Dual reactive coating compositions, their preparation and use

Abstract

The present invention provides a dual-reactive coating composition comprising: a) 24% to 90% by weight of a crosslinkable silane-functional monomer and / or oligomer and / or polymer; b) 9% to 75% by weight of one monomer and / or unsaturated oligomer and / or unsaturated polymer; c) 0.5% to 10% by weight of one initiator; and d) 0.5% to 10% by weight of one catalyst, all weight percentages being based on the total weight of the coating composition. The present invention also provides a dual-reactive coating composition, a film obtained by curing and drying the coating composition, and a substrate coated with the dual-reactive coating composition. The present invention also provides a method for making the dual-reactive coating composition, and a roll-to-roll coating composition and 1K clearcoat composition comprising the dual-reactive coating composition.

Description

[Technical Field]

[0001] The present invention relates to dual reactive coating compositions, and more particularly to dual reactive coating compositions used as automotive topcoats, their preparation and use. [Background technology]

[0002] Nanocomposites are materials composed of finely dispersed inorganic nanoparticles in a continuous polymer matrix. Inorganic nanoparticles are often produced by a sol-gel process, starting with their respective precursors, which are hydrolyzed and then condensed to form particles of different morphologies. Transparent organic-inorganic composite films can be fabricated by dispersing preformed particles in a polymer using common polymer processes, such as extrusion, or by dispersing them in a monomer and then polymerizing them to form a continuous polymer phase. However, in both cases, the structure of the organic and inorganic phases, their morphology, and the presence of covalent bonds between them significantly affect the properties of these composites.

[0003] For automotive coatings that require high visual appearance and long-term durability, reactive polymer systems with silane functionality are potentially attractive because they offer new properties (e.g., improved scratch resistance and chemical resistance) to conventional coatings based on organic-inorganic hybrids, while enabling various curing approaches and meeting environmental requirements. Summary of the Invention [Problem to be solved by the invention]

[0004] Hybrid silane-containing polymers have been widely applied in moisture-reactive sealants, adhesives, and construction materials. These reactive resins contain hydrolyzable alkoxysilanes at the end or side chains, which react via a hydrolysis mechanism to form silsesquioxane networks. Finely dispersed inorganic domains provide the polymer matrix with excellent properties, such as good chemical resistance, improved scratch resistance, good weather resistance, and improved surface adhesion. However, typical drawbacks of reactive silane-based systems, such as cracking and phase separation, appear after curing, which result in performance degradation, such as durability, chemical resistance, and appearance, severely limiting their use in automotive coatings. [Means for solving the problem]

[0005] In one aspect, the present invention provides a dual reactive coating composition, the coating composition comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of one unsaturated monomer and / or oligomer and / or polymer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0006] In another aspect, the present invention provides a dual reactive coating composition, the coating composition comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% by mass to 75% by mass of unsaturated polyester and / or polyurethane-modified oligomer and / or polyester-modified oligomer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0007] In another aspect, the present invention provides a dual reactive coating composition, the coating composition comprising: a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by mass of unsaturated polyester; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0008] In another aspect, the present invention provides a film obtained by curing and drying the dual reactive coating composition of the present invention.

[0009] In another aspect, the present invention provides a substrate coated with the dual reactive coating composition of the present invention.

[0010] In another aspect, the present invention provides a method for making the dual reactive coating composition of the present invention, the method comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of one unsaturated monomer and / or oligomer and / or polymer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0011] In another aspect, the present invention provides a method for making the dual reactive coating composition of the present invention, the method comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% by mass to 75% by mass of unsaturated polyester and / or polyester-modified oligomer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0012] In another aspect, the present invention provides a method for making the dual reactive coating composition of the present invention, the method comprising: a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by mass of unsaturated polyester; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0013] In another aspect, the present invention provides a roll-to-roll coating composition comprising the duplex reactive coating composition of the present invention, a reactive diluent, and an additive, wherein the solids content of the resulting roll-to-roll coating composition is 90% by weight or more, and preferably 95% by weight or more.

[0014] In a further aspect, the present invention provides a 1K clearcoat composition comprising the duplex reactive coating composition of the present invention, a reactive diluent, an additive, and a co-solvent, wherein the VOC (volatile organic compounds) of the resulting clearcoat composition is 420 g / L or less, and preferably 350 g / L or less.

[0015] Surprisingly, it has been found that by using a dual reaction system, the resulting laid down coating exhibits good performance in terms of durability, chemical resistance, appearance, etc. DETAILED DESCRIPTION OF THE INVENTION

[0016] As used in this specification and the appended claims, the following terms are defined below.

[0017] The terms "a," "an," and "the," when used to define a term, include both the plural and the singular form of that term. All percentages are stated by weight unless otherwise specified.

[0018] The term "and / or" includes the meanings "and", "or" and all other possible combinations of the elements connected to this term.

[0019] As used herein, the term "oligomer" refers to a homopolymer having 2 to 3 repeating units of a single monomeric compound.

[0020] As used herein, the term "1K" refers to a composition containing one component, which may be a mixture of multiple compounds.

[0021] As used herein, the term "2K" or "two-component" refers to a composition containing two components, each of which may be a mixture of compounds. The two components may be blended together if necessary, or the two components may be in two separate barrels that can be mixed at the application site.

[0022] As used herein, the term "solids content" refers to the weight percent of non-volatile material contained in a suspension, such as a coating, paint, or the like.

[0023] As used herein, the term "dual reactive" refers to two reactions in the coating composition: (1) polymerization of the olefinic double bonds contained in the monomers and / or oligomers and / or polymers, and (2) reaction of the hydrolyzable alkoxysilane or organoalkoxysilane groups in the monomers and / or oligomers and / or polymers.

[0024] As used herein, the term "crosslinkable silane-functional polymer" refers to polymers and copolymers containing crosslinkable silane functional groups derived from the (co)polymerization of silane-functional monomers, such as vinylsilanes.

[0025] As used herein, the term "crosslinkable silane-functional oligomer" refers to oligomers and co-oligomers containing crosslinkable silane functional groups derived from the (co)oligomerization of silane-functional monomers, such as vinylsilanes.

[0026] As used herein, the term "reactive diluent" refers to a substance that reduces the viscosity of the coating for processing and then becomes part of the coating through (co)polymerization with any other component(s) of the coating.

[0027] As used herein, the term "co-solvent" refers to a substance added in small amounts to a primary solvent or reactive diluent to enhance the solubility of a poorly soluble compound.

[0028] Silane-functional monomers and / or oligomers and / or polymers The silane-functional monomer in the present invention is preferably a vinylalkoxysilane monomer. In the coating composition, the vinyl group participates in radical polymerization, while the alkoxyl group undergoes hydrolysis and (self-)condensation reactions. Preferably, the vinylalkoxysilane monomer is at least one selected from vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltris(isopropoxy)silane, and 3-methacryloxypropyltrimethoxysilane.

[0029] The silane-functional oligomer and / or polymer is an acrylosilane oligomer and / or polymer, which is comprised of 20% to 50% by weight of a compound of the general formula I H2C=CH-(CH2) n -Si-(R1) m (R2) 3-m (wherein R1 is an aryl or alkyl group having C1 to C6, R2 is an alkoxyl group having C1 to C6, m is 0 or 1, and n is an integer of 0 to 3), 50% to 80% by mass of an ethylenically unsaturated acrylate monomer, and 0 to 30% by mass of an ethylenically unsaturated monomer selected from one or both of a styrene and a methacrylate monomer, the mass % being based on the total mass of the acrylosilane polymer.

[0030] The ethylenically unsaturated acrylate monomer is preferably an alkyl acrylate having a C1 to C12 alkyl group, and more preferably at least one selected from methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, ethylhexyl acrylate, nonyl acrylate, and lauryl acrylate. Alicyclic acrylates such as isobornyl acrylate, trimethylcyclohexyl acrylate, and t-butylcyclohexyl acrylate may be used. Aryl acrylates such as benzyl acrylate may be used. Polyacrylate monomers, such as 1,3-butanediol diacrylate and cyclohexanedimethanol diacrylate, can be used. Neopolyacrylate monomers, such as 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, cyclohexanedimethanol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, diurethane diacrylate, and urethane triacrylate can also be used. Other acrylate monomers, such as silane-functional acrylates, can also be used. Mixtures of the above monomers can also be used.

[0031] The methacrylate monomer is preferably an alkyl methacrylate monomer, and more preferably at least one selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, and lauryl methacrylate. Alicyclic methacrylates, such as trimethylcyclohexyl methacrylate and t-butylcyclohexyl methacrylate, may be used. Aryl methacrylates, such as benzyl methacrylate, may be used. The styrene monomer is preferably a vinyl aromatic, such as styrene and methylstyrene.

[0032] The acrylosilane polymer may contain hydroxy functionality provided by hydroxyalkyl acrylates and methacrylates having C1-C4 alkyl groups, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

[0033] Preferably, the crosslinkable silane-functional oligomer or polymer has a weight average molecular weight of less than 30,000, and preferably less than 20,000, and the crosslinkable silane-functional polymer has a hydroxyl number of 0 to 150 mg KOH / g and an acid number of 0 to 50 mg KOH / g.

[0034] The solvent used to form the acrylosilane polymer is a petroleum fraction. Alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, sec-butanol, isobutanol, and propanol may be used. Ketones such as acetone, butanone, pentanone, hexanone, and methyl ethyl ketone may be used. Alkyl esters of acetic acid, propionic acid, and butyric acid, such as ethyl acetate, butyl acetate, and amyl acetate, may also be used. Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol, polyethylene glycol monoalkyl and dialkyl ethers, such as cellosolve and carbitol, and glycols such as ethylene glycol and propylene glycol may also be used. The above monomers may be mixed for use.

[0035] Peroxy or azo polymerization initiators may be used in the production of acrylosilane polymers, such as benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, t-butyl peroxy 2-ethylhexanoate, 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-methylbutyronitrile, and 1,1'-azobis-cyanocyclohexane.

[0036] Surprisingly, a synthesis procedure based on an optimized feeding strategy has been discovered in which the composition of the monomer feed is varied at multiple steps during the reaction. These optimized feeding strategies result in homogeneous incorporation of vinylalkoxysilane and, at the same time, a significant reduction in residual monomers after polymerization. Homogeneous silane-functional polymers are obtained that have excellent film-forming and crosslinking properties and offer excellent flexibility. Thus, crack formation is significantly suppressed without the addition of any film-forming polymers or additives, such as curing agents and plasticizers.

[0037] Preferably, the crosslinkable silane-functional polymer is prepared by a two-step process: in the first step, a vinylalkoxysilane monomer, a (meth)acrylate monomer, an optional styrene monomer, and an initiator are blended with an organic solvent and heated; and in the second step, the (meth)acrylate monomer, the optional styrene monomer, and an initiator are added. In this second step, the (meth)acrylate monomer and the optional styrene monomer are added in two or more batches, with a time of 30 minutes or more between each batch, and the weight ratio of the (meth)acrylate monomer and the optional styrene monomer added in each batch is 1:15 to 15:1.

[0038] More preferably, the crosslinkable silane-functional polymer is prepared by a two-step process: in the first step, a vinylalkoxysilane monomer, a (meth)acrylate monomer, an optional styrene monomer, and an initiator are blended with an organic solvent and heated, and in the second step, the (meth)acrylate monomer, the optional styrene monomer, and an initiator are added. In this second step, the (meth)acrylate monomer and the optional styrene monomer are added in four or more batches, with the time between each batch being one hour or more, and the mass ratio of the (meth)acrylate monomer and the optional styrene monomer added in each batch being 1:15 to 15:1.

[0039] As an example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of Shellsol A, and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). Then, over a period of 4 to 7 hours, an initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of Shellsol A) is metered in at a uniform rate with stirring. Starting 0 to 30 minutes after the start of the initiator feed, Feed 1, consisting of an ethylenically unsaturated vinylalkoxysilane monomer, is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. Starting 0 to 30 minutes after the start of the initiator feed, 500 to 1500 parts by weight of Feeds 2 to 6, consisting of methyl methacrylate and n-butyl acrylate in a weight ratio of 0.1 to 10, are metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the stated pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of Shellsol A is added again at a uniform rate over 0.5-2 hours. The batch is then held at the stated temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0040] As another example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of Shellsol A, and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). Then, over a period of 4 to 7 hours, an initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of Shellsol A) is metered in at a uniform rate with stirring. Starting 0 to 30 minutes after the start of the initiator feed, Feed 1, consisting of an ethylenically unsaturated vinylalkoxysilane monomer, is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. Starting 0 to 30 minutes after the start of the initiator feed, 500 to 1500 parts by weight of Feeds 2 to 6, consisting of styrene, methyl methacrylate, and n-butyl acrylate in a weight ratio of 0.1 to 10, are metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the stated pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of Shellsol A is added again at a uniform rate over 0.5-2 hours. The batch is then held at the stated temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0041] As another example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of Shellsol A, and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). Then, over a period of 4 to 7 hours, an initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of Shellsol A) is metered in at a uniform rate with stirring. Starting 0 to 30 minutes after the start of the initiator feed, Feed 1, consisting of an ethylenically unsaturated vinylalkoxysilane monomer, is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. Starting 0 to 30 minutes after the start of the initiator feed, 500 to 1500 parts by weight of Feeds 2 to 6, consisting of styrene, methyl methacrylate, and ethylhexyl acrylate in a mass ratio of 0.1 to 10, are metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the stated pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of Shellsol A is added again at a uniform rate over 0.5-2 hours. The batch is then held at the stated temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0042] As another example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of butyl acetate and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). An initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of butyl acetate) is then metered in at a uniform rate with stirring over a period of 4 to 7 hours. 0 to 30 minutes after the start of the initiator feed, 300 to 700 parts by weight of an ethylenically unsaturated vinylalkoxysilane monomer is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. In a first step, a monomer mixture consisting of 50 to 150 parts by weight of methyl methacrylate and 50 to 150 parts by weight of n-butyl acrylate is simultaneously metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. In the second step, a monomer mixture consisting of 100 to 200 parts by weight of methyl methacrylate and 100 to 200 parts by weight of n-butyl acrylate is metered in at a uniform rate over 0.5 to 2 hours while stirring. In the third step, a monomer mixture consisting of 50 to 150 parts by weight of methyl methacrylate and 50 to 150 parts by weight of n-butyl acrylate is metered in at a uniform rate over 0.5 to 2 hours while stirring. In the fourth step, a monomer mixture consisting of 50 to 100 parts by weight of methyl methacrylate and 50 to 100 parts by weight of n-butyl acrylate is metered in at a uniform rate over 0.5 to 2 hours while stirring. In the fifth step, a monomer mixture consisting of 25 to 75 parts by weight of methyl methacrylate and 25 to 75 parts by weight of n-butyl acrylate is metered in at a uniform rate over 0.5 to 2 hours while stirring. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the specified pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of butyl acetate is added again at a uniform rate over 0.5-2 hours. The batch is then held at the specified temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0043] As another example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of butyl acetate, and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). An initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of butyl acetate) is then metered in at a uniform rate with stirring over a period of 4 to 7 hours. Starting 0 to 30 minutes after the start of the initiator feed, Feed 1, consisting of an ethylenically unsaturated vinylalkoxysilane monomer, is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. Starting 0 to 30 minutes after the start of the initiator feed, 500 to 1500 parts by weight of Feeds 2 to 6, consisting of styrene, methyl methacrylate, and n-butyl acetate in a mass ratio of 0.1 to 10, are metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the specified pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of butyl acetate is added again at a uniform rate over 0.5-2 hours. The batch is then held at the specified temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0044] As another example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of butyl acetate, and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). An initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of butyl acetate) is then metered in at a uniform rate with stirring over a period of 4 to 7 hours. Starting 0 to 30 minutes after the start of the initiator feed, Feed 1, consisting of an ethylenically unsaturated vinylalkoxysilane monomer, is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. Starting 0 to 30 minutes after the start of the initiator feed, 500 to 1500 parts by weight of Feeds 2 to 6, consisting of styrene, methyl methacrylate, and ethylhexyl acrylate in a mass ratio of 0.1 to 10, are metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the specified pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of butyl acetate is added again at a uniform rate over 0.5-2 hours. The batch is then held at the specified temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0045] As a further example, a crosslinkable silane-functional polymer is prepared as follows: The reactor is charged with 100 to 500 parts by weight of Shellsol A, and this initial charge is heated to 90 to 160°C. The reactor is placed under pressure (1.5 to 6.5 bar). Then, over a period of 4 to 7 hours, an initiator solution (50 to 100 parts by weight of di-tert-butyl peroxide in 50 to 100 parts by weight of Shellsol A) is metered in at a uniform rate with stirring. Starting 0 to 30 minutes after the start of the initiator feed, Feed 1, consisting of an ethylenically unsaturated vinylalkoxysilane monomer, is metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. Starting 0 to 30 minutes after the start of the initiator feed, 500 to 1500 parts by weight of Feeds 2 to 6, consisting of styrene, methyl methacrylate, and ethylhexyl acrylate in a mass ratio of 0.1 to 10, are metered in at a uniform rate with stirring over a period of 0.5 to 2 hours. After complete addition of the initiator solution (0-60 minutes after the end of the monomer mixture addition), the reactor is heated to 100-180°C and stirring is continued for 5-90 minutes at the stated pressure, after which a solution of 5-50 parts by weight of di-tert-butyl peroxide in 5-50 parts by weight of Shellsol A is added again at a uniform rate over 0.5-2 hours. The batch is then held at the stated temperature and pressure for an additional 0.5-2 hours. The reaction mixture is then cooled to 25-80°C and let down to atmospheric pressure.

[0046] The approach to synthesizing acrylosilane polymers according to the present invention results in reduced residual monomer (less than 5%), and the resulting acrylosilane polymers have solids contents of 70% by weight or greater and Tg's less than 15°C.

[0047] Monomers and / or unsaturated oligomers and / or unsaturated polymers Any common monomers, their unsaturated oligomers, and unsaturated polymers for producing coating compositions, such as (meth)acrylic acid esters, unsaturated carboxylic acids, and unsaturated alcohols, may be used here.Preferably, the monomers are phenoxyethyl acrylate, 1,6-hexanediol diacrylate, and trimethylolpropane triacrylate, the unsaturated oligomers are polyurethane-modified acrylate oligomers, such as Laromer® UA8987, Laromer® UA19T, Laromer® UA9050, and Laromer® UA9136, and polyester-modified acrylate oligomers, such as Laromer® PE55F, Laromer® PE9121, and Laromer® PE9105, and the unsaturated polymers are unsaturated polyesters.

[0048] Preferably, the monomer or unsaturated oligomer or unsaturated polymer has a weight average molecular weight of 200 to 20,000, a hydroxyl number of 0 to 350 mg KOH / g, and an acid number of 0 to 150 mg KOH / g.

[0049] Preferably, the unsaturated polyester is produced from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride thereof with at least one saturated aliphatic diol, and more preferably, the unsaturated polyester is produced from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride thereof selected from maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and fumaric acid with at least one saturated aliphatic diol selected from neopentyl glycol, 1,4 butanediol, 1,6 hexanediol, and cyclohexyldimethanol.

[0050] As an example, an unsaturated polyester is prepared as follows: 200-500 parts by weight of trimethylolpropane (TMP), 500-1000 parts by weight of itaconic acid (IA), and 300-600 parts by weight of 1,4-butanediol (BD) are charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a N2 inlet. Subsequently, 5-50 parts by weight of xylene as an entraining agent, 0.05-0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol (BHT) as a stabilizer, and 0.5-1 part by weight of tetra-n-butyl titanate (TBT) as a catalyst are added. The resulting reaction mixture is heated under N2 for 2-8 hours. The temperature of the reaction mixture does not exceed 200°C during the entire reaction time. After the acid value reaches 5-100 mgKOH / g, the reaction mixture is cooled to 50-100° C., and 300-700 parts by mass of butyl acetate (BA) is added to dilute the polymer.

[0051] As another example, an unsaturated polyester is prepared as follows: 200-500 parts by weight of trimethylolpropane (TMP), 400-800 parts by weight of maleic anhydride (MAH), and 400-800 parts by weight of neopentyl glycol (NPG) are charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a nitrogen inlet. Subsequently, 5-50 parts by weight of xylene is added as an entrainer. The resulting reaction mixture is heated under nitrogen for 2-8 hours. The temperature of the reaction mixture does not exceed 200°C during the entire reaction time. After the acid value reaches 5-50 mg KOH / g, the reaction mixture is cooled to 50-100°C, and 300-700 parts by weight of butyl acetate (BA) is added to dilute the polymer.

[0052] As another example, an unsaturated polyester is prepared as follows: 200-500 parts by weight of trimethylolpropane (TMP), 400-800 parts by weight of maleic anhydride (MAH), and 400-800 parts by weight of neopentyl glycol (NPG) are charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a nitrogen inlet. Subsequently, 5-50 parts by weight of xylene as an entrainer and 0.05-0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol (BHT) as a stabilizer are added. The resulting reaction mixture is heated under nitrogen for 2-8 hours. The temperature of the reaction mixture does not exceed 200°C during the entire reaction time. After the acid value reaches 5-50 mgKOH / g, the reaction mixture is cooled to room temperature. The resulting polymer has a solids content of 95-100%.

[0053] As another example, an unsaturated polyester is prepared as follows: 150-400 parts by weight of trimethylolpropane (TMP), 400-800 parts by weight of itaconic acid (IA), and 200-600 parts by weight of 1,4-butanediol (BD) are charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a N2 inlet. Subsequently, 5-50 parts by weight of xylene as an entrainer and 0.1-1 part by weight of 4-methoxyphenol (MEHQ) as a stabilizer are added. The resulting reaction mixture is heated under N2 for 2-8 hours. The temperature of the reaction mixture does not exceed 230°C during the entire reaction time. After the acid value reaches 5-50 mgKOH / g, the reaction mixture is cooled to room temperature.

[0054] As a further example, an unsaturated polyester is prepared as follows: A reactor is charged with 100 to 400 parts by mass of trimethylolpropane, 300 to 600 parts by mass of itaconic acid, 200 to 500 parts by mass of 1,4-butanediol, 5 to 50 parts by mass of xylene, 0.1 to 1 part by mass of 4-methoxyphenol (MEHQ), and 1 to 5 parts by mass of 2,6-di-tert-butyl-4-methylphenol (BHT), and the mixture is heated to 50 to 150°C and maintained for 0.5 to 2 hours. The temperature is then raised to 100 to 200°C and maintained for an additional hour, after which it is raised to 220 to 260°C and maintained for 1 to 4 hours. The xylene is distilled off during the reaction. After cooling to 50-100°C, 200-400 parts by weight of hexohydrophthalic anhydride, 0.05-0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol (BHT), and 0.05-0.5 parts by weight of 4-methoxyphenol (MEHQ) are added to the mixture, which is then heated to 120-180°C for several hours. 400-800 parts by weight of Cadura E10P, 0.05-0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol (BHT), and 0.05-0.5 parts by weight of 4-methoxyphenol (MEHQ) are added to the reaction mixture over 0.5-3 hours, the mixture is cooled to 25-80°C, and 300-700 parts by weight of trimethylolpropane triacrylate and 300-700 parts by weight of 1,6-hexanediol diacrylate are added.

[0055] The resulting unsaturated polyester has a solids content of 65% by weight or greater and a Tg of less than 100°C.

[0056] Initiators and Catalysts Any initiator commonly used in radical polymerization may be used here, such as dibenzoyl peroxide (BPO), azobisisobutyronitrile, ethyl-2-oxocyclopentanecarboxylate (EOC) and benzopinacol (BP).

[0057] Any catalyst commonly used in silane condensation may be used here, such as phenyl acid phosphate (PAP), amine-neutralized p-toluenesulfonic acid (NARCURE 2500) and amine-neutralized phosphate (NARCURE 4575).

[0058] Dual reactive coating composition The dual reactive coating composition comprises a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of one monomer and / or unsaturated oligomer and / or unsaturated polymer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0059] Preferably, the dual reactive coating composition comprises: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% by mass to 75% by mass of unsaturated polyester and / or polyester-modified oligomer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0060] More preferably, the dual reactive coating composition comprises: a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by mass of unsaturated polyester; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0061] As an example, a dual-reactive coating composition is prepared by mixing 24% to 90% by weight of an acrylosilane polymer and 9% to 75% by weight of an unsaturated polyester with 0.5% to 10% by weight of an initiator selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC) or benzopinacol (BP), and 0.5% to 10% by weight of the catalyst phenyl acid phosphate (PAP, IsleChem, LLC), diluting with butyl acetate to a solids content of 50% by weight, and stirring until a uniform mixture is obtained.

[0062] As another example, a dual-reactive coating composition is prepared by mixing 49% to 85% by weight of an acrylosilane polymer and 14% to 50% by weight of an unsaturated polyester with 0.5% to 5% by weight of an initiator selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC), or benzopinacol (BP), and 0.5% to 5% by weight of the catalyst phenyl acid phosphate (PAP, IsleChem, LLC), diluting with butyl acetate to a solids content of 50% by weight, and stirring until a uniform mixture is obtained.

[0063] As another example, a dual-reactive coating composition is prepared by mixing 24% to 90% by weight of an acrylosilane polymer and 9% to 75% by weight of a polyurethane and / or polyester modified acrylate oligomer with 0.5% to 10% by weight of an initiator selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC) or benzopinacol (BP), and 0.5% to 10% by weight of the catalyst phenyl acid phosphate (PAP, IsleChem, LLC), diluting with butyl acetate to a solids content of 50% by weight, and stirring until a uniform mixture is obtained.

[0064] As another example, a dual-reactive coating composition is prepared by mixing 49% to 85% by weight of an acrylosilane polymer and 14% to 50% by weight of a polyester-modified acrylate oligomer with 0.5% to 5% by weight of an initiator selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC), or benzopinacol (BP), and 0.5% to 5% by weight of the catalyst phenyl acid phosphate (PAP, IsleChem, LLC), diluting with butyl acetate to a solids content of 50% by weight, and stirring until a uniform mixture is obtained.

[0065] As another example, a dual-reactive coating composition is prepared by mixing 24% to 90% by weight of an acrylosilane polymer and 9% to 75% by weight of a (meth)acrylic acid ester monomer selected from phenoxyethyl acrylate, 1,6-hexanediol diacrylate, or trimethylopropane triacrylate with 0.5% to 10% by weight of an initiator selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC), or benzopinacol (BP), and 0.5% to 10% by weight of the catalyst phenyl acid phosphate (PAP, IsleChem, LLC), diluting with butyl acetate to a solids content of 50% by weight, and stirring until a uniform mixture is obtained.

[0066] As a further example, a dual-reactive coating composition is prepared by mixing 49% to 85% by weight of an acrylosilane polymer and 14% to 50% by weight of a (meth)acrylic acid ester monomer selected from phenoxyethyl acrylate, 1,6-hexanediol diacrylate, or trimethylopropane triacrylate with 0.5% to 5% by weight of an initiator selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC), or benzopinacol (BP), and 0.5% to 5% by weight of the catalyst phenyl acid phosphate (PAP, IsleChem, LLC), diluting with butyl acetate to a solids content of 50% by weight, and stirring until a uniform mixture is obtained.

[0067] The mixture is applied to a tin test panel with a doctor blade to a wet film thickness of 200 μm and allowed to stand at 140°C for 20 minutes to yield a tack-free film of approximately 35-55 μm. After three days of post-cure, single-layer tests are conducted to verify performance, evaluating hardness (K-pendulum), crosslinking performance (MEK rub test), gel content, and cracking performance (bend test). Test results are no cracking in the bend test, 60-140 in the K-pendulum test, and 200-500 in the MEK rub test.

[0068] The resulting dual reactive coating composition allows for balanced performance of flexibility and hardness, while completely inhibiting brittleness and cracking of the topcoat or clearcoat.

[0069] Roll-to-roll coating composition Based on the dual reactive coating composition, a roll-to-roll coating composition may be prepared by adding a reactive diluent, such as phenoxyethyl acrylate (Laromer® POEA), 1,6-hexanediol diacrylate and / or trimethylolpropane triacrylate, and an additive, such as HYDROPALAT®. The solids content of the resulting roll-to-roll coating composition is 90% by weight or more, and preferably 95% by weight or more.

[0070] As an example, a roll-to-roll coating composition is prepared as follows: A roll-to-roll coating composition is obtained by uniformly mixing 40% to 60% by weight of an aliphatic urethane acrylate resin (Laromer® UA8987), 10% to 30% by weight of a polyester-modified acrylate oligomer (Laromer® PE55F), 9% to 50% by weight of an unsaturated silane-functional monomer (3-methacryloxypropyltrimethoxysilane), 19.5% to 39.5% by weight of an acrylate-based reactive diluent (1,6-hexanediol diacrylate, HDDA), 0.5% to 10% by weight of a catalyst (Narcore 2500, King Industries), 0.5% to 10% by weight of an initiator (benzopinacol, BP), and 0.5% to 10% by weight of an additive wetting agent (Hydropalat WE3220).

[0071] The coating compositions were coated onto tin panels using an Erichsen bar coater and left at 140°C for 20 minutes. After 3 days of post-cure, single-layer tests were conducted to verify performance, evaluating hardness (König pendulum), crosslink density (MEK double rub test), cupping performance (Erickson cupping), and gloss and haze measurements (specular reflection). The results show that the resulting roll-to-roll coating compositions can achieve high solids content, exceptionally high crosslinking performance, and good appearance and cupping (Erickson Index, EI).

[0072] 1K clear coat composition Based on the dual reactive coating composition, a 1K clearcoat composition may be prepared by adding reactive diluents such as phenoxyethyl acrylate (Laromer® POEA), 1,6-hexanediol diacrylate and / or trimethylolpropane triacrylate, additives such as BYK3190, and cosolvents such as 1-butanol. The VOC of the resulting clearcoat composition is 420 g / L or less, and preferably 350 g / L or less.

[0073] As an example, a 1K clearcoat composition is prepared as follows: A 1K clear coat composition is obtained by uniformly mixing 10% to 60% by weight of an acrylate / styrene resin having a silane functional group, 10% to 60% by weight of an unsaturated polyester resin, 19.5% to 69.5% by weight of an acrylate-based reactive diluent (trimethylolpropane triacrylate, TMPTA), 4% to 10% by weight of a silane-based sag control agent (SCA), 1% to 10% by weight of a catalyst (Narcure 4575, King Industries), 0.4% to 10% by weight of an initiator (benzopinacol, BP), 5% to 20% by weight of a co-solvent (1-butanol), and 0.1% to 2% by weight of an additive leveling agent (BYK3190). The coating composition exhibited thixotropic behavior with a low-shear viscosity to high-shear viscosity ratio of η2 (shear rate = 1 s-1) / η1 (shear rate = 1000 s-1) > 8. The VOC value of the coating composition was measured to be 325 g / L, which is a significant reduction in VOC levels compared to conventional 1K coating compositions (VOC = 450-550 g / L).

[0074] The compositions were sprayed onto tin panels coated with a black basecoat and allowed to stand at 140°C for 20 minutes. After three days of post-curing, single-layer tests were conducted to verify performance, evaluating hardness (König pendulum), crosslink density (MEK double rub test), alkaline and acid etching resistance, cupping performance (Erickson cupping), appearance (Wavescan), and gloss and haze measurements (specular reflection). The results show that the resulting 1K coating composition can achieve high solids content and low VOC values, excellent crosslinking performance, good appearance, cupping (Erickson Index, EI), and acid and alkaline etching resistance.

[0075] Implementation A first embodiment is a dual reactive coating composition, the coating composition comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of one monomer and / or unsaturated oligomer and / or unsaturated polymer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0076] A second embodiment is a dual reactive coating composition, the coating composition comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% by mass to 75% by mass of unsaturated polyester and / or polyurethane-modified oligomer and / or polyester-modified oligomer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0077] A third embodiment is a dual reactive coating composition, the coating composition comprising: a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by mass of unsaturated polyester; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0078] A fourth embodiment is the dual reactive coating composition of any one of embodiments 1 to 3, wherein the crosslinkable silane-functional polymer is i) 20% to 50% by weight of a compound of formula I H2C=CH-(CH2) n -Si-(R1) m (R2) 3-m (wherein R1 is an aryl or alkyl group having 1 to 6 carbon atoms, R2 is an alkoxyl group having 1 to 6 carbon atoms, m is 0 or 1, and n is an integer of 0 to 3), ii) 50% to 80% by weight of a (meth)acrylate monomer, and iii) 0 to 30% by mass of styrene monomer and all weight percents are based on the total weight of the silane-functional polymer.

[0079] A fifth embodiment is the dual reactive coating composition of any one of embodiments 1 to 4, wherein the crosslinkable silane functional polymer is i) 20% by mass to 50% by mass of vinyltrimethoxysilane; ii) 50% to 80% by weight of at least one (meth)acrylate monomer selected from methyl methacrylate, n-butyl acrylate, ethylhexyl acrylate, and hydroxypropyl methacrylate; and iii) 0% to 30% by mass of styrene and all weight percents are based on the total weight of the silane-functional polymer.

[0080] A sixth embodiment is the dual-reactive coating composition of any one of the first to fifth embodiments, wherein the crosslinkable silane-functional oligomer or polymer has an average molecular weight of less than 30,000, and preferably less than 20,000.

[0081] A seventh embodiment is the dual-reactive coating composition of any one of the first to sixth embodiments, wherein the crosslinkable silane-functional polymer has a hydroxyl number of 0 to 150 mg KOH / g and an acid number of 0 to 50 mg KOH / g.

[0082] An eighth embodiment is the dual reactive coating composition of any one of embodiments 1 and 4 to 7, wherein the monomer or unsaturated oligomer or unsaturated polymer has a weight average molecular weight of 200 to 20,000.

[0083] A ninth embodiment is the dual-reactive coating composition of any one of embodiments 1 and 4 to 8, wherein the monomer or unsaturated oligomer or unsaturated polymer has a hydroxyl number of 0 to 350 mg KOH / g and an acid number of 0 to 150 mg KOH / g.

[0084] A tenth embodiment is the dual-reactive coating composition of any one of embodiments 2 to 3, wherein the unsaturated polyester is made from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride thereof with at least one saturated aliphatic diol.

[0085] An eleventh embodiment is the dual-reactive coating composition according to embodiment 10, wherein the unsaturated polyester is prepared from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride selected from maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and fumaric acid with at least one saturated aliphatic diol selected from neopentyl glycol, 1,4 butanediol, 1,6 hexanediol, and cyclohexyldimethanol.

[0086] A twelfth embodiment is the dual-reactive coating composition of any one of the first to eleventh embodiments, wherein the initiator is at least selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC), and benzopinacol (BP).

[0087] A thirteenth embodiment is the dual-reactive coating composition of any one of the preceding embodiments, wherein the catalyst is at least selected from phenyl acid phosphate (PAP), amine-neutralized p-toluenesulfonic acid (NARCURE 2500), and amine-neutralized phosphate (NARCURE 4575).

[0088] A fourteenth embodiment is the dual-reactive coating composition of any one of the preceding embodiments, wherein the crosslinkable silane-functional polymer is prepared by a two-step process: in a first step, a vinylalkoxysilane monomer, a (meth)acrylate monomer, and an optional styrene monomer and an initiator are blended with an organic solvent and heated; and in a second step, a (meth)acrylate monomer, an optional styrene monomer, and an initiator are added, wherein the (meth)acrylate monomer and the optional styrene monomer are added in two or more batches, the time between each batch being 30 minutes or more, and the weight ratio of the (meth)acrylate monomer and the optional styrene monomer added in each batch is 1:15 to 15:1.

[0089] A fifteenth embodiment is the dual-reactive coating composition of any one of the first to fourteenth embodiments, further comprising a silane-functional sag control agent.

[0090] A sixteenth embodiment is a film obtained from curing and drying the dual reactive coating composition of any one of embodiments 1 to 15.

[0091] A seventeenth embodiment is a substrate coated with the dual reactive coating composition of any one of embodiments 1 to 15.

[0092] An eighteenth embodiment is the substrate of embodiment 17, wherein the substrate is an automobile or truck.

[0093] A nineteenth embodiment is a method for making the dual reactive coating composition of embodiment 1, comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of one monomer and / or unsaturated oligomer and / or unsaturated polymer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0094] A twentieth embodiment is a method for making the dual reactive coating composition of embodiment 2, comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% by mass to 75% by mass of unsaturated polyester and / or polyurethane-modified oligomer and / or polyester-modified oligomer; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0095] A twenty-first embodiment is a method for making the dual reactive coating composition of embodiment 3, comprising: a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by mass of unsaturated polyester; c). 0.5% to 10% by weight of one initiator, and d). 0.5% to 10% by mass of one catalyst and all weight percentages are based on the total weight of the coating composition.

[0096] A twenty-second embodiment is a roll-to-roll coating composition comprising the duplex reactive coating composition of any one of embodiments 1 to 15, a reactive diluent, and an additive, wherein the solids content of the resulting roll-to-roll coating composition is 90% by weight or more, and preferably 95% by weight or more.

[0097] A 23rd embodiment is a 1K clearcoat composition comprising the duplex reactive coating composition of any one of embodiments 1 to 15, a reactive diluent, an additive, and a co-solvent, wherein the resulting clearcoat composition has a VOC of 420 g / L or less, and preferably 350 g / L or less. [Example]

[0098] The present invention will now be described with reference to examples which are not intended to limit the invention.

[0099] Examples 1-3: Preparation of vinylsilane-containing acrylate polymers The reactor was charged with 378 parts by weight of Shellsol A, and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). Then, over a period of 5.38 hours, an initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of Shellsol A) was metered in at a uniform rate with stirring. Starting 15 minutes after the start of the initiator feed, Feed 1, consisting of VTMS, was metered in at a uniform rate with stirring over a period of 1 hour. Starting 15 minutes after the start of the initiator feed, Feeds 2-a to 2-e, consisting of methyl methacrylate and n-butyl acrylate with the compositions shown in Table 1 below, were metered in at a uniform rate over a period of 1 hour with stirring, each feed. After complete addition of the initiator solution (0.15 hours after the end of the monomer mixture addition), the reactor was heated to 155°C and stirring was continued for 45 minutes at the stated pressure, after which a solution of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of Shellsol A was added at a uniform rate over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content, number average molecular weight, glass transition temperature, and monomer residue of the resulting copolymer solution are shown in Table 2 below.

[0100] [Table 1]

[0101] [Table 2]

[0102] Examples 4-13: Preparation of vinylsilane-containing acrylate / styrene copolymers The reactor was charged with 378 parts by weight of Shellsol A, and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). Then, over a period of 5.38 hours, an initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of Shellsol A) was metered in at a uniform rate with stirring. Starting 15 minutes after the start of the initiator feed, Feed 1, consisting of VTMS, was metered in at a uniform rate with stirring over a period of 1 hour. Starting 15 minutes after the start of the initiator feed, Feeds 3-a to 3-e, consisting of styrene, methyl methacrylate, and n-butyl acrylate, with the compositions shown in Table 3 below, were metered in at a uniform rate over a period of 1 hour with stirring, each feed being added at a uniform rate. After complete addition of the initiator solution (0.15 hours after the end of the monomer mixture addition), the reactor was heated to 155°C and stirring continued at the stated pressure for 45 minutes, after which a solution consisting of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of Shellsol A was added again at a uniform rate over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content, number average molecular weight, glass transition temperature, and monomer residue of the resulting copolymer solution are shown in Table 4 below.

[0103] [Table 3]

[0104] [Table 4]

[0105] Examples 14-15: Preparation of vinylsilane-containing acrylate / styrene / ethylhexyl acrylate copolymers The reactor was charged with 378 parts by weight of Shellsol A, and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). Then, over a period of 5.38 hours, an initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of Shellsol A) was metered in at a uniform rate with stirring. Starting 15 minutes after the start of the initiator feed, Feed 1, consisting of VTMS, was metered in at a uniform rate with stirring over a period of 1 hour. Starting 15 minutes after the start of the initiator feed, Feeds 4-a to 4-e, consisting of styrene, methyl methacrylate, and ethylhexyl acrylate, with the compositions shown in Table 5 below, were metered in at a uniform rate over a period of 1 hour with stirring, each feed being added at a uniform rate. After complete addition of the initiator solution (0.15 hours after the end of the monomer mixture addition), the reactor was heated to 155°C and stirring continued at the stated pressure for 45 minutes, after which a solution consisting of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of Shellsol A was added at a uniform rate again over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content, number average molecular weight, glass transition temperature, and monomer residue of the resulting copolymer solution are shown in Table 6 below.

[0106] [Table 5]

[0107] [Table 6]

[0108] Example 16: Preparation of vinylsilane-containing acrylate polymer in butyl acetate The reactor was charged with 378 parts by weight of butyl acetate and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). An initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of butyl acetate) was then metered in uniformly over a period of 5.38 hours while stirring. Starting 15 minutes after the start of the initiator feed, 659.2 parts by weight of VTMS were metered in uniformly over a period of 1 hour while stirring. In a first step, a monomer mixture consisting of 91.2 parts by weight of methyl methacrylate and 91.2 parts by weight of n-butyl acrylate was simultaneously metered in uniformly over a period of 1 hour while stirring. In a second step, a monomer mixture consisting of 167.8 parts by weight of methyl methacrylate and 167.8 parts by weight of n-butyl acrylate was metered in uniformly over a period of 1 hour while stirring. In a third step, a monomer mixture consisting of 102 parts by weight of methyl methacrylate and 102 parts by weight of n-butyl acrylate was metered in at a uniform rate over 1 hour while stirring. In a fourth step, a monomer mixture consisting of 74 parts by weight of methyl methacrylate and 74 parts by weight of n-butyl acrylate was metered in at a uniform rate over 1 hour while stirring. In a fifth step, a monomer mixture consisting of 59.4 parts by weight of methyl methacrylate and 59.4 parts by weight of n-butyl acrylate was metered in at a uniform rate over 1 hour while stirring. After complete addition of the initiator solution (0.15 hours after the end of the addition of the monomer mixture), the reactor was heated to 155°C and stirring was continued for 45 minutes at the stated pressure. After that, a solution consisting of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of butyl acetate was added again at a uniform rate over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content of the resulting copolymer solution was 73.0%. The weight average molecular weight of the copolymer was 5002 g / mol. The glass transition temperature of the copolymer was -21.0°C. The residual monomer contents of methyl methacrylate, n-butyl acrylate, and vinyltrimethoxysilane were 0.03%, <0.01%, and 0.26%, respectively.

[0109] Examples 17-19: Preparation of vinylsilane-containing acrylate / styrene copolymers in butyl acetate The reactor was charged with 378 parts by weight of butyl acetate, and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). An initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of butyl acetate) was then metered in at a uniform rate with stirring over a period of 5.38 hours. Starting 15 minutes after the start of the initiator feed, Feed 1, consisting of VTMS, was metered in at a uniform rate with stirring over a period of 1 hour. Starting 15 minutes after the start of the initiator feed, Feeds 3-f to 3-j, consisting of styrene, methyl methacrylate, and n-butyl acetate, with the compositions shown in Table 7 below, were metered in at a uniform rate over a period of 1 hour with stirring, each time. After complete addition of the initiator solution (0.15 hours after the end of the monomer mixture addition), the reactor was heated to 155°C and stirring was continued for 45 minutes at the stated pressure, after which a solution of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of butyl acetate was added again at a uniform rate over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content, number average molecular weight, glass transition temperature, and monomer residue of the resulting copolymer solution are shown in Table 8 below.

[0110] [Table 7]

[0111] [Table 8]

[0112] Examples 20-21: Preparation of vinylsilane-containing acrylate / styrene / ethylhexyl acrylate copolymer in butyl acetate The reactor was charged with 378 parts by weight of butyl acetate, and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). An initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of butyl acetate) was then metered in at a uniform rate with stirring over a period of 5.38 hours. Starting 15 minutes after the start of the initiator feed, Feed 1, consisting of VTMS, was metered in at a uniform rate with stirring over a period of 1 hour. Starting 15 minutes after the start of the initiator feed, Feeds 4-a to 4-e, consisting of styrene, methyl methacrylate, and ethylhexyl acrylate, with the compositions shown in Table 9 below, were metered in at a uniform rate over a period of 1 hour with stirring, each feed being added at a uniform rate. After complete addition of the initiator solution (0.15 hours after the end of the monomer mixture addition), the reactor was heated to 155°C and stirring was continued for 45 minutes at the stated pressure, after which a solution of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of butyl acetate was added again at a uniform rate over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content, number average molecular weight, glass transition temperature, and monomer residue of the resulting copolymer solution are shown in Table 10 below.

[0113] [Table 9]

[0114] [Table 10]

[0115] Examples 22-23: Preparation of vinylsilane-containing acrylate / styrene / hydroxy-functional acrylate copolymers The reactor was charged with 378 parts by weight of Shellsol A, and this initial charge was heated to 145°C. The reactor was placed under pressure (3.5 bar). Then, over a period of 5.38 hours, an initiator solution (82.9 parts by weight of di-tert-butyl peroxide in 68.6 parts by weight of Shellsol A) was metered in at a uniform rate with stirring. Starting 15 minutes after the start of the initiator feed, Feed 1, consisting of VTMS, was metered in at a uniform rate with stirring over a period of 1 hour. Starting 15 minutes after the start of the initiator feed, Feeds 5-a to 5-e, consisting of styrene, methyl methacrylate, and hydroxypropyl methacrylate, with the compositions shown in Table 11 below, were metered in at a uniform rate over a period of 1 hour with stirring, each feed. After complete addition of the initiator solution (0.15 hours after the end of the monomer mixture addition), the reactor was heated to 155°C and stirring continued at the stated pressure for 45 minutes, after which a solution consisting of 27 parts by weight of di-tert-butyl peroxide in 22.4 parts by weight of Shellsol A was added again at a uniform rate over 1.2 hours. The batch was then held at the stated temperature and pressure for an additional 1.1 hours. The reaction mixture was then cooled to 60°C and let down to atmospheric pressure. The solids content, number average molecular weight, glass transition temperature, and monomer residue of the resulting copolymer solution are shown in Table 12 below.

[0116] [Table 11]

[0117] [Table 12]

[0118] Example 24: Unsaturated polyester based on itaconic acid in butyl acetate 342.3 parts by weight of trimethylolpropane (TMP), 819.2 parts by weight of itaconic acid (IA), and 536.2 parts by weight of 1,4-butanediol (BD) were charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a nitrogen inlet. Subsequently, 20 parts by weight of xylene was added as an entrainer, 0.252 parts by weight of 2,6-di-tert-butyl-4-methylphenol (BHT) as a stabilizer, and 0.756 parts by weight of tetra-n-butyl titanate (TBT) as a catalyst. The resulting reaction mixture was heated under nitrogen for 5 hours. The temperature of the reaction mixture did not exceed 200°C during the entire reaction time. After the acid value reached 52 mg KOH / g, the reaction mixture was cooled to 80°C, and 580.4 parts by weight of butyl acetate (BA) was added to dilute the polymer. The solids content of the resulting polymer solution was 69.03%. The unsaturated polyester obtained had a number average molecular weight of 509 g / mol, a mass average molecular weight of 1260 g / mol, an OH value of 301.7 mgKOH / g, and a glass transition temperature of 65.9°C.

[0119] Example 25: Unsaturated polyester based on maleic anhydride in butyl acetate 341.3 parts by weight of trimethylolpropane (TMP), 615.7 parts by weight of maleic anhydride (MAH), and 618 parts by weight of neopentyl glycol (NPG) were charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a nitrogen inlet. Subsequently, 20 parts by weight of xylene was added as an entrainer. The resulting reaction mixture was heated under nitrogen for 4 hours. The temperature of the reaction mixture did not exceed 200°C during the entire reaction time. After the acid value reached 12 mg KOH / g, the reaction mixture was cooled to 80°C, and 525 parts by weight of butyl acetate (BA) was added to dilute the polymer. The solids content of the resulting polymer solution was 69.00%. The resulting unsaturated polyester had a number average molecular weight of 801 g / mol, a weight average molecular weight of 2047 g / mol, an OH value of 272.2 mg KOH / g, and a glass transition temperature of 0.6°C.

[0120] Example 26: Maleic anhydride-based unsaturated polyester 341.3 parts by weight of trimethylolpropane (TMP), 615.7 parts by weight of maleic anhydride (MAH), and 618 parts by weight of neopentyl glycol (NPG) were charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a nitrogen inlet. Subsequently, 20 parts by weight of xylene as an entrainer and 0.158 parts by weight of 2,6-di-tert-butyl-4-methylphenol (BHT) as a stabilizer were added. The resulting reaction mixture was heated under nitrogen for 4 hours. The temperature of the reaction mixture did not exceed 200°C during the entire reaction time. After the acid value reached 17 mg KOH / g, the reaction mixture was cooled to room temperature. The solids content of the resulting polymer was 100%. The resulting unsaturated polyester had a number average molecular weight of 805 g / mol, a mass average molecular weight of 1937 g / mol, an OH value of 264.4 mg KOH / g, and a glass transition temperature of -14.0°C.

[0121] Example 27: Unsaturated polyester based on maleic anhydride in reactive diluents 1595.2 parts by weight of Example 23 was charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a N2 inlet and heated to 80°C. 262 parts by weight of hexanediol diacrylate (HDDA) and 262 parts by weight of trimethylolpropane triacrylate (TMPTA) were then added to dilute the polymer. The solids content of the resulting polymer solution was 75.00%. The resulting unsaturated polyester had a number average molecular weight of 805 g / mol, a weight average molecular weight of 1937 g / mol, an OH number of 256.6 mg KOH / g, and a glass transition temperature of -14.0°C.

[0122] Example 28: Itaconic Acid-Based Unsaturated Polyester 273.8 parts by weight of trimethylolpropane (TMP), 655.3 parts by weight of itaconic acid (IA), and 429.0 parts by weight of 1,4-butanediol (BD) were charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a N2 inlet. Subsequently, 16 parts by weight of xylene as an entrainer and 0.4 parts by weight of 4-methoxyphenol (MEHQ) as a stabilizer were added. The resulting reaction mixture was heated under N2 for 4 hours. The temperature of the reaction mixture did not exceed 230°C during the entire reaction time. After the acid value reached 43 mg KOH / g, the reaction mixture was cooled to room temperature. The solids content of the resulting polymer was 100.00%. The resulting unsaturated polyester had a number average molecular weight of 907 g / mol, a weight average molecular weight of 2030 g / mol, an OH value of 255.6 mg KOH / g, and a glass transition temperature of 9.6°C.

[0123] Example 29: Itaconic Acid-Based Unsaturated Polyester in Reactive Diluent 1374.5 parts by weight of the unsaturated polyester obtained from Example 28 was charged into a stainless steel reactor equipped with a reflux condenser, a water separator, and a N2 inlet and heated to 80°C. 363 parts by weight of hexanediol diacrylate (HDDA) and 363 parts by weight of trimethylolpropane triacrylate (TMPTA) were then added to dilute the polymer. The solids content of the resulting polymer solution was 65.00%. The resulting unsaturated polyester had a number average molecular weight of 805 g / mol, a weight average molecular weight of 1937 g / mol, an OH number of 248.3 mg KOH / g, and a glass transition temperature of 9.6°C.

[0124] Example 30: Hydrophobically modified itaconic acid and hexahydrophthalic anhydride based unsaturated polyester in a reactive diluent 210 g of trimethylolpropane, 503 g of itaconic acid, 329 g of 1,4-butanediol, 12 g of xylene, 0.5 g of MEHQ, and 1.5 g of BHT were added to a reactor and heated to 100°C and held for 1 hour. The temperature was increased to 160°C and held for an additional hour, then increased to 230°C and held for 2 hours. Xylene was distilled off during the reaction. After cooling to 80°C, 322 g of hexohydrophthalic anhydride, 100 mg of BHT, and 80 mg of MEHQ (hydroquinone monomethyl ether) were added to the mixture and heated to 140°C for several hours. 623 g of Cadura E10P, 100 mg of BHT, and 80 mg of MEHQ were added to the reaction mixture over 1.5 hours, cooled to 40°C, and 500 g of trimethylolpropane triacrylate and 500 g of 1,6-hexanediol diacrylate were added. The reaction yielded a solvent-free, low-viscosity unsaturated polyester resin (67% in reactive diluent) with an acid number of 10-50 mg KOH / g, a hydroxyl number of 100-300 mg KOH / g, and a glass transition temperature of -55°C.

[0125] Example 31: Silane-based sag control agent (12% by weight in butyl acetate) 44.25 g of 3-aminopropyltriethoxysilane was dissolved in 37.05 g of butyl acetate and then poured into a 1 L metal bucket containing 370.43 g of butyl acetate. This solution was stirred in a dissolver for 2 minutes at 2000 rpm. Next, 16.53 g of hexamethylene diisocyanate was dissolved in 31.74 g of butyl acetate and poured into an automatic dispenser. The liquid in the metal bucket was stirred in a dissolver at a speed of 2000 rpm. The isocyanate solution was then added dropwise over 20 minutes. After this step, the solution was held in the disperser for an additional 2 minutes. A total solids content of 12% by weight, η (shear rate = 1000 s -1 ) = 46 mPas, η2 (shear rate = 1 s -1 )=13759 mPa.s.

[0126] Example 32: Silane-based sag control agent (12% by weight in butyl acetate) 88.50 g of 3-aminopropyltriethoxysilane was dissolved in 37.05 g of butyl acetate and then poured into a 1 L metal bucket containing 293.78 g of butyl acetate. This solution was stirred in a dissolver at 2000 rpm for 2 minutes. Next, 33.06 g of hexamethylene diisocyanate was dissolved in 47.61 g of butyl acetate and poured into an automatic dispenser. The liquid in the metal bucket was stirred in a dissolver at a speed of 2000 rpm. The isocyanate solution was then added dropwise over 30 minutes. After this step, the solution was held in the disperser for an additional 2 minutes. A total solids content of 24% by weight, η (shear rate = 1000 s -1 ) = 60 mPas, η2 (shear rate = 1 s -1 )=16833 mPa.s.

[0127] Examples 33-50: Dual Reactive Coating Compositions The components of Examples 33-50 were mixed with initiators dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC) or benzopinacol (BP), and phenyl acid phosphate catalyst (PAP, IsleChem, LLC) as shown in the table below, diluted with butyl acetate to a solids content of 50% by weight, and stirred until a homogeneous mixture was obtained. The mixture was applied to a tin test panel with a doctor blade to a wet film thickness of 200 nm and allowed to stand at 140°C for 20 minutes to yield a tack-free film of approximately 35-55 nm. After three days of post-cure, single-layer testing was performed to evaluate performance, evaluating hardness (K pendulum), crosslinking performance (MEK rub test), gel content, and cracking performance (flex test). The values ​​are shown in Table 13 below. The dried and cured films of Examples 33-50 were obtained as tack-free, clear coatings.

[0128] [Table 13]

[0129] Examples 51-53: Preparation and application of roll-to-roll coating compositions Aliphatic urethane acrylate resin (Laromer® UA8987), polyester-modified acrylate oligomers (Laromer® PE55F, Laromer® PE9121, Laromer® PE9105), unsaturated silane-functional monomer (3-methacryloxypropyltrimethoxysilane), acrylate-based reactive diluent (1,6-hexanediol diacrylate, HDDA; Laromer® POEA), catalyst (Narcure 2500, King Industries), initiator (benzopinacol, BP), and additive wetting agent (Hydropalat WE3220) were uniformly mixed in the amounts shown in Table 14 below to obtain roll-to-roll coating compositions for Examples 51 to 53. The coating compositions were applied to tin panels using an Erichsen bar coater and allowed to stand at 140°C for 20 minutes. After three days of post-cure, single layer tests were conducted to verify performance and evaluated hardness (Koenig pendulum), crosslink density (MEK double rub test), cupping performance (Erickson cupping), and gloss and haze measurements (specular reflection). The dried and cured films of Examples 51-53 were obtained as tack-free, clear coatings. The values ​​are shown in Table 14 below.

[0130] [Table 14]

[0131] Example 54: Preparation and spray application of a 1K clearcoat composition A silane-functionalized acrylate / styrene resin, an unsaturated polyester resin, an acrylate-based reactive diluent (trimethylolpropane triacrylate, TMPTA), a silane-based sag control agent (SCA), a catalyst (Narcure 4575, King Industries), an initiator (benzopinacol, BP), a cosolvent (1-butanol), and an additive leveling agent (BYK 3190) were uniformly mixed in the amounts shown in Table 15 below to obtain a 1K clearcoat composition (Example 54). The coating composition exhibited thixotropic behavior, with a low-shear viscosity to high-shear viscosity ratio (η2 (shear rate = 1 s-1) / η1 (shear rate = 1000 s-1)) of >8. The VOC value of the coating composition was measured to be 325 g / L, which is a significant reduction in VOC levels compared to conventional 1K coating compositions (VOC = 450-550 g / L). The compositions were sprayed onto tin panels coated with a black basecoat and allowed to stand at 140°C for 20 minutes. After three days of post-cure, single-layer tests were conducted to verify performance, evaluating hardness (König pendulum), crosslink density (MEK double rub test), alkaline and acid etch resistance, cupping performance (Erickson cupping), appearance (Wavescan), and gloss and haze measurements (specular reflection). The dried and cured film of Example 62 was obtained as a tack-free, transparent coating on the black basecoat. The values ​​are shown in Table 15 below. Example 54 clearly demonstrates that the technical approach of the present invention can achieve higher solids content, lower VOC values, significantly higher crosslinking performance, better appearance, comparable cupping (Erickson Index, EI), and better acid and alkaline etch resistance compared to conventional 1K polyurethane or acid / epoxy clearcoats.

[0132] [Table 15]

[0133] <Resin characteristic evaluation> Those skilled in the art know how to determine the acid number, OH number, epoxy equivalent weight, solids content, number average molecular weight and weight average molecular weight, which are determined according to the standards set out below.

[0134] The acid number is determined in accordance with DIN EN ISO 2114 (date: June 2002). The OH number is determined in accordance with DIN 53240-2 (date: November 2007). The epoxy equivalent weight is determined in accordance with DIN EN ISO 3001 (date: November 1999). The solids content is determined in accordance with DIN EN ISO 3251 (date: June 2008). The number-average and weight-average molecular weights are determined in accordance with DIN 55672-1 (date: August 2007).

[0135] <Solid content> The solids content of the clear coat compositions of Examples 51 to 54 is calculated based on the mass loss of the composition at 130°C for 60 minutes.

[0136] <Performance test> (1) Hardness The surface hardness of a coating is measured mechanically using a pendulum damping test according to König or Persoz. The hardness of a coating is determined by the frequency of oscillations made by the pendulum between two defined angles (6 to 3 degrees for the König pendulum, or 12 to 4 degrees for the Persoz pendulum). The frequency of oscillations increases as the coating surface hardens. The measurement method is standardized in ISO 1522.

[0137] (2) Solvent friction test To assess crosslinking and confirm that a coating system has cured, a solvent rub test using methyl ethyl ketone (MEK) as the solvent is performed. This test is widely used in the coatings industry because it provides a quick, relative assessment of the degree of cure without waiting for long-term exposure results. Rubs are counted as double rubs (one forward and one backward constitutes a double rub), which provides a measure of MEK resistance and the degree of cure. The MEK double rub value for a traditional 2K polyurethane or acid / epoxy clearcoat is approximately 200 rubs.

[0138] (3) Bending test The flexural test is used to determine the effect of bending on the elasticity, adhesion, and elongation properties of cured coatings on metal panels. The cone flexural tester consists of a frame with a roller-mounted bending lever that pivots on a steel conical mandrel with a diameter of 3.2 to 38.1 mm. Specimens can be bent along part or all of the length of the mandrel, and results (cracking) corresponding to different test diameters can be observed in a single run.

[0139] (4) VOC testing A gravimetric method was applied to measure the volatile organic compound (VOC) emissions of the coating compositions. The VOC content was measured based on the mass loss of the composition when heated at 105°C for 60 minutes.

[0140] (5) Rheological testing The thixotropic effect of the sauce-making agent and coating composition was characterized using an Anton Paar rheometer. 2D rheological profiles were measured by rapid shear rate changes. The test consisted of two sections with two different shear rates (shear rate 1 = 1 s -1 ), shear rate 2 = 1000 s -1 The thixotropy index is defined as the ratio of the viscosity of a sample at high shear (η2) and low shear (η1).

[0141] (6) Cupping test Erickson cupping is used to evaluate flexibility by testing the resistance of the coating to fracture. In this test, a 20mm diameter hemispherical punch is used to slowly stretch a dried and cured coating on a metal panel at room temperature. The test is continued until fracture of the coating is observed, and the depth of the dent (in mm) at fracture is called the Erickson Index, or IE. Conventional coatings have an IE greater than 5mm.

[0142] (7) Appearance The appearance of the dried and cured coating is evaluated by surface texture, measured with a BYK Wavescan Dual. Surface texture is a mixture of various textures, ranging from very fine to very coarse. The BYK Wavescan Dual measures surface texture at different scale levels and classifies it into six categories identified by wavelength (Du, Wa, Wb, Wc, Wd, We). Based on these measurement data, Du, Lw, and Sw are calculated, indicating the level of appearance of the coating. Smaller values ​​of Du, Lw, and Sw indicate better appearance performance. Good appearance performance is usually defined as simultaneously meeting Lw<5 and Sw<20.

[0143] (8) Gloss and haze measurement The gloss and haze of dried and cured coatings are evaluated by measuring the specular gloss of the surface with a glossmeter. Gloss is determined by shining a beam of light of a constant intensity and angle onto the surface and measuring the amount of light reflected at equal reflection angles of 20° and 60°. Haze is the result of subtle changes in the direction of reflected light due to microscopic surface structure, resulting in bloom adjacent to the specular (gloss) angle. The surface has reduced reflection contrast and a slight milky white effect. Glossmeters can quantify orange peel by measuring the distinctness of image (DOI) as well as haze. Good appearance performance is typically defined as simultaneously achieving DOI > 90 and haze < 20.

[0144] (9) Acid resistance Acid etch resistance is evaluated by the 20° gloss retention after acid treatment. Acid treatment was performed by immersion in 0.35M Fe(II)SO4 solution in 0.5M H2SO4. During testing, the coating was completely covered in acid and stored at 70°C for 60 minutes. The 20° gloss before and after acid treatment was compared. Higher gloss retention indicates better oxidation resistance. 20° gloss retention for conventional 2K polyurethane or acid / epoxy clearcoats is approximately 70%.

[0145] (10) Alkaline etching resistance Alkaline etching resistance is evaluated by the 20° gloss retention after alkaline treatment. The alkaline treatment was performed by immersing the coating in a 1% sodium hydroxide solution. During the test, the coating was completely covered with the alkaline solution and stored at 70°C for 60 minutes. The 20° gloss before and after alkaline treatment was compared. A higher gloss retention indicates better alkaline etching resistance. The 20° gloss retention of a conventional 2K polyurethane or acid / epoxy clear coat is approximately 60%.

Claims

1. a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of an unsaturated polyester; c). 0.5% to 10% by weight of one radical polymerization initiator, and d). 0.5% to 10% by weight of one silane condensation catalyst 1. A dual reactive coating composition comprising: the unsaturated polyester is prepared from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride thereof with at least one saturated aliphatic diol; A dual reactive coating composition, wherein all weight percentages are based on the total weight of said coating composition.

2. a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by weight of an unsaturated polyester; c). 0.5% to 10% by weight of one radical polymerization initiator, and d). 0.5% to 10% by weight of one silane condensation catalyst 1. A dual reactive coating composition comprising: the unsaturated polyester is prepared from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride thereof with at least one saturated aliphatic diol; A dual reactive coating composition, wherein all weight percentages are based on the total weight of said coating composition.

3. the crosslinkable silane-functional polymer i) 20% to 50% by weight of a compound of formula I H ２ C=CH-(CH ２ ) ｎ -Si-(R １ ) ｍ (R ２ ) ３－ｍ (In the formula, R １ is an aryl or alkyl group having C1 to C6, and R ２ is an alkoxyl group having 1 to 6 carbon atoms, m is 0 or 1, and n is an integer of 0 to 3; ii) 50% to 80% by weight of a (meth)acrylate monomer, and iii) 0 to 30% by weight of styrene monomer 3. The dual reactive coating composition of claim 1 or 2, prepared by polymerization of a monomer comprising:

4. the crosslinkable silane-functional polymer i) 20% to 50% by weight of vinyltrimethoxysilane; ii) 50% to 80% by weight of at least one (meth)acrylate monomer selected from methyl methacrylate, n-butyl acrylate, ethylhexyl acrylate, and hydroxypropyl methacrylate; and iii) 0 to 30% by weight of styrene 4. The dual reactive coating composition of claim 1, wherein the dual reactive coating composition is prepared by polymerization of a monomer comprising:

5. 5. The dual reactive coating composition of claim 1, wherein the crosslinkable silane-functional oligomer or polymer has a weight average molecular weight of less than 30,000.

6. The dual reactive coating composition of any one of claims 1 to 5, wherein the crosslinkable silane functional polymer has a hydroxyl number of 0 to 150 mg KOH / g and an acid number of 0 to 50 mg KOH / g.

7. The dual reactive coating composition of any one of claims 3 to 6, wherein the unsaturated monomer or oligomer or polymer has a weight average molecular weight of 200 to 20,000.

8. 8. The dual reactive coating composition of any one of claims 3 to 7, wherein the unsaturated monomer or oligomer or polymer has a hydroxyl number of 0 to 350 mg KOH / g and an acid number of 0 to 150 mg KOH / g.

9. 10. The dual reactive coating composition of claim 1, wherein the unsaturated polyester is prepared from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride selected from maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and fumaric acid with at least one saturated aliphatic diol selected from neopentyl glycol, 1,4 butanediol, 1,6 hexanediol, and cyclohexyldimethanol.

10. 10. The dual reactive coating composition of any one of claims 1 to 9, wherein the radical polymerization initiator is at least selected from dibenzoyl peroxide (BPO), ethyl-2-oxocyclopentanecarboxylate (EOC), and benzopinacol (BP).

11. 11. The dual reactive coating composition of any one of claims 1 to 10, wherein the silane condensation catalyst is at least selected from phenyl acid phosphate (PAP), amine-neutralized p-toluenesulfonic acid (NARCURE 2500), and amine-neutralized phosphate (NARCURE 4575).

12. 12. The dual reactive coating composition of any one of claims 1 to 11, further comprising a silane-functional sag control agent.

13. 13. A film obtained from curing and drying the dual reactive coating composition of any one of claims 1 to 12.

14. 13. A substrate coated with the dual reactive coating composition of any one of claims 1 to 12.

15. The substrate of claim 14, wherein the substrate is an automobile or truck.

16. 10. A method for producing the dual reactive coating composition of claim 1, comprising: a). 24% to 90% by weight of crosslinkable silane-functional monomers and / or oligomers and / or polymers; b). 9% to 75% by weight of an unsaturated polyester; c). 0.5% to 10% by weight of one radical polymerization initiator, and d). 0.5% to 10% by weight of one silane condensation catalyst wherein the unsaturated polyester is prepared from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride with at least one saturated aliphatic diol, all weight percentages being based on the total weight of the coating composition.

17. 3. A method for producing the dual reactive coating composition of claim 2, comprising: a). 24% to 90% by weight of a crosslinkable silane-functional polymer; b). 9% to 75% by weight of an unsaturated polyester; c). 0.5% to 10% by weight of one radical polymerization initiator, and d). 0.5% to 10% by weight of one silane condensation catalyst wherein the unsaturated polyester is prepared from the condensation of at least one monounsaturated linear aliphatic dicarboxylic acid or anhydride thereof with at least one saturated aliphatic diol, all weight percentages being based on the total weight of the coating composition.

18. A roll-to-roll coating composition comprising the duplex reactive coating composition of any one of claims 1 to 12, a reactive diluent, and an additive, wherein the solids content is 90 wt% or more.

19. 13. A 1K clearcoat composition comprising the duplex reactive coating composition of any one of claims 1 to 12, a reactive diluent, an additive, and a co-solvent, wherein the VOC (volatile organic compounds) is 420 g / L or less.

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