Peelable coating composition and use thereof

Abstract

A peelable coating composition that can be applied to a surface of a substrate and can then be dried / cured into a peelable coating. The composition comprises a combination of an aqueous copolymer emulsion binder based on vinyl (meth) acrylic acid and a silicone polyether copolymer and one or more optional additives. The resulting peelable coating provides temporary protection to the article and / or substrate during construction, storage or transportation, and is designed to be waterproof such that the peelable coating continues to protect the substrate after exposure to a natural environment, such as rainwater, outdoors for a period of time.

Description

[0001] The present disclosure relates to a strippable coating composition that dries / cures to form a strippable coating. The composition comprises a combination of a vinyl (meth)acrylic acid-based aqueous copolymer emulsion binder and a silicone polyether copolymer. The resulting strippable coating provides temporary protection for articles and / or substrates during construction, storage, or transportation, etc., and is designed to be waterproof so that the strippable coating can continue to protect the substrate after being exposed to the elements outdoors for a period of time, such as rain.

[0002] In recent years, as described in US8440759, US6822012, US6620890 and CN102850923, the demand of the strippable coating that can be applied to the substrate on a wide range is increasing day by day.Strippable coating (sometimes alternatively being called strippable coating) is designed to fully and well adhere to the substrate, so that when coating can not spontaneously peel off from the protected substrate surface, this coating keeps durable and can easily peel off from substrate when needed and can not make coating crack, tear or rupture in any other way.Therefore, these strippable coatings are temporary protective coatings that can be removed by peeling off from the substrate surface after use.The strippable coating composition needs to provide the substrate that it is applied to, and this substrate has suitable physical property to provide the strippable coating with excellent film characteristic (such as light resistance and thermal stability), also provides chemical and / or physical protection simultaneously and makes coating can be peeled off from substrate with continuous and quite large sheet material after using for a period of time.

[0003] They are designed to be a cost-effective and time-efficient means of protecting a wide range of substrate surfaces such as metals, plastics, glass and construction materials such as concrete during construction, storage or transportation. Thus, in the case of construction applications, such strippable coatings can be used to protect glass, such as facade glass and window glass, as well as metal, plastic and / or wooden door and window frames, and even concrete products, etc., during construction, while being easily removed after the construction is completed. Similarly, strippable coatings can be used to protect vehicles, machine parts, metal household products and other ferrous and non-ferrous products, wooden products, glass products, rubber products and coated rubber products during transportation or storage.

[0004] For example, these strippable coatings are used to protect substrate surfaces from damage and / or contamination caused by weathering caused by sun, wind and rain, as well as scratches, stains and discoloration caused by sand, dust, iron powder, salt, alkali, acid, soot and smoke, insect and bird excrement, and the like.

[0005] Many commercially available strippable coatings require the use of one or more release agents to prevent the film from permanently adhering to the substrate and to enhance the strippability of the film from the substrate surface to which it is applied after the protection period has expired. It is generally preferred in the industry to avoid release agents because historically these release agents have often been based on materials containing fatty acids, which are prone to undesirable reactions with metals and stained masonry and wood. It is said that many strippable coatings are known not to function well after being subjected to the effects of weathering, such as after being rained on and then dried in the sun. Such conditions of the coating in exterior situations can result in a severe loss of durability of the coating, with cracking and tearing of the coating when removed from the substrate, which can be a result of the coating adhering too firmly to the substrate surface to allow the coating to be removed by hand.

[0006] This is the case for coatings prepared from strippable coating compositions having one or more binders or film formers (hereinafter referred to as "binders") which comprise or consist of aqueous emulsions or dispersions.

[0007] The present invention provides a peelable coating composition, which comprises

[0008] (a) an aqueous copolymer emulsion binder based on vinyl (meth) acrylic acid;

[0009] (b) a silicone polyether copolymer, wherein the amount of the silicone polyether copolymer is 0.75 wt.% to 10 wt.% of the strippable coating composition, and the silicone polyether copolymer is selected from one or both of the following:

[0010] (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 ,in:-

[0011] R and R 1 can be the same or different and are each selected from H or an alkyl group,

[0012] (C3 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;

[0013] (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;

[0014] R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons,

[0015] x is 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50;

[0016] or

[0017] (ii)(CH 3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3 ;

[0018] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR;

[0019] Where R, x, m', n' and (OC 3 H 6 ) is the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is 1 to about 100; and optionally

[0020] (c) one or more additives selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof.

[0021] Also provided is a substrate coated with a temporary peelable coating, which is a cured / dried product of the peelable coating composition described above.

[0022] A method for forming a strippable coating on a substrate is also provided, the method comprising the steps of:

[0023] (I') combining the following to form a peelable coating composition: a vinyl (meth)acrylic acid-based aqueous copolymer emulsion binder (a); and

[0024] Silicone polyether copolymer (b), the amount of the silicone polyether copolymer is 0.75wt.% to 10wt.% of the strippable coating composition, and the silicone polyether copolymer is selected from one or both of the following:

[0025] (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 , where: -R and R 1 can be the same or different and are each selected from H or an alkyl group,

[0026] (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;

[0027] (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;

[0028] R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons, x is 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50;

[0029] or (ii) (CH 3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3 ;

[0030] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR;

[0031] Where R, x, m', n' and (OC 3 H 6 ) is the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is 1 to about 100; and optionally

[0032] one or more additives (c) selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof,

[0033] (II') applying the strippable coating composition onto a substrate surface;

[0034] (III') drying the peelable coating composition applied in step (II') to form a

[0035] The strippable coating produced by this method is a temporary coating that protects the surface of the substrate to which the strippable coating composition has been applied.

[0036] A substrate coated with a strippable coating obtained or obtainable according to the above method is also provided. The substrate coated with the strippable coating is thus provided with a temporary coating, which protects the substrate surface to which the strippable coating composition has been applied. When necessary, the strippable coating can be removed from the substrate surface by stripping.

[0037] Also provided is the use of a silicone polyether copolymer (b) in a peelable coating composition, wherein the amount of the silicone polyether copolymer is 0.75 wt.% to 10 wt.% of the peelable coating composition, and the silicone polyether copolymer (b) is selected from one or both of the following:

[0038] (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 ,in:-

[0039] R and R 1 can be the same or different and are each selected from H or an alkyl group,

[0040] (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;

[0041] (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;

[0042] R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons, x is 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50;

[0043] or (ii) (CH 3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3 ;

[0044] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR;

[0045] Where R, x, m', n' and (OC 3 H 6) Same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is 1 to about 100; the strippable coating composition further comprises

[0046] (a) an aqueous copolymer emulsion binder based on vinyl (meth) acrylic acid; and optionally

[0047] (c) one or more additives selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof.

[0048] For the avoidance of doubt, the total wt.% of all ingredients in the composition is 100 wt.%. The term "strippable" is intended to mean that the coating applied to the substrate as described above is strippable, i.e., removably or temporarily adhered to the substrate. Thus, the strippable coating adheres to the substrate but can be removed from the substrate as needed or when desired by peeling the film from the substrate surface. The term "(meth)" in (meth)acrylate used throughout the disclosure is intended to mean acrylate or methacrylate or a mixture thereof.

[0049] Strippable coating is a temporary coating provided for protecting the substrate surface. This strippable coating is designed to be waterproof, and plays the role of protective coating on the substrate to which it is applied. This strippable coating is designed to be removed from the substrate surface by peeling off from the substrate surface. The use of the term "waterproof" is intended to mean that the strippable coating as described herein can resist water penetration to such an extent that after being exposed to water in the form of rainwater, the strippable coating will not be significantly negatively affected to the strippability and adhesion of the substrate. This strippable coating is intended to be used as a temporary protection means for a period of one year, but can also be used for long-term protection if desired.

[0050] The components of the strippable coating composition are described in more detail below.

[0051] Binder (a)

[0052] The binder (a) in the above peelable coating composition is an aqueous copolymer emulsion based on vinyl (meth) acrylic acid.

[0053] Aqueous copolymer emulsion based on vinyl (meth) acrylic acid

[0054] The vinyl (meth)acrylic acid based copolymers as described herein may be random, block or alternating copolymers or mixtures thereof. Standard vinyl (meth)acrylic acid copolymers are copolymers of vinyl acetate monomers and at least one (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomers may include (meth)acrylic acid, C 1 -C 20 Alkyl esters, alternatively C (meth)acrylic acid 1 -C 10 Alkyl ester or (meth) acrylic acid C 1 -C 8 Alkyl esters 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.

[0055] Copolymers based on vinyl (meth)acrylic acid can be prepared using more than one alkyl (meth)acrylate and can incorporate other organic monomers, such as aryl (meth)acrylate monomers, such as phenyl (meth)acrylate and tolyl (meth)acrylate; aryl (meth)acrylate monomers such as benzyl (meth)acrylate and phenylethyl (meth)acrylate; cycloalkyl (meth)acrylate monomers such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate; (meth)acrylamide; (meth)acrylonitrile; urea-functional monomers such as hydroxyethylethylene urea methacrylate; cycloalkyl (meth)acrylates such as (meth)acrylic acid; cyclohexyl acrylate, methylcyclohexyl acrylate, isobornyl methacrylate, isobornyl acrylate and dihydrodicyclopentadienyl acrylate; monomers with acetoacetate functional groups, such as acetoacetoxyethyl methacrylate (AAEM); monomers with carbonyl-containing groups, such as diacetone acrylamide (DAAM); vinyl aromatic monomers, including styrene and substituted styrenes, such as α-methylstyrene, p-methylstyrene, tert-butylstyrene, vinyl toluene or mixtures thereof; butadiene; α-olefins, such as ethylene, propylene and 1-decene; vinyl acetate, vinyl butyrate, vinyl versatate and other vinyl esters; glycidyl (meth)acrylate; or combinations thereof.

[0056] The vinyl (meth)acrylic acid-based copolymers may alternatively or additionally incorporate silicon-containing monomers such as vinyl trialkoxysilanes such as vinyl trimethoxysilane, vinyl triethoxysilane and vinyl tri(2-methoxyethoxy)silane, vinyl dimethylethoxysilane, vinyl methyl diethoxysilane and (meth)acryloxy alkyl trialkoxysilanes such as (meth)acryloxy ethyl trimethoxy silane and (meth)acryloxy propyl trimethoxy silane or combinations thereof.

[0057] Any suitable combination of the above monomers and the vinyl acetate polymer may be used to prepare the vinyl (meth)acrylic acid-based copolymers herein.

[0058] Copolymers based on vinyl (meth) acrylic acid can be prepared, for example, by emulsion polymerization, which can be initiated / catalyzed by thermal, redox (using redox catalysts), photochemical and electrochemical initiation, however, typically the polymerization process is initiated / catalyzed using one or more conventional free radical initiators, such as peroxides, such as hydrogen peroxide, sodium or potassium hydroperoxide, tert-alkyl peroxides, tert-alkyl hydroperoxides, such as dicumyl hydroperoxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide; tert-alkyl peresters, wherein the tert-alkyl group includes at least 5 carbon atoms; perboric acid and their salts, such as, for example, sodium perborate; perphosphoric acid and their salts; ammonium and / or alkali persulfates, potassium permanganate; and ammonium or alkali metal salts of peroxodisulfuric acid. Such initiators can be used in an amount ranging from 0.01 wt % to 3.0 wt % (weight percent), based on the total weight of the monomers.

[0059] The vinyl (meth) acrylic acid-based copolymers herein may have any suitable weight average molecular weight in the range of 10,000 g / mole to 5,000,000 g / mole, for example 10,000 g / mole to 1,000,000 g / mole, alternatively 10,000 g / mole to 750,000 g / mole. As used herein, unless otherwise specified, the phrase "molecular weight" of the vinyl (meth) acrylic acid-based copolymer refers to the weight average molecular weight measured by gel permeation chromatography (GPC) relative to polystyrene (PS) standards. The vinyl (meth) acrylic acid-based copolymers may have any suitable glass transition temperature (Tg) in the range of -10°C to 100°C, for example -10°C to 75°C or alternatively -10°C to 50°C. As used herein, unless otherwise indicated, the term "Tg" or "glass transition temperature" of a polymer with respect to aqueous vinyl (meth)acrylic acid-based copolymer emulsions and components thereof refers to the Tg of the polymer calculated by using the Fox equation (TGFox, Bull. Am. Physics Soc., Vol. 1, No. 3, p. 123 (1956)).

[0060] Meanwhile, the vinyl (meth) acrylic acid-based copolymers herein can be prepared from any suitable combination of (meth) acrylic acid ester monomers and vinyl acetate monomers. Typically, at least 50 wt.% of the monomers are vinyl acetate monomers, alternatively 60 wt.% to 90 wt.% of the monomers. The remaining monomers are typically (meth) acrylic acid alkyl ester monomers or a combination of (meth) acrylic acid alkyl ester monomers and (meth) acrylic acid, aromatic derivatives of (meth) acrylic acid, (meth) acrylamide and acrylonitrile, etc., with a wt.% ratio of 20:1 to 1:1, alternatively 20:1 to 2.5:1, alternatively 20:1 to 5.0:1.

[0061] If desired, mixtures of vinyl (meth)acrylic acid based copolymers may be present, the copolymer(s) being an emulsion of a liquid in water and / or an emulsion of small polymer particles in water.

[0062] When vinyl (meth) acrylic acid based copolymer particles are present, they may have an average particle size (diameter) in the following range: 75 nm to 450 nm, alternatively 100 nm to 375 nm, alternatively 115 nm to 375 nm or alternatively 150 nm to 300 nm. As used herein, unless otherwise indicated, the term "average particle size" means the particle size measured by light scattering (LS) using a BI-90 particle size analyzer from Brookhaven Instruments Corp. (Holtsville, NY). Such vinyl (meth) acrylic acid based copolymer aqueous emulsions may be obtained under the trade name POLYCO TM Emulsion or ROVACE TM Emulsions are commercially available from manufacturers such as The Dow Chemical Company.

[0063] The vinyl (meth)acrylic acid-based copolymer is present in the peelable coating composition in an amount of 70 wt.% to 99.25 wt.% of the peelable coating composition. Silicone polyether copolymer (b)

[0064] The silicone polyether copolymer (b) is present in the composition in an amount of 0.75 wt.% to 10 wt.% of the peelable coating composition. The silicone polyether copolymer is selected from one or both of the following:

[0065] (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 ,in:-

[0066] R and R 1 can be the same or different and are each selected from H or an alkyl group,

[0067] (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;

[0068] (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;

[0069] R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons,

[0070] x is 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50;

[0071] or

[0072] (ii)(CH 3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3;

[0073] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR;

[0074] Where R, x, m', n' and (OC 3 H 6 ) is the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is 1 to about 100.

[0075] It should be understood that, structurally, (C 3 H 6 O) and (OC 3 H 6 ) unit and

[0076] (CH 2 (CH 3 )CHO) and (OCH(CH 3 )CH 2 );

[0077] (CH 2 CH 2 CH 2 O) and (OCH 2 CH 2 CH 2 );and

[0078] ((CH 3 )CHCH 2 O) and (OCH 2 CH(CH 3 ))same;

[0079] In one embodiment, (C 3 H 6 O) and (OC 3 H 6 ) units are (CH 2 (CH 3 )CHO) and (OCH(CH 3 )CH 2 ), which may alternatively be referred to as propylene oxide (PO) units, and (CH 2 CH 2 O) and (OCH 2 CH 2 ) units may alternatively be referred to as ethylene oxide (EO) units.

[0080] In the alternative (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 In the case

[0081] R and R 1 can be the same or different and are each selected from H or an alkyl group.

[0082] In the most preferred embodiment of alternative (i), (C 3 H 6 O) is (CH 2 (CH 3 )CHO) and (OC 3 H 6 ) is (OCH(CH 3 )CH 2 );

[0083] In another embodiment of alternative (i), (C 3 H 6 O) is (CH 2 (CH 3 )CHO) and (OC 3 H 6 ) is (OCH 2 CH(CH 3 ).

[0084] In another embodiment of alternative (i), (C 3 H 6 O) is (CH 2 CH 2 CH 2 O) and (OC 3 H 6 ) is (OCH 2 CH 2 CH 2 ).

[0085] When R and R1 When one or both of R and R are alkyl groups, the alkyl groups may contain 1 to 12 carbons, alternatively 1 to 10 carbons, alternatively 1 to 6 carbons, alternatively methyl or ethyl. 1 At least one of R and R is H or a methyl group; alternatively, R and R 1 In one embodiment, R and R 1 All are H or methyl groups.

[0086] R 15 , R 16 and R 17 Each is an alkylene group having 2 to 6 carbons. The alkylene group may be linear or branched, but is preferably linear, and is, for example, -(CH 2 ) k -, wherein k is 2 to 6, alternatively 2 to 5, alternatively 2 to 4, alternatively -(CH 2 ) 3 -group.

[0087] The subscript x is 2 to 500, the subscript x can alternatively be 3 to 450, the subscript x can alternatively be 4 to 400, the subscript x can alternatively be 5 to 375.

[0088] Subscripts m and m' may be the same or different and are each selected from 0 to about 50, alternatively one or both of subscripts m and m' are 0 to 45, alternatively one or both of subscripts m and m' are 0 to 40. In one embodiment, subscripts m and m' both have the same value of 0 to 40.

[0089] Subscripts n" and n' may be the same or different and are each selected from 3 to about 50, alternatively each of subscripts n" and n' is 3 to 40, alternatively each of subscripts n" and n' is 4 to 35, alternatively each of subscripts n" and n' is 5 to 30. In one embodiment, subscripts n" and n' are the same and are 5 to 30.

[0090] In one embodiment of alternative (i) with respect to silicone polyether copolymer (b) (i.e., (b)(i)), R and R 1 are hydrogen, each of m and m' is 0 to 40, preferably m and m' are equal; each of subscripts n" and n' is 5 to 30, preferably n" and n' are equal and x is 5 to 375. In such embodiments, preferably R 15 and R 16 Same and -(CH 2 ) 3 -.

[0091] In the case of substitution (ii) (CH3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3 In the case of

[0092] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR

[0093] That is, R'=-R 17 -(OCH 2 CH 2 ) n’ (OCH(CH 3 )CH 2 ) m’ OR

[0094] R'=-R 17 -(OCH 2 CH 2 ) n’ (OCH 2 CH(CH 3 ) m’ OR

[0095] R'=-R 17 -(OCH 2 CH 2 ) n’ (OCH 2 CH 2 CH 2 ) m’ OR.

[0096] Preferably, in the case of alternative (ii), R'=-R 17 -

[0097] (OCH 2 CH 2 ) n’ (OCH(CH 3 )CH 2 ) m’ OR;

[0098] Among them, R 17 , x, m' and n' are the same as above, and

[0099] y is 1 to about 100, alternatively y is 1 to 75, alternatively y is 1 to 50, alternatively y is 1 to 40, alternatively y is 1 to 30, alternatively y is 1 to 25. In one embodiment of (b)(ii), m' is 0 to 45, y is 1 to 25 and n' is 4 to 35. In preferred embodiments of each of the above, R 17 For -(CH 2 ) 3 -.

[0100] Additive (c)

[0101] The strippable coating composition may further comprise one or more additives (c). The additives (c) are all optional and may be selected from aqueous solvents, coalescing agents, defoamers (otherwise known as antifoams or antifoams), rheology modifiers, wetting agents, plasticizers, pigments and / or colorants and mixtures thereof; alternatively, selected from aqueous solvents, coalescing agents, defoamers (otherwise known as antifoams or antifoams), rheology modifiers, wetting agents and mixtures thereof; in one embodiment, the strippable coating composition comprises at least one of the additives (c).

[0102] Aqueous solvent

[0103] As previously mentioned, binding agent (a), i.e., the aqueous copolymer emulsion based on vinyl (meth) acrylic acid comprises an aqueous liquid continuous phase. If desired, other aqueous solvents can be introduced into the strippable coating composition during the preparation of the strippable coating composition, but this is usually not necessary. When introducing, this aqueous solvent can only be water again, but it can contain a small amount of other solvents in addition, such as alcohol, such as methanol, ethanol, isopropanol, butanols and / or hexanol. When present, other aqueous solvents are with 10wt.% at the most of the strippable coating composition, alternatively the amount of 5.0wt.% at the most of the strippable coating composition is added.

[0104] Coagulant

[0105] Optionally, the strippable coating composition of the present invention may include one or more coalescing agents to help form a continuous strippable coating on the substrate surface. "Coalescent" herein refers to a slowly evaporating solvent that fuses polymer particles into a continuous film under ambient conditions. When the strippable coating is formed on the substrate surface, the presence of the coalescing agent herein helps prevent cracks from forming on the film surface. The coalescing agent may include some hydrophobic organic solvents having a volatility lower than that of water, including 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 mixtures of any two or more thereof. Preferred coalescing agents include dipropylene glycol n-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, n-butyl ether, or mixtures thereof. When present, the coalescing agent can be present in an amount of up to 12 wt.% of the strippable coating composition, alternatively in an amount of up to 10 wt.% of the strippable coating composition, alternatively in an amount of up to 7.5 wt.% of the strippable coating composition, alternatively in an amount of up to 5.0 wt.% of the strippable coating composition.

[0106] Defoaming agent

[0107] The peelable coating composition may include one or more defoamers. "Defoamer" herein refers to a chemical additive that reduces and hinders foam formation. The defoamer may be an ethylene oxide / propylene oxide based defoamer, a silicone based defoamer including silicone polyethers (SPE), polyoxyalkylene substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides; a mineral oil based defoamer, an alkyl polyacrylate or a mixture thereof.

[0108] When present, the silicone polyether defoamer may have a rake-type structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto the siloxane backbone, or the SPE may have an ABA block copolymer structure in which A represents the polyether portion and B represents the siloxane portion of the ABA structure. Suitable SPEs include DOWSIL® from Dow Silicones Corporation, Midland, Michigan, USA. TMOFX-5329 fluid. When SPE is used as a defoamer herein, it typically has a hydrophile-lipophile balance (HLB) of about 2 to 3. The defoamer can be an emulsion of a polyether siloxane copolymer in combination with fumed silica, such as TEGO supplied by Evonik. TM Airex 902 W. For the avoidance of doubt, defoamers are distinct from component (b) herein.

[0109] When present, the defoaming agent may be incorporated into the composition in an amount of up to 2 wt.% of the strippable coating composition, alternatively in an amount of up to 1.5 wt.% of the strippable coating composition, alternatively in an amount of up to 1.0 wt.% of the strippable coating composition, for example in a range of 0.1 wt.% to 1 wt.% of the strippable coating composition.

[0110] Rheology Modifiers

[0111] The peelable coating composition may contain one or more rheology modifiers, sometimes referred to as thickeners. These may include one or more clay materials, acid derivatives, naturally occurring polymers having, for example, polysaccharide or amino acid building blocks, such as starch, modified starch, proteins and modified proteins, dimerized and trimerized fatty acids and / or imidazolines. Alternatively, they may include polyvinyl alcohol (PVA), acid copolymers, urethane associative thickeners (UAT), polyether urea polyurethane (PEUPU), polyether polyurethane (PEPU), alkali swellable emulsions (ASE) such as sodium or ammonium neutralized acrylic polymers; hydrophobically modified alkali swellable emulsions (HASE) such as hydrophobically modified acrylic copolymers; associative thickeners such as hydrophobically modified ethoxylated urethanes (HEUR); and cellulosic thickeners such as methyl cellulose ethers, 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.

[0112] ASE rheology modifiers are similar in polymer structure to HASE rheology modifiers but do not contain hydrophobic groups, i.e. they are dispersions of insoluble acrylic polymers in water that have a high percentage of acid groups distributed throughout their polymer chains. When the acid groups are neutralized, the salt formed is "hydrated" and the salt swells in aqueous solution or becomes completely soluble in water. As the concentration of neutralized polymer increases in the aqueous formulation, the swollen polymer chains begin to overlap until they "entangle." It is this overlap and entanglement that causes the viscosity to increase. Again, the concentration of acid groups, the molecular weight of the polymer, and the degree of crosslinking are important in determining rheology and thickening efficiency. Examples include ACRYSOL from Dow TM ASE-75.

[0113] HASE polymers are of great commercial importance as associative rheology modifiers in waterborne paints and coatings. They are dispersions in water of water-insoluble acrylic polymers which are rendered water soluble by neutralization of acid groups on the polymer chain and which also contain long chain hydrophobic groups, sometimes referred to as "hydrophobes". Typically, they are aqueous dispersions of the following copolymers:

[0114] (i) acrylate or methacrylate monomers, such as methyl methacrylate, ethyl acrylate, butyl acrylate or ethylhexyl acrylate);

[0115] (ii) methacrylic acid, acrylic acid or itaconic acid; and

[0116] (iii) Monomers containing long chain hydrophobic groups, such as ethylenically unsaturated polyethylene oxide (polyEO) macromonomers, for example alkylated ethoxylate monomers, preferably alkylated ethoxylate acrylates or methacrylates.

[0117] The alkylated chain may range from C10 to C25, alternatively C12 to C20.

[0118] For example, the following commercially available HASE from The Dow Chemical Company contains polymerized units of ethyl acrylate and methacrylic acid monomers to which a hydrophobe is attached, ACRYSOL TM DR-6600、ACRYSOL TM DR-5500, ACRYSOL TM RM-7, ACRYSOL TM TT-615, ACRYSOL TM DR-72 and ACRYSOL TM TT-935. Other commercially available HASEs include ACRYSOL from The Dow Chemical Company TM Primal HT-400, ACULYN TM 88.ACULYNTM 28.ACULYNL TM 88 and Romax TM 7011, and RHEOTECH from Coatex TM 4800.

[0119] Hydrophobically modified ethoxylated urethane (HEUR) associative rheology modifiers are widely used in waterborne coatings because of their desirable rheological and application properties. The hydrophobically modified alkylene oxide urethane polymer is a polyethylene oxide, polypropylene oxide, or polybutylene oxide urethane polymer, preferably a polyethylene oxide urethane polymer modified with a suitable hydrophobe and can be prepared, for example, by reacting: a diisocyanate; a water-soluble polyalkylene glycol; and a capping agent comprising a hydrophobe. The hydrophobe is then introduced by capping this isocyanate-terminated prepolymer with, for example, a hydrophobic alcohol or amine. Commercially available HEURs include ACRYSOL TM RM-8W Rheology Modifier and ACRYSOL TM RM-5000 rheology modifier, both available from The Dow Chemical Company.

[0120] Hydroxyethylcellulose polymers (HEC) are nonionic water-soluble polymers that thicken, suspend, bind, emulsify, form films, stabilize, disperse, retain water, and provide protective colloid effects. They are readily soluble in hot or cold water and can be used to prepare solutions over a wide range of viscosities. Examples include Natrosol TM 250HBR (a water soluble nonionic hydroxyethyl cellulose surface treated with glyoxal from Ashland Specialty Chemical). Preferably, the rheology modifier selected when present is selected from HEC, HUER or mixtures thereof.

[0121] When present in the strippable coating composition, the rheology modifier may be present in an amount up to 5 wt.% of the strippable coating composition, alternatively up to 4.0 wt.% of the strippable coating composition, alternatively in a range of 0.01 wt.% to 4 wt.% of the strippable coating composition, alternatively 0.05% to 3 wt.% of the strippable coating composition.

[0122] Wetting Agents

[0123] As described above, the strippable coating composition may also include one or more wetting agents. "Wetting agent" herein refers to a chemical additive that reduces the surface tension of the coating composition, thereby making the strippable coating composition easier to diffuse across the substrate surface or penetrate the substrate surface. The wetting agent may be an anionic, zwitterionic or nonionic polycarboxylate.

[0124] Anionic wetting agents may 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, phosphoric 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 glycerides of fatty acids, such as sulfonated monoglycerides of coconut oil; salts of sulfonated monovalent alcohol esters, such as sodium oleyl isethionate; amides of aminosulfonic acid, such as oleyl methylamino ethanesulfonic acid sodium salt; sulfonation products of fatty acid nitriles, such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons, such as sodium α-naphthalene monosulfonate; condensation products of naphthalenesulfonic acid with formaldehyde; sodium octahydroanthracenesulfonate; ether sulfates having an alkyl group with 8 or more carbon atoms; alkylaryl sulfonates having 1 or more alkyl groups with 8 or more carbon atoms; sodium dodecylbenzenesulfonate; dioctylsulfosuccinate; sodium polyoxyethylene lauryl ether sulfate; diphenylsulfonic acid derivatives, such as sodium dodecyl diphenyl oxide disulfonate and sodium tert-octylphenoxyethoxypoly (39)ethoxyethyl sulfate.

[0125] Anionic wetting agents that are commercially available and useful herein may include, but are not limited to, 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 manufactured by Hoechst-Celanese TM SAS; HAMPOSYL manufactured by WRGRACE & CO., Lexington, MA TM C30 and L30. Silicone polyether wetting agents may include DOWSIL 9000 from Dow Silicones, Midland, Michigan, USA TM OFX-5329 fluid or BYK-346 commercially available from Byk-Chemie GmbH.

[0126] Nonionic wetting agents include polyethoxylates such as ethoxylated alkyl polyethylene glycol ethers; polyoxyalkylene alkyl ethers; polyoxyalkylene sorbitan esters; polyoxyalkylene esters; polyoxyalkylene alkylphenyl ethers, ethoxylated amides; ethoxylated alcohols; ethoxylated esters; polysorbates; polyoxypropylene compounds such as propoxylated alcohols; ethoxylated / propoxylated block polymers and propoxylated esters; alkanolamides; amine oxides; fatty acid esters of polyols such as ethylene glycol esters, diethylene glycol esters, propylene glycol esters, glycerol esters, polyglycerol fatty acid esters, sorbitan esters, sucrose esters, and glucose esters. Commercial nonionic wetting agents include, for example, TERGITOL manufactured by The Dow Chemical Company of Midland, Michigan. TM TMN-6, TERGITOL TM 15S40、TERGITOL TM 15S9, TERGITOL TM 15S12, TERGITOL TM 15S15 and TERGITOL TM 15S20 and TRITON TM X405; BRIJ manufactured by Croda (UK) TM 30 and BRIJ TM 35; MAKON manufactured by Stepan Company (Chicago, Illinois) TM 10; and ETHOMID manufactured by Akzo Nobel Surfactants (Chicago, IL). TM O / 17.

[0127] The wetting agent may alternatively or additionally include a silicone polyether (SPE). The silicone polyether as a wetting agent may have a rake-type structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto the siloxane backbone, or the SPE may have an ABA block copolymer structure in which A represents a polyether portion and B represents a siloxane portion of an ABA structure. Alternatively, the wetting agent may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. When SPE is used as a wetting agent herein, it typically has a hydrophilic-lipophilic balance (HLB) of about 7 to 9 as determined by the above method.

[0128] For the avoidance of doubt, SPE used as a wetting agent is distinct from component (b) herein.A commercial example of an SPE wetting agent is BYK-346 commercially available from BYK-Chemie GmbH.

[0129] When present, the wetting agent may be present in an amount up to 5 wt. % based on the total weight of the strippable coating composition, alternatively 0.01 wt. % to 4 wt. % of the strippable coating composition, or alternatively 0.1 wt. % to 3 wt. % of the strippable coating composition.

[0130] Additives (c) may additionally include plasticizers and / or pigments and colorants.

[0131] Plasticizers

[0132] Any suitable plasticizer may be incorporated, for example phthalates such as di-n-octyl phthalate (DOP), di-isononyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP), and di-isodecyl phthalate (DIDP); citrates such as acetyl tributyl citrate (ATBC); adipates such as dioctyl adipate (DOA), di-2-ethylhexyl adipate (DEHA), diisononyl adipate (DINA); and diisononyl 1,2-cyclohexanedicarboxylate and mixtures thereof.

[0133] Pigments and colorants

[0134] Examples of pigments include titanium dioxide, chromium oxide, bismuth vanadium oxide, iron oxide, and mixtures thereof.

[0135] Examples of colorants that can be used herein include pigments, vat dyes, reactive dyes, acid dyes, chrome dyes, disperse dyes, cationic dyes and mixtures thereof. Pigments and / or colorants can be colorful, white, black, metallic and luminescent, such as fluorescent and phosphorescent. Pigments are used to color the composition as required. Any suitable pigment that provides compatibility with the composition herein can be used. In a two-part moisture-curing organopolysiloxane composition, pigments and / or colored (non-white) fillers such as carbon black can be used in a catalyst package to color the final sealant product.

[0136] Suitable white pigments and / or colorants include titanium dioxide, zinc oxide, lead oxide, zinc sulfide, lithopone, zirconium oxide, and antimony oxide.

[0137] Suitable non-white inorganic pigments and / or colorants include, but are not limited to, iron oxide pigments such as goethite, lepidocrocite, hematite, maghemite and maghemite black iron oxides, yellow iron oxides, brown iron oxides and red iron oxides; blue iron pigments; chromium oxide pigments; cadmium pigments such as cadmium yellow, cadmium red and cadmium cinnabar; bismuth pigments such as bismuth vanadate and bismuth vanadate molybdate; mixed metal oxide pigments such as cobalt titanate green; chromate and molybdate pigments such as chrome yellow, molybdenum red and molybdenum orange; ultramarine pigments; cobalt oxide pigments; nickel antimony titanate; lead chromium; carbon black; lamp black and metallic effect pigments such as aluminum, copper, copper oxide, bronze, stainless steel, nickel, zinc and brass.

[0138] Suitable organic non-white pigments and / or colorants include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; monoarylate yellows, diarylate yellows, benzimidazolone yellows, heterocyclic yellows, DAN oranges, quinacridone pigments such as quinacridone magenta and quinacridone violet; organic reds including metallized azo reds and non-metallized azo reds as well as other azo pigments, monoazo pigments, diazo pigments, azo pigment lakes, β-naphthol pigments, naphthol AS pigments, benzimidazolone pigments, diazo condensation pigments, isoindolinone and isoindolinone pigments, polycyclic pigments, perylene and perindole pigments, thioindigo pigments, anthrapyrimidone pigments, flavonoid pigments, anthraquinone pigments, dioxazine pigments, triarylcarbonium pigments, quinophthalone pigments, and diketopyrrolopyrrole pigments.

[0139] Cumulatively, the total amount of additive (c) present in the strippable coating composition may range from 0 (zero) to 19.25 wt. % of the strippable coating composition, alternatively from 0 (zero) to 15.0 wt. % of the strippable coating composition.

[0140] 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.

[0141] Therefore, the present invention provides a peelable coating composition, which comprises

[0142] (a) a vinyl (meth) acrylic acid-based aqueous copolymer emulsion binder, the amount of the vinyl (meth) acrylic acid-based aqueous copolymer emulsion binder is 70 wt.% to 99.25 wt.% of the strippable coating composition; and

[0143] (b) a silicone polyether copolymer, wherein the amount of the silicone polyether copolymer is 0.75 wt.% to 10 wt.% of the strippable coating composition, and the silicone polyether copolymer is selected from one or both of the following:

[0144] (i)RO(C3 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 ,in:-

[0145] R and R 1 can be the same or different and are each selected from H or an alkyl group,

[0146] (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;

[0147] (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;

[0148] R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbon atoms, preferably -

[0149] (CH 2 ) 3 -; x is 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50;

[0150] or

[0151] (ii)(CH 3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3 ;

[0152] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR;

[0153] Where R, x, m', n' and (OC 3 H 6 ) is the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is 1 to about 100. Preferably, in the case of alternative (ii), R'=-(CH 2 ) 3 (OCH 2 CH 2 ) n’ (OCH(CH 3 )CH 2 ) m’ OR;

[0154] and optional

[0155] One or more additives (c) selected from aqueous solvents, coalescing agents, defoamers, wetting agents, rheology modifiers, plasticizers, pigments and / or colorants and / or mixtures thereof; alternatively one or more additives (c) selected from aqueous solvents, coalescing agents, defoamers, wetting agents, rheology modifiers and / or mixtures thereof, in an amount of 0 (zero) to 19.25 wt.% of the strippable coating composition.

[0156] The peelable coating formed after applying the peelable coating composition is provided to temporarily protect the substrate surface for a predetermined period of time, and can then be removed by peeling from the substrate surface.

[0157] A method for forming a strippable coating on a substrate comprises the following steps:

[0158] (I') combining the following to form a peelable coating composition: a vinyl (meth)acrylic acid-based aqueous copolymer emulsion binder (a); and

[0159] Silicone polyether copolymer (b), the amount of the silicone polyether copolymer is 0.75wt.% to 10wt.% of the strippable coating composition, and the silicone polyether copolymer is selected from one or both of the following:

[0160] (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 ,in:-

[0161] R and R 1 can be the same or different and are each selected from H or an alkyl group,

[0162] (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;

[0163] (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;

[0164] R 15 and R 16 are the same or different and are alkylene groups having 2 to 6 carbons,

[0165] x is 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50;

[0166] or

[0167] (ii)(CH 3 ) 3 SiO-((CH 3 ) 2 SiO) x -(CH 3 R'SiO) y -Si(CH 3 ) 3 ;

[0168] Where R'=-R 17 -(OCH 2 CH 2 ) n’ (OC 3 H 6 ) m’ OR;

[0169] Where R, x, m', n' and (OC 3 H 6 ) is the same as above, R 17 is an alkylene group having 2 to 6 carbons, and y is 1 to about 100. Preferably, in the case of alternative (ii), R'=

[0170] -R 17 -(OCH 2 CH 2 ) n’ (OCH(CH 3 )CH 2 ) m’ OR, where R 17 Preferably -(CH 2 ) 3 -;

[0171] and optional

[0172] one or more additives (c) selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments or colorants and / or mixtures thereof,

[0173] (II') applying the strippable coating composition onto a substrate surface;

[0174] (III') drying the peelable coating composition applied in step (II') to form a peelable coating on the substrate.

[0175] The peelable coating composition can be prepared in any suitable manner in the above-mentioned step (I). For example, component (a) can be introduced into a suitable mixer, and then stirred when any optional additive is introduced into the mixture. After adding any optional additive, the silicone polyether copolymer (b) of the desired amount can be added, and then fully mixed with other components to ensure that the silicone polyether copolymer (b) is uniformly dispersed in the entire peelable coating composition. In one embodiment, component (a) is stirred in a mixer until all optional additives are added, and then the silicone polyether copolymer (b) is added, and mixed for a period of up to 10 minutes at 700rpm. Any type of mixing equipment can be used, such as Terrell TM Neulander TM or Ross TM Mixer or FlackTek SpeedMixer from FlackTek of Landrum, South Carolina, USA TM .

[0176] After preparation, in step (II') of the method, the strippable coating composition is applied to the substrate surface by any suitable method, for example, it can be sprayed, brushed, rolled, dipped or otherwise applied to the substrate, but spraying technology is preferred. Usually, the strippable coating composition is applied as a single layer, but if desired, the strippable coating composition coating can be applied in multiple layers. Usually, the target wet coating thickness of the strippable coating composition on the substrate is 100 μm to 750 μm, alternatively the wet coating thickness is 200 μm to 700 μm, alternatively the wet coating thickness is 250 μm to 600 μm. Use a coating rod to measure the wet thickness.

[0177] In step (III') of the method, the strippable coating composition is then dried / cured into a strippable coating on the substrate surface. The resulting strippable coating is visually transparent (see-through). This can usually be done at room temperature and standard conditions, such as atmospheric pressure at 50% relative humidity. Step (III') can be carried out for 2 hours to 12 hours, alternatively any time between 2 hours and 6 hours.

[0178] The substrate to which the strippable coating composition is applied includes materials used in construction or for protecting the surface of the substrate during transportation, storage or construction. After the strippable coating composition is applied, the resulting strippable coating is provided as a temporary means of temporarily protecting the material before and / or after use to protect the surface until, for example, the substrate is ready for use, such as after construction of a building is completed or after transportation has been completed.

[0179] The strippable coatings produced from the strippable coating compositions are demonstrated to be temporary protective coatings that, in the absence of an intermediate layer, can be removed by stripping from the substrate to which they are applied. The strippable coatings that are temporarily applied to the substrate surface and can be removed by stripping are stripped from the substrate surface as intact films by hand, demonstrating that they have suitable tensile strength, with no or minimal cracking or tearing occurring during the stripping operation, even after simulated weathering.

[0180] After applying the strippable coating to the substrate, the method further comprises the step of removing the strippable coating by stripping the strippable coating from the substrate surface to which it was applied.

[0181] Therefore, a method for temporarily protecting a substrate by preparing and applying a strippable coating composition as described above onto a substrate surface; forming a strippable coating on the substrate, transporting, storing and / or using the substrate in construction; and subsequently removing the strippable coating by stripping the strippable coating from the substrate surface may alternatively be provided. In this method, the strippable coating is a temporarily removable coating that is removed when necessary by stripping the coating from the substrate surface.

[0182] Although no quantitative tests have been performed, the fact that the strippable coatings can be removably adhered to the substrate means that they also maintain a sufficiently low peel strength so that the stripping action can be performed manually by hand. The general consensus in the industry is that for a strippable coating to be manually stripped, the peel strength must be no more than about 400 N / m, but preferably no more than about 200 N / m, and preferably less than about 100 N / m, so that the peel strength of the coating to the surface is low enough, and the action of stripping the coating can be performed manually. It was surprisingly found that when a silicone polyether copolymer different from component (b) of this invention was used, much worse results were observed, so that in many cases the resulting coating could not be manually stripped or cracking or tearing was seen, especially after simulated weathering. These results were determined using the naked eye.

[0183] Thus, the strippable coatings resulting from the application of the strippable coating compositions described herein can be considered weather-resistant and / or rainproof and / or water-resistant, enabling them to be used in both exterior and interior situations. In exterior situations where the strippable coating compositions are applied to exterior glass, the strippable coatings obtained herein can protect the exterior-facing glass substrate because the strippable coatings have good water resistance, which will not be damaged or washed off after exposure to rain, even for long periods of time, and the strippable coatings can then be dried but will not be damaged, even in situations of direct exposure to sunlight, because they remain strippable. In fact, it appears to be waterproof, because even after harsh testing, rain / water failed to affect the strippable properties of the strippable coating.

[0184] The peelable coatings herein are provided as protective coatings derived from visually transparent (see-through) peelable coating compositions 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 may also include painted walls and painted metal.

[0185] For example, the strippable coating composition as described herein can be used to provide a strippable coating to protect the paint, glass, plastic or metal parts of vehicles such as automobiles, airplanes, ships, snowmobiles or motorcycles during storage and transportation. Other applications can include temporary protective coatings for bathroom fixtures, plumbing fixtures, kitchen accessories, white appliances such as refrigerators, microwave ovens, electroplated or chrome-plated parts, dashboards, etc. When desired, the strippable coating can be stripped from the substrate together with any dirt and contaminants that have affected the strippable coating during its presence on the substrate surface.

[0186] Specifically designed to provide a strippable coating on interior and exterior glass to provide a water resistant protective coating to the glass substrate during transportation or construction, etc., which can be manually removed as a single film without cracks and / or tears. The glass substrate to which the strippable coating composition is applied can be virtually any glass substrate, such as borosilicate glass, soda lime glass, silica glass, alkali barium glass, aluminosilicate glass, lead glass, phosphate glass, alkali borosilicate glass, xena glass, fluorosilicate glass, or pre-treated glass, such as vacuum deposited reflective metal coated flat glass, which can be used, for example, in commercial building and architectural spandrel applications. The strippable coating composition can also protect glass substrates used in a wide range of indoor and outdoor applications, for example for or for optical glass, architectural glass, facade glass, dark box glass, decorative glass, technical glass, construction glass such as structural glass, float glass, shatterproof glass, laminated glass, extra-clear glass, colored glass, tinted glass, tempered glass, glass bricks, frosted glass and / or bulletproof glass, elevator glass, glass products such as windows, and building fixtures and fittings, such as bathroom and kitchen fixtures, for example chrome or brass surfaces must be protected not only during transportation, but also during installation or assembly to avoid scratching and damage before construction or during construction. Example

[0187] A variety of coating compositions were prepared with the goal of comparing their strippability after application to a suitable substrate. An evaluation was conducted to compare the strippability of these coating compositions before and after spraying with water (simulating rain) with the goal of determining the feasibility of the coatings as strippable coatings for temporary protection of substrate surfaces that are exposed to the elements during building construction, storage and / or transportation, etc. Several combinations of binder and silicone polyether were used as the basis for the coating compositions. Six formulations (in the form of n ), wherein the changes of the binder and the silicone polyether are as follows. shape Mode n )I to VI are described in Table 1a.

[0188] Table 1a. Formulations used in the examples (wt.%)

[0189] <![CDATA[Form n I]]> <![CDATA[Form n II]]> <![CDATA[Form n III]]> <![CDATA[Form n IV]]> <![CDATA[Form n V]]> <![CDATA[Form n VI]]> Binder 90 90 90 84 95 95 SPE 1.0 0.5 2.0 8.0 2.0 0 Coagulant 3 3 3 3 3 3 Defoaming agent 0.3 0.3 0.3 0.3 0 1 Wetting Agents 0.3 0.3 0.3 0.3 0 1 RM 1 1.0 1.0 1.0 1.0 0 0 RM 2 1.0 1.0 1.0 1.0 0 0 water 3.4 3.9 2.4 2.4 0 0 total 100 100 100 100 100 100

[0190] In Table 1a :

[0191] The coalescing agent used in the examples is Texanol commercially available from Eastman Chemical Company. TM Ester alcohol.

[0192] The defoamer used was TEGO commercially available from Evonik Operations GmbH. TM Airex 902W.

[0193] The wetting agent used was BYK-346 commercially available from BYK-Chemie GmbH.

[0194] Rheology Modifier 1 (RM 1) is ACRYSOL commercially available from The Dow Chemical Company. TM RM-8W rheology modifier.

[0195] Rheology Modifier 2 (RM 2) is ACRYSOL commercially available from The Dow Chemical Company. TM RM-5000 rheology modifier.

[0196] The following binders were evaluated:

[0197] Binder 1 was manufactured by Dow Chemical Company under the name ROVACE according to the disclosure herein. TM 662 Emulsion A commercially available vinyl acrylic based aqueous copolymer emulsion;

[0198] Binder 2 is a 100% acrylic polymer emulsion made from ELASTENE TM 3776 acrylic emulsion is a comparative adhesive sold commercially from The Dow Chemical Company;

[0199] Binder 3 is a styrene acrylic copolymer emulsion, which is based on PRIMAL TM SF-155 emulsion is a commercially available comparative adhesive;

[0200] Thirteen different silicone polyethers (SPEs) were evaluated when combined with a binder. In each case as described above, some conformed to structure b(i), some conformed to structure b(ii), and the others were provided as comparisons. The structure of each of the SPEs is described in Table 1b below, where R 2 -R 13 In the above formula, (EO) is ethylene oxide unit (OCH 2 CH 2 ) and (PO) is a propylene oxide unit (OCH(CH 3 )CH 2 ), Ac is an acetate group and Me is a methyl group.

[0201] Table 1b. Formulas of silicone polyethers (SPEs) tested in this article

[0202]

[0203]

[0204] For the avoidance of doubt, the SPEs indicated as comparative are outside the present disclosure and were evaluated for comparative reasons.

[0205] By introducing all ingredients except SPE into the binder and mixing them in a FlackTek SpeedMixer from FlackTek, Inc., Landrum, South Carolina, USA TM Different compositions were prepared by stirring at 700 rpm for a few minutes. The selected SPE was then added and mixing was continued at 700 rpm for another 10 minutes to ensure that the SPE was evenly dispersed in the composition.

[0206] Each resulting composition was then applied to glass, ceramic or polyvinylidene fluoride (PVDF) plates (unless otherwise stated). The wet coating thickness of each applied liquid coating was an average value of about 400 μm as measured using a coating bar.

[0207] The applied liquid coating was then allowed to dry / cure at room temperature (RT) and 50% relative humidity for approximately 4 hours.

[0208] After drying / curing, each coating was evaluated for strippability relative to the substrate to which it was applied in three ways:

[0209] 1) At room temperature

[0210] Peelability was tested shortly after the 4-hour drying / curing process was completed;

[0211] 2) At 5°C

[0212] The coated samples were dried / cured at 5°C to simulate winter temperatures, after which the strippability was evaluated;

[0213] 3) After spraying with water

[0214] After curing / drying, the coated substrates were placed in a suitable laboratory fog box and sprayed with water for 7 hours to simulate rainy weather. The coated substrates were then dried in an oven at 50°C before evaluating the strippability of the strippable coatings. This is considered to be a harsher condition than any natural weather to which the strippable coatings may be exposed, even in hot climates such as those in Southeast Asia.

[0215] The strippability of the sample strippable coatings was graded from 1 (worst) to 5 (best) by visually inspecting the strippable coatings for defects (such as shrinkage after water spraying, color change, etc.) and comparing to a standard panel according to the following definitions:

[0216] Rating 5: The entire peelable coating is easily peeled off, no residual peelable coating remains on the substrate, no cracks occur during peeling, and no damage to the substrate occurs.

[0217] Rating 4: Almost completely peeled off, but slightly more force was required. Minimal (5% or less) residue was left on the substrate. The strippable coating may have slight cracks or fissures.

[0218] Rating 3: Greater force is required to peel the peelable coating from the substrate. The peelable coating is more easily torn than (4 or 5 above), and more than 30% of the residual peelable coating may remain on the substrate.

[0219] Grade 2: It can be peeled, but the peelable coating is easily torn. More than 50% of the peelable coating may remain on the substrate, and the substrate may be damaged.

[0220] Level 1: Difficult to peel, too well adhered, requires solvents or tools to remove.

[0221] Table 2 provides an indication of the target levels for each test performed. For the avoidance of doubt, the symbol ≥ means equal to or greater than.

[0222] Table 2. Acceptable coating properties in clearcoat formulations :

[0223] performance Target Peelability on glass at room temperature (RT) ≥4 Strippability on ceramics at RT ≥4 Strippability on polyvinylidene fluoride (PVDF) at RT ≥4 Peelability on glass at 5°C ≥4 Strippability on PVDF at 5°C ≥4 Strippability after 7 hours of water spraying and then drying overnight at 50°C (glass, ceramics) ≥4 Strippability after 7 hours of water spraying and then drying at 50 °C overnight on PVDF ≥3

[0224] Table 3a. Strippable coatings on several substrates at room temperature for Ex. 1 to 13 based on the above classification method The peelability results of the case

[0225]

[0226] Table 3b. Strippable coatings at 5°C and after water spraying based on the above grading scheme for Ex. 1 to 13. Separation results

[0227]

[0228]

[0229] As can be seen in Table 3b, it was found that the composition using Binder 1 in combination with an SPE according to the definition herein in an amount of at least 0.75 wt.% provided excellent peelability after water spraying. The above results indicate that the peelable coatings are still peelable by hand and durable even after the water spray test and drying, as they do not tear during peeling after being subjected to the water spray test. In addition, this peelability also indicates that the peelable coatings retain sufficient adhesion after being exposed to water spray simulating rain water.

[0230] Several comparative examples were also conducted using the same test methods and evaluation means. The results are described in Table 4a and Table 4b.

[0231] Table 4a. Strippability results based on the above grading scheme for comparative coatings on several substrates at room temperature

[0232]

[0233] Table 4b. Strippability results of comparative coatings at 5°C and after water spray based on the above grading scheme

[0234]

[0235] The results described in Table 4a and Table 4b were obtained using compositions outside the scope of the present disclosure. It can be seen that based on the above classification scheme, they give significantly poor strippability results. C.1-9 all contain SPE outside the required formulation, while C.10 and C.11 do not contain SPE at all. Many of these coatings are no longer durable for the required use, especially on PVDF, and crack and / or tear when trying to peel by hand, especially after drying after extreme water spray testing. This leads to the conclusion that such strippable coatings are not suitable for the purpose shown by the results of Table 4a and especially Table 4b.

Claims

1. A peelable coating composition, comprising: (a) an aqueous copolymer emulsion binder based on vinyl (meth) acrylic acid; and (b) a silicone polyether copolymer, wherein the amount of the silicone polyether copolymer is 0.75 wt.% to 10 wt.% of the strippable coating composition, and the silicone polyether copolymer 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 , in which: - R and R 1 can 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 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50; or <h2 style=";text-align:left;direction:ltr">(ii)(CH3)3SiO-((CH3)2SiO)<h2 style=";text-align:left;direction:ltr"> x <h2 style=";text-align:left;direction:ltr"> -(CH3 R'SiO)<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> -Si(CH3)3; Where 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 1 to about 100; and optional One or more additives (c) selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof.

2. The strippable coating composition according to claim 1, wherein the silicone polyether copolymer (b)(i) has the formula RO(C3H6O) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 -(OCH2CH2) n’ (OC3H6)m ’ OR 1 Where R and R 1 is 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.

3. The peelable coating composition according to claim 1 or 2, wherein the silicone polyether copolymer (b)(i) has the formula RO(CH2(CH3)CHO) m (CH2CH2O) n” R 15 -((CH3)2SiO) x (CH3)2Si-R 16 (OCH2CH2) n’ (OCH(CH3)CH2) m’ OR 1 , Where R and R 1 is hydrogen, m and m' are the same or different and are 0 to 40, n" and n' are the same or different and are 5 to 30 and x is 5 to 375.

4. The strippable coating composition according to claim 1 or 2, wherein the silicone polyether copolymer (b)(ii) has the formula (CH3)3SiO-((CH3)2SiO) x -(CH3 R'SiO) y -Si(CH3)3; Where R'=-R 17 -(OCH2CH2) n’ (OC3H6) m’ OR; wherein m′ is 0 to 45, y is 1 to 25 and n′ is 4 to 35.

5. The strippable coating composition according to claim 4, wherein the silicone polyether copolymer (b)(ii) has the formula (CH3)3SiO-((CH3)2SiO) x -(CH3R'SiO) y -Si(CH3)3; Where R'=-R 17 -(OCH2CH2) n’ (OCH(CH3)CH2) m’ OR wherein m′ is 0 to 45, y is 1 to 25 and n′ is 4 to 35.

6. The strippable coating composition of claim 1, 2, 3, 4 or 5, wherein component (a) is present in an amount of 70 wt.% to 99.25 wt.% of the strippable coating composition, and the additive of component (c), when present, is present cumulatively in an amount of up to 19.25 wt.% of the strippable coating composition.

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

8. A strippable coating composition according to any preceding claim, wherein R 15 , R 16 and R 17 is -CH2)3- and / or the additive (c) is selected from aqueous solvents, coalescing agents, defoaming agents, rheology modifiers, wetting agents and / or mixtures thereof.

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

10. A method for forming a strippable coating on a substrate, the method comprising the steps of: (I') combining the following to form a strippable coating composition: (a) a vinyl (meth) acrylic acid-based aqueous copolymer emulsion binder and a silicone polyether copolymer (b), wherein the amount of the silicone polyether copolymer is 0.75 wt.% to 10 wt.% of the strippable coating composition, and the silicone polyether copolymer 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 , Among them:- R and R 1 can 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; (OC3H 6) (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 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50; or <h2 style=";text-align:left;direction:ltr">(ii)(CH3)3SiO-((CH3)2SiO)<h2 style=";text-align:left;direction:ltr"> x <h2 style=";text-align:left;direction:ltr"> -(CH3 R'SiO)<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> -Si(CH3)3; Where 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 1 to about 100; and optionally one or more additives (c) selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof, (II') applying the strippable coating composition onto a substrate surface; (III') drying the peelable coating composition applied in step (II') to form a peelable coating on the surface of the substrate.

11. The method for forming a strippable coating on a substrate according to claim 10, wherein R 15 , R 16 and R 17 is -CH2)3- and / or the additive (c) is selected from aqueous solvents, coalescing agents, defoaming agents, rheology modifiers, wetting agents and / or mixtures thereof.

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

13. The method for forming a strippable 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 painted wall and painted metal.

14. A method of forming a strippable coating on a substrate according to claim 11, 12 or 13, wherein the method further comprises the step of removing the strippable coating by stripping it from the substrate surface to which it is applied.

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

16. Use of a silicone polyether copolymer (b) in a strippable coating composition, wherein the amount of the silicone polyether copolymer is 0.75 wt.% to 10 wt.% of the strippable coating composition, and the silicone polyether copolymer (b) 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 , in which: - R and R 1 can 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 2 to about 500, m and m' can be the same or different and are each in the range of 0 to about 50, and n" and n' can be the same or different and are in the range of 3 to about 50; or <h2 style=";text-align:left;direction:ltr">(ii)(CH3)3SiO-((CH3)2SiO)<h2 style=";text-align:left;direction:ltr"> x <h2 style=";text-align:left;direction:ltr"> -(CH3 R'SiO)<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> -Si(CH3)3; Where 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 1 to about 100; the strippable coating composition further comprises (a) an aqueous copolymer emulsion binder based on vinyl (meth) acrylic acid; and optionally (c) one or more additives selected from aqueous solvents, coalescing agents, defoamers, rheology modifiers, wetting agents, plasticizers, pigments and colorants and / or mixtures thereof.

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

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