and mixtures thereof. The pigments and / or colorants can be colored, white, black, metallic effect, and luminescent, for example, fluorescent and phosphorescent. Pigments are utilized as needed to color the composition. Any suitable pigment may be used as long as it is compatible with the compositions herein. In the binary moisture-curing organopolysiloxane composition, pigments and / or colored (non-white) fillers, such as carbon black, may be used in the catalyst package to color the end-sealant product.

[0066] Suitable white pigments and / or colorants include titanium dioxide, zinc oxide, lead oxide, zinc sulfide, lithopone, zirconium oxide, and antimony oxide.

[0067] Suitable non-white inorganic pigments and / or colorants include goethite, lepidocrocite, hematite, maghemite, and magnetite black iron oxide, yellow iron oxide, brown iron oxide, and red iron oxide such as iron oxide pigments, blue iron pigments; chromium oxide pigments; cadmium pigments such as cadmium yellow, cadmium red, and cadmium vermilion; bismuth pigments such as bismuth vanadate and bismuth molybdate vanadate; mixed metal oxide pigments such as cobalt titanate green; chromate and molybdate pigments such as chromium yellow, molybdate red, and molybdate orange; ultramarine pigments; cobalt oxide pigments; nickel antimony titanate; lead chromate; carbon black, lamp black, and metallic effect pigments such as aluminum, copper, copper oxide, bronze, stainless steel, nickel, zinc, and brass, but are not limited thereto.

[0068] Suitable organic non-white pigments and / or colorants include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, monoarylide yellow, diarylide yellow, benzimidazolone yellow, heterocyclic yellow, DAN orange, quinacridone pigments such as quinacridone magenta and quinacridone violet, metallized azo red and non-metallized azo red and other azo pigments including organic red, monoazo pigments, diazo pigments, azo pigment lakes, β-naphthol pigments, naphthol AS pigments, benzimidazolone pigments, diazo condensation pigments, isoindolinone, and isoindoline pigments, polycyclic pigments, perylene and perinone pigments, thioindigo pigments, anthrapyrimidine pigments, flavanthrone pigments, anthrone pigments, dioxazine pigments, triarylcarbonium pigments, quinophthalone pigments, and diketopyrrolopyrrole pigments.

[0069] Cumulatively, the total amount of additive (c) present in the strippable coating composition may be from 0 (zero) to 19.25 wt% of the strippable coating composition, or from 0 (zero) to 15.0 wt% of the strippable coating composition.

[0070] The total wt% of the strippable coating composition described herein is 100 wt%, and the total wt% of the additional additive (c) present is the difference between 100 wt% and the cumulative wt% of components (a) and (b) of the strippable coating composition.

[0071] Accordingly, provided herein is a strippable coating composition comprising: (a) an aqueous vinyl (meth)acrylic copolymer emulsion binder in an amount of 70 wt% to 99.25 wt% of the strippable coating composition, and (b) a silicone polyether copolymer in an amount of 0.75 to 10 wt% of the strippable coating composition selected from one or both of the following: (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x(CH3)2Si-R 16 (OCH2CH2) n’ (OC3H6) m’ OR 1 [wherein: - R and R 1 may be the same or different, and are each selected from H or an alkyl group, (C3H6O) is (CH2(CH3)CHO), (CH2CH2CH2O), ((CH3)CHCH2O), or a mixture thereof, (OC3H6) is (OCH2CH(CH3)), (OCH2CH2CH2), (OCH(CH3)CH2), or a mixture thereof, R 15 and R 16 may be the same or different, are alkylene groups having 2 to 6 carbons, preferably -(CH2)3-, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n" and n' may be the same or different and are in the range of 3 to about 50], or (ii)(CH3)3SiO-((CH3)2SiO) x -(CH3R’SiO) y -Si(CH3)3 [wherein, R’ = -R 17 -(OCH2CH2) n’ (OC3H6) m’ OR, and wherein, R, x, m’, n’ and (OC3H6) are the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100. Preferably, in the case of option (ii), R’ = -(CH2)3(OCH2CH2) n’ (OCH(CH3)CH2) m’ OR], and optionally, One or more additives (c) selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a wetting agent, a rheology modifier, a plasticizer, a pigment and / or a colorant, and / or a mixture thereof, or one or more additives (c) selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a wetting agent, a rheology modifier, and / or a mixture thereof in an amount of 0 (zero) to 19.25 wt% of the peelable coating composition.

[0072] The peelable coating formed after application of the peelable coating composition is provided to temporarily protect the substrate surface for a predetermined period and can then be removed by peeling it from the substrate surface.

[0073] A method of forming a peelable coating on a substrate is (I’) an aqueous vinyl (meth)acrylic copolymer emulsion binder (a) together with That is, a silicone polyether copolymer (b) in an amount of 0.75 to 10 wt% of the peelable coating composition selected from one or both of the following: (i) RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 -(OCH2CH2) n’ (OC3H6) m’ OR 1 [wherein: - R and R 1 may be the same or different and are each selected from H or an alkyl group, (C3H6O) is (CH2(CH3)CHO), (CH2CH2CH2O), ((CH3)CHCH2O) or a mixture thereof, (OC3H6) is (OCH2CH(CH3)), (OCH2CH2CH2), (OCH(CH3)CH2) or a mixture thereof, R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range from 0 to about 50, n" and n' may be the same or different and are in the range from 3 to about 50, or (ii) (CH3)3SiO-((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3 [wherein, R' = -R 17 -(OCH2CH2) n’ (OC3H6) m’ OR, wherein, R, x, m', n' and (OC3H6) are the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100. Preferably, in the case of option (ii), R' = -R 17 -(OCH2CH2) n’ (OCH(CH3)CH2) m’ OR, and in the formula, R 17 is preferably -(CH2)3- and optionally, combining with one or more additives (c) selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, a plasticizer, a pigment or a colorant, and / or a mixture thereof for forming a strippable coating composition, (II') applying the strippable coating composition to a substrate surface, (III') drying the strippable coating composition applied in step (II') to form a strippable coating on the substrate, and the method includes these steps.

[0074] The peelable coating composition can be prepared in any suitable manner in step (I) above. For example, component (a) may be introduced into a suitable mixer, and then optional additives may be introduced into the mixture and stirred. Following the addition of any optional additives, an amount of silicone polyether copolymer (b) as desired may be added, and then thoroughly mixed with other component(s) to ensure that the silicone polyether copolymer (b) is evenly dispersed throughout the peelable coating composition. In one embodiment, component (a) is stirred in a mixer until all optional additives are added, then the silicone polyether copolymer (b) is added and mixed for up to 10 minutes at 700 rpm. Any type of mixing device may be used, such as a Terrell (trademark), Neulander (trademark) or Ross (trademark) mixer, or a FlackTek SpeedMixer (trademark) manufactured by FlackTek of Landrum, South Carolina, USA.

[0075] Once prepared, in step (II’) of the process, the peelable coating composition is applied onto the substrate surface by any suitable method, which may, for example, be spray coating, brushing, roll coating, dipping, or other methods of coating the substrate, although spray techniques are preferred. Typically, the peelable coating composition is applied as a single layer, although, if desired, the coating with the peelable coating composition can be applied in multiple layers. Typically, the target wet coating thickness of the peelable coating composition on the substrate is a wet coating thickness of 100 μm to 750 μm, or a wet coating thickness of 200 to 700 μm, or a wet coating thickness of 250 μm to 600 μm. The wet thickness was determined using a coating bar.

[0076] Next, in step (III’) of the present process, the peelable coating composition is left to dry / harden to obtain a peelable coating on the substrate surface. The resulting peelable coating is visually transparent (see-through). This can generally be completed at room temperature and standard conditions, for example, under atmospheric pressure with a relative humidity of 50%. Step (III’) can be carried out over any period between 2 to 12 hours, or between 2 to 6 hours.

[0077] Examples of substrates on which the peelable coating composition is intended to be applied include materials used in construction or used to protect the substrate surface during transportation, storage, or construction. The peelable coating formed after application of the peelable coating composition serves as a temporary means to protect the material before use and / or, for example, to protect the surface after use until the substrate is ready for use, for example, after completion of building construction or after transportation is completed.

[0078] It has been demonstrated that the peelable coating obtained from the peelable coating composition is a temporary protective coating that can be removed by peeling from the substrate on which it is applied without the presence of an intervening layer. The peelable coating, which is temporarily applied to the substrate surface and removable by peeling, is removed by hand from the substrate surface as a complete film having a suitable tensile strength that causes no or minimal breakage or tearing during the peeling operation, even after simulated weathering.

[0079] Subsequent to the application of the peelable coating on the substrate, the method additionally includes a step of removing the peelable coating by peeling the peelable coating from the substrate surface to which the peelable coating has been applied.

[0080] Accordingly, alternatively, a method of temporarily protecting a substrate can be provided by preparing the peelable coating composition described above in the present specification and applying it onto the substrate surface, forming a peelable coating on the substrate, transporting, storing and / or using the substrate during construction, and then peeling and removing the peelable coating from the substrate surface. In such a process, the peelable coating is a temporary removable coating that is removed by peeling the coating from the substrate surface as desired and when desired.

[0081] Although not quantitatively tested, the fact that the peelable coatings can be removably adhered to the substrate means that they also maintain a peel strength low enough to allow the act of peeling to be performed manually by hand. For the peelable coating to be peeled off by hand, the peel strength of the coating with respect to the surface should be at most about 400 N / m, preferably about 200 N / m or less, and preferably less than about 100 N / m so that the act of peeling the coating can be performed manually by hand. Surprisingly, when silicone polyether copolymers other than component (b) herein were used, much worse results were observed, and in many cases, the resulting coatings could not be peeled off by hand or were found to have cracks or tears, especially after simulated weathering. These results were determined by the naked eye.

[0082] Therefore, the peelable coating obtained by applying the peelable coating composition described herein is considered to be weather-resistant and / or rain-resistant and / or waterproof, enabling it to be used in both outdoor and indoor situations. In the case of an outdoor situation where the peelable coating composition is applied on outdoor glass, the peelable coating obtained herein has good water resistance and is not damaged or washed away even after being exposed to rain, or even after being exposed to rain for a long period of time. Then, the peelable coating can dry, but even when directly exposed to the sun, it remains peelable and is not damaged, so it can protect the glass substrate facing the outdoors. In fact, even after severe tests, rain / water does not affect the peelable performance of the peelable coating, so it seems to be water-resistant.

[0083] The peelable coating herein is provided as a protective coating derived from a visually transparent (see-through) peelable coating composition that can be applied to a wide range of substrates such as metal, plastic, glass, cloth, ceramic, clay, fiber, concrete, brick, rock, or wood. The substrate surface can also include painted walls and painted metals.

[0084] For example, the peelable coating composition described herein can be utilized to form a peelable coating for protecting the paint, glass, plastic, or metal parts of vehicles such as automobiles, airplanes, boats, snowmobiles, or motorcycles during storage and transportation. Other uses include temporary protective coatings for bathroom fixtures, plumbing fixtures, kitchen appliances such as refrigerators, microwave ovens, plated or chrome-plated parts, instrument panels, etc. The peelable coating can be peeled off from the substrate together with all the dirt and contaminants that have affected the peelable coating during the presence of the substrate surface, as needed and when necessary.

[0085] This is designed to provide a water-resistant protective coating, especially on indoor and outdoor glass, that can be manually removed as a single film without cracking and / or tearing, to a glass substrate during transportation or construction, for example. The glass substrate coated with the peelable coating composition can be substantially any glass substrate, such as, for example, borosilicate glass, soda-lime glass, silica glass, alkali barium glass, aluminosilicate glass, lead glass, phosphate glass, alkali borosilicate glass, xena glass, fluorosilicate glass, or a pretreated glass, such as, for example, a vacuum-deposited reflective metal-coated plate glass (which can be used, for example, for commercial building and architectural spandrel applications). This can also protect glass substrates used in or for a wide variety of indoor and outdoor applications, such as, for example, architectural glass, such as optical glass, architectural glass, facade glass, glass for shadow boxes, decorative glass, high-performance glass, structural glass, etc., float glass, anti-spatter glass, laminated glass, extra-clear glass, colored glass, tinted glass, tempered glass, glass bricks, ground glass and / or bulletproof glass, elevator glass, windows, etc., and furthermore, ancillary equipment for buildings, such as in bathrooms and kitchen facilities, for example, chrome-plated surfaces or brass surfaces, must be protected not only during shipping but also during installation or assembly to avoid scratching and damage before or during construction.

Example

[0086] For the purpose of comparing the peelability after application on a suitable substrate, a plurality of coating compositions were prepared. For the purpose of determining the feasibility of the coating as a peelable coating for temporarily protecting the substrate surface exposed to elements during construction, storage and / or transportation, etc., evaluations were carried out to compare their peelability before and after spraying with water (simulating rain). Several combinations of binders and silicone polyethers were used as the basis of the coating composition. Six formulations (forms n ) were used with the binders and silicone polyethers varied as shown below. Formulations (formsn )I to VI are shown in Table 1a.

[0087] [Table 1]

[0088] In Table 1a: The film-forming aid used in the examples was Texanol (trademark) Ester Alcohol commercially available from Eastman Chemical Company.

[0089] The defoaming agent used was TEGO (trademark) Airex 902 W commercially available from Evonik Operations GmbH.

[0090] The wetting agent used was BYK-346 commercially available from Byk-Chemie GmbH. Rheology modifier 1 (RM1) was ACRYSOL (trademark) RM-8W Rheology Modifier commercially available from The Dow Chemical Company.

[0091] Rheology modifier 2 (RM2) was ACRYSOL (trademark) RM-5000 Rheology Modifier commercially available from The Dow Chemical Company.

[0092] The following binders were evaluated. Binder 1 was an aqueous vinyl acrylic copolymer emulsion commercially available as ROVACE (trademark) 662 Emulsion from The Dow Chemical Company according to the disclosure of this specification. Binder 2 was a comparative binder commercially available as ELASTENE (trademark) 3776 Acrylic Emulsion from The Dow Chemical Company, a 100% acrylic polymer emulsion. Binder 3 is a styrene acrylic copolymer emulsion, a comparative binder commercially available as PRIMAL (trademark) SF-155 Emulsion. And Thirteen different silicone polyethers (SPEs) were evaluated when combined with the binder. Some match structure b(i), some match structure b(ii) (both as described above), while others are provided as comparative examples. The structure of each SPE is shown in Table 1b below, where the Rs shown 2 ~R 13 In which, (EO) is an ethylene oxide unit (OCH2CH2), (PO) is a propylene oxide unit (OCH(CH3)CH2), Ac is an acetate group, and Me is a methyl group.

[0093]

Table 2

[0094] To avoid misunderstanding, the SPEs shown as comparative examples are outside the scope of this disclosure and are evaluated for comparison purposes.

[0095] All components other than the SPE were introduced into the binder and various compositions were prepared by stirring in a FlackTek SpeedMixer (trademark) manufactured by FlackTek (Landrum, South Carolina, USA) at 700 rpm for several minutes. Subsequently, the selected SPE was added and mixing was continued at 700 rpm for an additional 10 minutes to ensure uniform dispersion of the SPE in the composition.

[0096] Next, each of the resulting compositions was applied (unless otherwise indicated) onto glass, ceramic, or polyvinylidene fluoride (PVDF) panels. The wet coating thickness of each applied liquid coating was measured using a coating bar and was approximately 400 μm on average.

[0097] Then, the applied liquid coatings were dried / cured at room temperature (RT) and 50% relative humidity for approximately 4 hours.

[0098] After drying / hardening, the peelability of each coating on the substrate to which it was applied was evaluated in three ways:

[0099] 1) At room temperature The peelability was tested immediately after completion of the 4-hour drying / hardening process.

[0100] 2) At a temperature of 5 °C The coated samples were subjected to drying / hardening at a temperature of 5 °C to mimic winter temperatures, and then the peelability was evaluated.

[0101] 3) After water spraying After hardening / drying, the coated substrate was placed in a suitable laboratory fog chamber and sprayed with water for 7 hours to mimic rainy weather. The coated substrate was then dried in an oven at 50 °C, and then the peelability of the removable coating was evaluated. This is a regime (pattern of natural events) that is more severe than any natural weather, and it is also considered that the removable coating may be exposed to natural weather even in tropical climates such as the Southeast Asian region.

[0102] The peelability of the removable coating of the sample was graded from 1 (worst) to 5 (best) according to the following definition by visually inspecting the removable coating for defects such as shrinkage and color change after water spraying and comparing it with a standard panel. Grade 5: The entire removable coating is easily peeled off, there is no residue of the removable coating on the substrate, no cracks or fissures occur during peeling, and there is no damage to the substrate. Grade 4: It peeled off almost completely, but some force was required. A minimal (less than 5%) residue remained on the substrate. The removable coating may have slight cracks or fissures. Grade 3: More force was required to peel the removable coating from the substrate. The removable coating was torn more easily than (grades 4 or 5 above), and more than 30% of the remaining removable coating may remain on the substrate. Level 2: It can be peeled off, but the peelable coating is easily torn. There may be cases where more than 50% of the peelable coating remains on the substrate, and the substrate may be damaged. Level 1: Peeling is difficult, the adhesion is too strong, and solvents or tools are required for removal.

[0103] Table 2 describes the display of the target grades for each test conducted. To avoid misunderstandings, the symbol ≧ means equal to or greater than.

[0104] [Table 3]

[0105] [Table 4]

[0106] [Table 5]

[0107] As can be seen in Table 3b, it has been found that compositions using Binder 1 in combination with at least 0.75 wt% of the SPE as defined herein have provided excellent peelability after water spraying. The above results indicate that the peelable coating does not tear during peeling after being subjected to the water spray test, and that the peelable coating maintains both hand peelability and durability even after the water spray test and drying. Furthermore, this peelability additionally indicates that the peelable coating retains sufficient adhesion ability after exposure to water spray simulating rain.

[0108] Using the same test methods and evaluation means, several comparative examples were also conducted. The results are shown in Tables 4a and 4b.

[0109] [Table 6]

[0110]

Table 7

[0111] The results shown in Table 4a and Table 4b were obtained using compositions outside the scope of the present disclosure. It can be seen that they resulted in significantly inferior peelability results based on the grading scheme specified above. All of C.1 to 9 included SPE outside the required formulation, and C10 and C11 contained no SPE at all. Many of such coatings, especially on PVDF, are no longer durable for the required applications, and cracks and / or tears occur when attempting to peel them by hand, especially after drying following an extreme water spray test. This led to the conclusion that such peelable coatings do not meet the purposes shown by the results of Table 4a and especially 4b.

Claims

1. (a) An aqueous vinyl (meth)acrylic copolymer emulsion binder, and (b) A silicone polyether copolymer in an amount of 0.75 to 10 wt% of the peelable coating composition selected from one or both of the following: (i) RO(C ３ H ６ O) ｍ (CH ２ CH ２ O) ｎ” R １５ -( (CH ３ ) ２ (SiO) ｘ (CH ３ ) ２ Si-R １６ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ OR １ [wherein: - R and R １ may be the same or different and are each selected from H or an alkyl group, (C ３ H ６ O) is (CH ２ (CH ３ )CHO), (CH ２ CH ２ CH ２ O), ((CH ３ )CHCH ２ O) or a mixture thereof, (OC ３ H ６ ) is (OCH ２ CH(CH ３ )), (OCH ２ CH ２ CH ２ ), (OCH(CH ３ )CH ２ ) or a mixture thereof, R １５ and R １６ are the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n" and n' may be the same or different and are in the range of 3 to about 50], or (ii) (CH ３ ) ３ SiO - ((CH ３ ) ２ SiO) ｘ - (CH ３ R'SiO) ｙ - Si(CH ３ ) ３ [wherein, R' = -R １７ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ is OR, wherein R, x, m', n' and (OC ３ H ６ ) are the same as above, R １７ is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100], And optionally, One or more additives (c) selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, a plasticizer, a pigment and a colorant and / or a mixture thereof A peelable coating composition comprising.

2. The silicone polyether copolymer (b)(i) has the following formula RO(C ３ H ６ O) ｍ (CH ２ CH ２ O) ｎ” R １５ -( (CH ３ ) ２ (SiO) ｘ (CH ３ ) ２ Si-R １６ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ OR １ [wherein, R and R １ are hydrogen, m and m' are the same or different and are 0 to 40, n" and n' are 5 to 30, and x is 5 to 375], the peelable coating composition according to claim 1.

3. The silicone polyether copolymer (b)(i) has the following formula RO(CH ２ (CH ３ )CHO) ｍ (CH ２ CH ２ ) ｎ” R １５ -( ((CH ３ ) ２ )SiO) ｘ (CH ３ ) ２ Si-R １６ (OCH ２ CH ２ ) ｎ’ (OCH(CH ３ )CH ２ ) ｍ’ OR １ [wherein, R and R １ are hydrogen, m and m' are the same or different and are from 0 to 40, n" and n' are the same or different and are from 5 to 30, and x is from 5 to 375], the peelable coating composition according to claim 1 or 2.

4. The silicone polyether copolymer (b)(ii) has the formula (CH ３ ), ３ SiO-( (CH ３ ), ２ SiO) ｘ -(CH ３ R'SiO) ｙ -Si(CH ３ ), ３ [wherein, R' = -R １７ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ is OR, The peelable coating composition according to claim 1 or 2, wherein m' is from 0 to 45, y is from 1 to 25, and n' is from 4 to 35].

5. Silicone polyether copolymer (b)(ii) is of the formula (CH ３ ), ３ SiO - ((CH ３ ), ２ SiO) ｘ - (CH ３ R'SiO) ｙ - Si(CH ３ ), ３ [wherein, R' = -R １７ -(OCH ２ CH ２ ) ｎ’ (OCH(CH ３ )CH ２ ) ｍ’ OR, and The peelable coating composition according to claim 4, wherein m' is from 0 to 45, y is from 1 to 25, and n' is from 4 to 35].

6. The peelable coating composition according to claim 1, 2, 3, 4 or 5, wherein component (a) is present in an amount of 70 wt% to 99.25 wt% of the peelable coating composition, and the additives of component (c), when present, are cumulatively present in an amount of at most 19.25 wt% of the peelable coating composition.

7. The peelable coating composition according to claim 1, 2, 3, 4, 5 or 6, wherein at least one additive (c) is present in the composition.

8. R １５ 、 R １６ and R １７ are -CH ２ ), ３ and / or the additive (c) is selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, and / or a mixture thereof. The peelable coating composition according to any one of claims 1 to 7.

9. A substrate coated with a peelable coating which is a cured product of the peelable coating composition according to any one of claims 1 to 8.

10. A method of forming a peelable coating on a substrate, comprising (I') (a) An aqueous vinyl (meth)acrylic copolymer emulsion binder and a silicone polyether copolymer (b) in an amount of 0.75 to 10 wt% of the peelable coating composition selected from one or both of the following: (i) RO(C ３ H ６ O) ｍ (CH ２ CH ２ O) ｎ” R １５ - ((CH ３ ) ２ SiO) ｘ (CH ３ ) ２ Si - R １６ - (OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ OR １ [wherein: - R and R １ may be the same or different and are each selected from H or an alkyl group, (C ３ H ６ O) is (CH ２ (CH ３ )CHO), (CH ２ CH ２ CH ２ O), ((CH ３ )CHCH ２ O) or a mixture thereof, (OC ３ H ６ ) is (OCH ２ CH(CH ３ )), (OCH ２ CH ２ CH ２ ), (OCH(CH ３ )CH ２ ) or a mixture thereof, R １５ and R １６ are the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, and n" and n' may be the same or different and are in the range of 3 to about 50], or (ii) (CH ３ ) ３ SiO - ((CH ３ ) ２ SiO) ｘ - (CH ３ R'SiO) ｙ - Si(CH ３ ) ３ [wherein, R' = -R １７ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ is OR, In the formula, R, x, m', n' and (OC ３ H ６ ) are the same as above, R １７ is an alkylene group having 2 to 6 carbons, y is from 1 to about 100], and optionally A step of combining with one or more additives (c) selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, a plasticizer, a pigment and a colorant and / or a mixture thereof for forming the peelable coating composition; (II') A step of applying the peelable coating composition onto a substrate surface; (III') A step of drying the peelable coating composition applied in step (II') to form a peelable coating on the substrate surface. A method comprising:

11. R １５ 、R １６ and R １７ are —CH ２ ), ３ and / or additive (c) is selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, and / or a mixture thereof, The method of forming a peelable coating on a substrate according to claim 10.

12. The method for forming a peelable coating on a substrate according to claim 10 or 11, wherein the wet coating thickness of the peelable coating composition after being applied onto the substrate is 100 μm to 750 μm as measured using a coating bar.

13. The method for forming a peelable coating on a substrate according to claim 11 or 12, wherein the substrate is metal, plastic, glass, cloth, ceramic, clay, fiber, concrete, brick, rock or wood, or a painted wall and a painted metal.

14. The method for forming a peelable coating on a substrate according to claim 11, 12, or 13, further comprising a step of removing the peelable coating by peeling the peelable coating from the substrate surface to which the peelable coating has been applied.

15. A substrate coated with a peelable coating obtained or obtainable by using the method according to claim 11, 12 or 13.

16. Use of the silicone polyether copolymer (b) in the peelable coating composition in an amount of 0.75 to 10 wt% of the peelable coating composition, wherein the silicone polyether copolymer (b) is as follows: (i) RO(C ３ H ６ O) ｍ (CH ２ CH ２ O) ｎ” R １５ -( (CH ３ ) ２ (SiO) ｘ (CH ３ ) ２ Si-R １６ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ OR １ [wherein: - R and R １ may be the same or different and are each selected from H or an alkyl group, (C ３ H ６ O) is (CH ２ (CH ３ )CHO), (CH ２ CH ２ CH ２ O), ((CH ３ )CHCH ２ O) or a mixture thereof, (OC ３ H ６ ) is (OCH ２ CH(CH ３ )), (OCH ２ CH ２ CH ２ ), (OCH(CH ３ )CH ２ ) or a mixture thereof, R １５ and R １６ are the same or different and are alkylene groups having 2 to 6 carbons, x is from 2 to about 500, m and m' may be the same or different and are each in the range of 0 to about 50, n'' and n' may be the same or different and are in the range of 3 to about 50], or (ii) (CH ３ ) ３ SiO - ((CH ３ ) ２ SiO) ｘ - (CH ３ R'SiO) ｙ - Si(CH ３ ) ３ [wherein, R' = -R １７ -(OCH ２ CH ２ ) ｎ’ (OC ３ H ６ ) ｍ’ is OR, wherein R, x, m', n' and (OC ３ H ６ ) are the same as above, R １７ is an alkylene group having 2 to 6 carbons, and y is from 1 to about 100] selected from one or both of the above, and in other respects, the peelable coating composition comprises (a) an aqueous vinyl (meth)acrylic copolymer emulsion binder, and optionally (c) one or more additives selected from an aqueous solvent, a film-forming aid, an antifoaming agent, a rheology modifier, a wetting agent, a plasticizer, a pigment and a colorant and / or a mixture thereof, including.

17. Use of the peelable coating composition according to any one of claims 1 to 8 in the preparation of a peelable coating on a substrate, wherein the substrate is selected from metal, plastic, glass, cloth, ceramic, clay, fiber, concrete, brick, rock or wood, or a painted wall and painted metal.

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