KR20030069981A - Dual cure coating compositions having improved scratch resistance, coated substrates and methods related thereto - Google Patents

Abstract

Coating compositions prepared from components, including radiation and thermosetting materials; A curing agent and a plurality of particles are provided, each of which is different. Also provided is a multicomponent composite coating comprising a cured topcoat deposited from a colored coating composition and a cured topcoat deposited from a topcoat composition. The multicomponent composite coating of the present invention provides a high scratch resistant color + transparent coating.

Description

DUAL CURE COATING COMPOSITIONS HAVING IMPROVED SCRATCH RESISTANCE, COATED SUBSTRATES AND METHODS RELATED THERETO}

Over the past decade, there has been cooperation to reduce air pollution due to volatile solvents released during the painting process. However, it is often difficult to achieve a high quality smooth coating finish as required by industry or the automotive industry without using organic solvents that play a large role in the flow and leveling of the coating. In addition to achieving a scratch-free appearance, these coatings must be robust, wear resistant, economical and easy to apply.

The use of conventional thermosetting resins for coating compositions, which can be cured by heat, is undesirable because the resin must be thinned with a solvent so as to be easily applied to the substrate. Using a solvent is economically and environmentally undesirable because the solvent must be removed from the coating composition during curing.

To reduce this problem, radiation sensitive materials have been developed which are cured by ionizing radiation or actinic radiation, which alleviate or eliminate the need for solvents. However, the flexibility of the radiation cured coatings is less than desirable and the properties of such coating compositions are not readily modified for different applications.

U.S. Patent No. 4,025,407 discloses thinning conventional thermosetting resins with radiation or actinic radiation sensitive materials and introducing the coatings into ionizing radiation or actinic radiation and then into conventional curing mechanisms for thermosetting resins. In Example 1 of this patent, a thermosetting resin, in particular a radiation sensitive monomer, is mixed with radiation insensitive aliphatic diisocyanate, TiO ₂ and black tint, the coating is irradiated with an electron beam and heated at 140 ° F. for 24 hours. Prepared by wet curing.

U. S. Patent No. 5,571, 297 discloses a binding membrane comprising a mixture of abrasion grit and a compound having at least one radiation curable action and at least one thermosetting action.

Color + transparent coating systems comprising applying a dyed or colored undercoat to a substrate and then applying a clear coat over the undercoat have become increasingly popular as an original finish for many consumer products, including for example automobiles. . The color + transparent coating system mostly has significant appearance characteristics such as gloss and clarity due to the transparent film. Such color + transparent coating systems have gained popularity for automotive, aerospace applications, flooring such as ceramic tiles and wooden floors, packaging coatings, and the like.

Topcoat film-forming compositions, particularly those used in the manufacture of clearcoats in automotive and industrial color + transparent coating systems, are susceptible to damage from a number of environmental factors as well as defects occurring during the assembly process. Defects during the assembling process include paint defects during application or curing of the undercoat or the transparent coat. Damage caused by environmental factors may include acidic precipitation, exposure to sunlight, high relative humidity and high temperatures, defects caused by contact with scratched surfaces, and small, hard objects that produce fragments on the coated surface. There is a defect due to the collision.

Typically, harder, more highly crosslinked films may exhibit improved scratch resistance, but the films are less flexible and are resistant to fragmentation or thermal cracking due to the film's softness resulting from high crosslink density. Much more sensitive. More flexible, less crosslinked films do not tend to fragment or thermally crack, but are susceptible to scratching, water staining, and susceptibility to acid corrosion due to the low crosslink density of the cured film.

Moreover, elastomeric automotive parts and accessories, such as elastomeric bumpers and hoods, are typically "separately" coated and shipped to an automobile assembly plant. Coating compositions applied to such elastomeric substrates are typically highly flexible and formulated such that the coating can bend with the substrate without cracking. In order to achieve this essential flexibility, coating compositions used in elastomeric substrates often employ flexible auxiliaries that act to produce coatings with lower crosslink density or lower the overall film glass transition temperature (Tg). It is formulated to include. Acceptable flexibility properties can be achieved by these blending techniques, while the techniques can also produce a more flexible film that is easy to scratch. As a result, much cost and care must be taken to pack the coated parts to prevent scratching the coated surface during shipment to the automotive assembly plant.

US Pat. No. 4,822,828 discloses (a) 50 to 85 weight percent vinyl functional silane based on the total weight of the dispersion, (b) 15 to 50 weight percent polyfunctional acrylate based on the total weight of the dispersion, and (c) Optionally, the use of vinyl functional silanes in aqueous radiation curable coating compositions comprising 1 to 3 weight percent photoinitiator. The vinyl functional silane is a partial condensate of silica and silane, wherein at least 60% of the silane is of the general formula (R) _a Si (R ') _b (R') _c where R is allyl or vinyl functional Alkyl and R 'is hydrolyzable alkoxy or methoxy and R "is non-hydrolyzable saturated alkyl, phenyl or siloxy, wherein a + b + c is 4 and a≥1; b≥1; c≥0 Vinyl functional silanes The patent discloses that the coating composition can be cured by applying it to a plastic material and exposing it to ultraviolet or electron beam irradiation to form a substantially transparent wear resistant layer.

Despite the recent improvements to color + transparent coating systems, there is still a need in the automotive coatings field for topcoats that have good scratch resistance without the appearance of films. Furthermore, it would be advantageous to provide a topcoat for elastomeric substrates used in the industrial and automotive industries, which is flexible and scratch resistant.

Summary of the Invention

In one embodiment, the present invention provides a kit comprising: (a) at least one first material comprising at least one radiation curable reactive functional group; (b) at least one second material comprising at least one thermally curable reactive functional group; (c) is reactive with at least one thermally curable reactive functional group and is selected from aminoplast resins, polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols and mixtures thereof One or more curing agents; And (d) components comprising a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof, wherein each of the components is different.

In another embodiment, the present invention provides a composition comprising (a) at least one material comprising at least one ultraviolet curable reactive functional group and at least one thermally curable reactive functional group; (b) one or more curing agents reactive to one or more thermally curable reactive functional groups and selected from polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols, and mixtures thereof; And (c) components comprising a plurality of particles, wherein each component is different.

Also disclosed in the scope of the invention is a coated substrate comprising a substrate and a cured composition according to the invention coated on at least a portion of the substrate. The present invention also provides a method of coating a substrate comprising forming a cured composition according to the invention on at least a portion of the substrate. The scope of the invention also discloses automotive substrates coated at least in part by the cured compositions according to the invention. The present invention also provides a method for producing a coated automotive substrate comprising obtaining an automotive substrate and forming a cured composition according to the invention on at least a portion of the automotive substrate.

Also provided is a multicomponent composite coating composition comprising a undercoat deposited from a colored coating composition and a cured composition according to the invention formed as a top coat on at least a portion of the undercoat. The present invention also relates to (a) applying a colored composition to a substrate to form a undercoat; (b) applying a coating composition according to the invention on at least a portion of the undercoat as a coating composition for coating; (c) providing a method for producing a multicomponent composite coating composition comprising curing the coating composition for top coat to produce a cured composition according to the present invention.

Another method of improving the scratch resistance of a polymer substrate or polymer coating comprising forming a cured composition according to the invention on a polymer substrate or polymer coating is also disclosed. The present invention also provides a method for maintaining the gloss of a polymer substrate or polymer coating for a predetermined time, comprising forming a coated composition according to the invention on at least a portion of the polymer substrate or polymer coating. Also provided is a method for restoring the gloss of a polymeric substrate or polymer coating, comprising forming a cured composition according to the invention on at least a portion of the polymeric substrate or polymer coating.

Except in the Examples, or where otherwise indicated, all numerical values indicating amounts of components, reaction conditions, and the like used in the specification and claims are to be understood as being modified in all instances by the term 'about'. Thus, unless indicated to the contrary, the numerical variables set forth herein and in the appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. Without presumably eliminating the application of the doctrine of equivalents to the claims, each numerical variable should be construed using the usual rounding techniques, at least in light of the reported meaningful figures.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as accurate as possible. However, all values inherently contain some errors that are essentially generated from the standard deviation found in their respective test measurements.

Some embodiments of the present invention relate to dual cured coating compositions made from radiation curable materials, heat curable materials, curing agents, and a plurality of particles, with the respective components being different. Other embodiments of the present invention generally include materials having at least one radiation curable group and at least one heat curable group; Curing agent; And dual cured coating compositions prepared from a plurality of particles, wherein each of the components is different. Another embodiment of the invention relates to a substrate coated with the cured composition. A further embodiment of the invention relates to a method for improving the scratch resistance of a substrate. It will be apparent to those skilled in the art that certain embodiments of the present invention may relate to some or all of the above aspects of the invention as well as other preferred embodiments.

In one embodiment, the present invention provides a kit comprising one or more first materials comprising one or more ultraviolet curable reactive functional groups; At least one second material comprising at least one thermally curable reactive functional group; One or more curing agents reactive with one or more thermally curable reactive functional groups; And to a coating composition prepared from components comprising a plurality of particles, each of which is different. As used herein, "material" may be a compound, monomer, oligomer or polymer. In alternative embodiments, the film-forming material may instead of or in addition to the first and second materials include one or more functional groups curable by thermal energy and one or more functional groups curable by ionizing radiation or actinic radiation.

As used herein, the expression "each component is different" refers to a component that does not have the same chemical structure as the other components in the composition.

As used herein, the term "curing", for example, "cured composition" means that at least some of the crosslinkable components that form the composition are at least partially crosslinked. In some embodiments of the invention, the crosslink density, ie the degree of crosslinking, of the crosslinkable components ranges from 5 to 100% of complete crosslinking. In other embodiments, the crosslink density ranges from 35 to 85% of complete crosslinking. In other embodiments, the crosslink density ranges from 50 to 85% of complete crosslinking. The crosslink density can be within any combination of values including the above values. One skilled in the art can determine the presence and extent of crosslinking, ie crosslink density, by various methods such as dynamic thermal analysis (DMTA) using a TA device DMA 2980 DMTA analyzer performed under nitrogen. Will understand. The method measures the glass transition temperature and the crosslink density of the glass film of the coating or polymer. The physical properties of the cured material are related to the structure of the crosslinked network.

As discussed above, the composition according to the present invention is prepared from components comprising one or more first materials comprising one or more radiation curable reactive functional groups curable by ionizing radiation and / or actinic radiation.

As used herein, 'ionizing radiation' means high energy radiation and / or secondary energy generated by the conversion of electrons or other particle energy into neutrons or gamma rays, wherein the energy is at least 30,000 electron volts and 50,000 to 300,000 electron volts. Can be. Although various types of ionizing radiation such as X-rays, gamma and beta rays are suitable for this purpose, radiation generated by accelerated high energy electron or electron beam devices can be used. The amount (rad) of ionizing radiation for the cured composition according to the present invention can be varied based on factors such as the composition of the coating formulation, the coating thickness on the substrate, the temperature of the coating composition, and the like. In general, the wet thickness of a coating composition according to the present invention, 1 mil (25 μm) thick, can be cured in the absence of tack upon exposure to ionizing radiation of 0.5 to 5 megarads through its thickness in the presence of oxygen.

'Chemical radiation' is light with a wavelength of electromagnetic radiation ranging from the ultraviolet (UV) range through the visible range to the infrared range. The actinic radiation that can be used to cure the coating composition of the present invention generally has an electromagnetic radiation wavelength in the range from 150 to 2,000 nm, can range from 180 to 1,000 nm, and can also range from 200 to 500 nm. In one embodiment, ultraviolet light having a wavelength of 10 to 390 nm can be used. Examples of suitable ultraviolet light sources are mercury arcs, carbon arcs, low, medium or high pressure mercury lamps, vortex plasma arcs and ultraviolet emitting diodes. Suitable ultraviolet emitting lamps are medium pressure mercury vapor lamps having an output in the range of 200 to 600 watts / in (79 to 237 watts / cm) across the length of the lamp tube. Generally, a 1 mil (25 μm) thick wet film of the coating composition according to the present invention may be used at a rate of 20 to 1000 ft / min (6 to 300 m / min) of 200 to 1000 milli Joules per cm 2 of the wet film. By passing under four medium pressure mercury vapor lamp exposures, the thickness can be cured without stickiness upon exposure to actinic radiation.

One or more radiation curable reactive functional groups may be selected from vinyl groups, vinyl ether groups, epoxy groups, maleimide groups, fumarate groups, and combinations thereof. Suitable first materials having vinyl functionality include those having unsaturated ester groups and vinyl ether groups as discussed below. Non-limiting examples of suitable epoxy groups include alicyclic epoxy groups.

Suitable first materials comprising unsaturated ester groups include materials comprising acrylate groups, methacrylate groups and / or ethacrylate groups. The unsaturated ester group can be an acrylate group. Useful materials comprising unsaturated ester groups include esters and amides of acrylic or methacrylic acid or comonomers of such esters with another copolymerizable monomer. Suitable esters are methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylic Latex, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, Glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1,2,4-butanetriol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,4-benzenediol Di (meth) acrylate, pentaerythritol te La (meth) acrylate, 1,5-pentanediol di (meth) acrylate, trimethylpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2,2-dimethyl-3-hydroxypropyl Aliphatic and aliphatic glycidyl ethers such as -2,2-dimethyl-3-hydroxypropionate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylate derived from diglycidyl ether, (meth) acrylamide, diacetone (meth) acrylamide, N- (betahydroxyethyl) (meth) acrylamide, N, N-bis (betahydro) Oxyethyl) (meth) acrylamide, methylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, bis (gamma- (meth) acrylamide Propoxy) ethane, beta- (meth) arc Acrylic or methacrylic amides such as rylamide ethylacrylate and mixtures thereof.

Useful other first materials comprising unsaturated ester groups include hydroxy functional unsaturated polycarboxylates and polycaprolactone. Suitable hydroxy functional unsaturated polycarboxylates can be prepared from ethylenically unsaturated carboxylic acids and polyhydric alcohols. Useful ethylenically unsaturated carboxylic acids have two or more acid functional groups and / or their corresponding anhydrides. Non-limiting examples of ethylenically unsaturated carboxylic acids and anhydrides are maleic acid, maleic anhydride, fumaric acid, itaconic acid and mixtures thereof. Unsaturated carboxylic acids include saturated carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, Malonic acid, pimelic acid, suberic acid, 2,2-dimethylsuccinic acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, anhydrides of the compounds may be blended as such or with a mixture.

Polyhydric alcohols useful for preparing the hydroxy functional unsaturated polycarboxylates include diethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, 1,6 -Hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis (hydroxyethyl) cyclohexane, 2,2-dimethyl-3-hydroxypropyl-2,2- Dimethyl-3-hydroxypropionate, neopentyl glycol, 2-methyl-1,3-propane diol and mixtures thereof. Monofunctional alcohols such as C ₁ -C ₁₅ monoalcohols can be blended with polyhydric alcohols as desired.

The number average molecular weight of the unsaturated ester material is from 500 to 50,000 g / mol as determined by gel permeation chromatography using polystyrene standards. The unsaturated ester material may be prepared by any method well known in the art, for example, the components are mixed and heated at 150 to 250 ° C. for 1 to 10 hours and formed during the esterification reaction. It can be prepared by removing. Conventional esterification catalysts such as paratoluenesulfonic acid, butyltin acid, dibutyltin oxide, tin fluoride and tin octoate can be used to increase the reaction rate.

Suitable vinyl ether functional materials for use in the present invention include vinyl ethers prepared by methods known to those skilled in the art under pressure from di-, tri- or tetrafunctional polyols, acetylenes and basic catalysts. do. In addition, vinyl terminated polyesters as disclosed in US Pat. No. 5,286,835 (incorporated herein by reference) may be used. Non-limiting examples of useful vinyl ether functional materials include tripropylene glycol divinyl ether, diethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethyl Olpropane trivinyl ether, polytetrahydrofuran divinyl ether, vinyl ether terminated polyester and mixtures thereof. As disclosed in US Pat. No. 5,942,556 (incorporated herein by reference), unsaturated ester materials and urethane vinyl ether materials with vinyl ether functional groups are also useful.

Other useful first materials including epoxy functional groups include epoxy functional monomers such as glycidyl methacrylate and polymers having two or more epoxide or oxirane groups per molecule. Such materials are often referred to as di- or polyepoxides. In general, the epoxide equivalent of the epoxy-functional polymer may be between 128 and 2800, as determined by titration with perchloric acid and quaternary ammonium bromide using methyl violet as an indicator.

Suitable epoxy-functional polymers are saturated or unsaturated cyclic or acyclic aliphatic, cycloaliphatic, aromatic or heterocyclic. The epoxy-functional polymer can optionally have pendant or terminal hydroxyl groups. These may contain substituents such as halogen, hydroxyl and ether groups. Useful classes of these materials include polyepoxides obtained by reacting epihalohydrin (such as epichlorohydrin or epibromohydrin) in the presence of dihydric or polyhydric alcohols and alkalis. Suitable polyhydric alcohols include resorcinol; Catechol; Hydroquinone; Bis (4-hydroxyphenyl) -2,2-propane, i.e. bisphenol A; Bis (4-hydroxyphenyl) -1,1-isobutane; 4,4-dihydroxybenzophenone; Bis (4-hydroxyphenol) -1,1-ethane; Polyphenols such as bis (2-hydroxyphenyl) -methane and 1,5-hydroxynaphthalene.

Examples of useful polyepoxides include diglycidyl ethers of bisphenol A, for example EPON 828® epoxy resins available from Shell Chemical Company. Other useful polyepoxides include polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides derived from epoxidation of olefinically unsaturated alicyclic compounds, and oxyalkylene groups in epoxy molecules. Containing polyepoxides, epoxy novolac resins, and polyepoxides partially defunctionalized by carboxylic acids, alcohols, water, phenols, mercaptans or other active hydrogen-containing compounds to provide hydroxyl-containing polymers. It includes.

The first material, when added to the other components forming the coating composition, comprises from 1 to 99 weight percent, from 25 to 95 weight percent or from 50 to 95 weight percent, based on the total weight of the resin solids of the components forming the coating composition. Present in the coating composition.

As used herein, 'based on the total weight of the resin solids' of the components forming the composition is that the amount of component added during the preparation of the coating composition is polysiloxane, any film forming component, any film present during the preparation of the composition. Pigments, including forming components, any polysiloxanes, any curing agents and any silyl-blocked materials (but particles, any solvents or any additive solids, such as hindered amine stabilizers, photoinitiators, pigment extenders and fillers) , Catalysts, flow modifiers, and UV light absorbers) are based on the total weight of solids (non-volatiles).

In one embodiment, the present invention is directed to a coating composition comprising at least one polysiloxane comprising reactive functional groups that can be cured by ionizing radiation or actinic radiation. In another embodiment, the polysiloxane may comprise one or more functional groups that can be cured by thermal energy and one or more functional groups that can be cured by ionizing or actinic radiation.

In one embodiment of the invention, the one or more polysiloxanes have one or more radiation curable functional groups selected from vinyl groups, epoxy groups, maleimide groups, fumarate groups, and combinations thereof, as described above. The general structure of the polysiloxane will be described below in the discussion of the thermoset second material. At least one polysiloxane having at least one radiation curable functional group is present in the components forming the coating composition at 0.5 to 95 weight percent, 25 to 95 weight percent or 50 to 95 weight percent based on the total weight of the resin solids of these components. . The amount of the first substance may range from any combination therein, including both ends of the numerical value.

The components forming the coating composition, in addition to the first material, include one or more other ethylenically unsaturated monomers or oligomers as necessary, including but not limited to vinyl monomers such as vinyl acetate, styrene, vinyl toluene, divinyl benzene, Methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and mixtures thereof). One or more other ethylenically unsaturated monomers or oligomers are present in the components forming the coating composition at 1 to 99 weight percent, 25 to 95 weight percent or 50 to 95 weight percent based on the total weight of the resin solids of these components. do. The amount of one or more other ethylenically unsaturated monomers or oligomers may range from any combination therein, including both ends of the numerical values.

In another embodiment in which the coating is cured by actinic radiation or a combination of actinic radiation and thermal energy, the components forming the coating composition add one or more photoinitiators or photosensitizers that provide free radicals or cations to initiate the polymerization process. It can be included as. Useful photoinitiators have absorbances in the range from 150 to 2,000 nm. Non-limiting examples of useful photoinitiators include benzoin, benzophenone, hydroxy benzophenone, anthraquinone, thioxanthone, substituted benzoin, for example the butyl isomer of benzoin ether, α, α-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl propane 1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide and mixtures thereof. Non-limiting examples of suitable cationic photoinitiators include iodine salts such as FC509® available from 3M, and sulfonium salts such as UVI-6991 and UVI-6974 available from Union Carbide. The photoinitiator may be a 50:50 blend of 2-hydroxy-2-methyl-1-phenyl propane-1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, for example Ciba-Geigy Corporation ( DAROCURE 4265 available from Ciba-Geigy Corporation.

In one embodiment, the components that form the coating composition include one or more second materials that include one or more thermally curable reactive functional groups. Useful thermally curable reactive functional groups include hydroxyl groups, vinyl groups, urethane groups, urea groups, amide groups, carbamate groups, isocyanate groups, blocked isocyanate groups, epoxy groups, acid groups, amine groups, anhydride groups, and aziridine groups do. In one embodiment, the one or more second materials may have one or more reactive functional groups selected from hydroxyl groups, carbamate groups, epoxy groups, isocyanate groups, and carboxyl groups. In one embodiment, the one or more second materials may have one or more reactive functional groups selected from hydroxyl groups and carbamate groups.

The second material is a hydroxyl functional polymer, polyester, acrylic polymer, polyurethane, polyurea, polyamide, carbamate functional polymer, polyisocyanate different from curing agent (c), blocked polyisocyanate different from curing agent (c) , Polyepoxides, polyethers different from the curing agent (c), polyacids, polyamines, polyanhydrides different from the curing agent (c), and film-forming polymers selected from copolymers and mixtures thereof.

Non-limiting examples of suitable hydroxyl group-containing polymers include acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and mixtures thereof. The hydroxyl group-containing polymer may be an acrylic polyol which may have from 1000 to 100 g of hydroxyl equivalent weight per solid equivalent. The term "equivalent" is a calculated value based on the relative amounts of the various components used to make a particular substance, based on the solids of the particular substance. The relative amount is to make the theoretical weight in grams of the same material as the polymer made from the components and to provide the theoretical number of specific functional groups present in the resulting polymer. Theoretical polymer weight is divided by theoretical figures to provide equivalents. For example, hydroxyl equivalents are based on the equivalent of reactive pendant and / or terminal hydroxyl groups in the hydroxyl-containing polymer.

Suitable hydroxyl groups and / or carbamate group-containing acrylic polymers may be prepared from polymerizable ethylenically unsaturated monomers and may be one or more other polymerizable with hydroxyalkyl esters of (meth) acrylic acid and / or (meth) acrylic acid. Alkyl esters of (meth) acrylic acid, including ethylenically unsaturated monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethyl hexyl acrylate, and vinyl aromatic compounds, For example, it may be a copolymer of styrene, alpha-methyl styrene and vinyl toluene. As used herein, '(meth) acrylate' and like terms are intended to include both acrylates and methacrylates.

The acrylic polymer can be prepared from ethylenically unsaturated beta-hydroxy ester functional monomers. Such monomers may be derived from the reaction of ethylenically unsaturated acid functional monomers such as monocarboxylic acids such as acrylic acid with epoxy compounds which are not involved in free radical initiated polymerization of said unsaturated acid monomers. Non-limiting examples of such epoxy compounds are glycidyl ethers and esters. Non-limiting examples of suitable glycidyl ethers include glycidyl ethers of alcohols and phenols such as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether and the like. Non-limiting examples of suitable glycidyl esters include the trade name CARDURA E from Shell Chemical Company; And those commercially available under the trade name GLYDEXX-10 from Exxon Chemical Company. On the one hand, beta-hydroxy ester functional monomers are ethylenically unsaturated epoxy functional monomers such as glycidyl (meth) acrylate and allyl glycidyl ether, and saturated carboxylic acids such as saturated From monocarboxylic acids such as isostearic acid.

Epoxy functional groups are polymerizable by copolymerizing oxirane group-containing monomers such as glycidyl (meth) acrylate and allyl glycidyl ether with other polymerizable ethylenically unsaturated monomers such as those discussed above. It can be introduced into polymers made from unsaturated monomers. Such methods for preparing epoxy functional acrylic polymers are described in detail in columns 3 to 6 of US Pat. No. 4,001,156, which is incorporated herein by reference.

Carbamate functional groups can be introduced into polymers prepared from polymerizable ethylenically unsaturated monomers, for example, by copolymerizing the aforementioned ethylenically unsaturated monomers with carbamate functional vinyl monomers such as carbamate functional alkyl esters of methacrylic acid. have. Useful carbamate functional alkyl esters can be prepared, for example, by reacting hydroxyalkyl carbamate (eg, the reaction product of ammonia with ethylene carbonate or propylene carbonate) with methacrylic anhydride.

Other useful carbamate functional vinyl monomers include, for example, the reaction products of hydroxyethyl methacrylate, isophorone diisocyanate and hydroxypropyl carbamate or the reaction products of hydroxypropyl methacrylate, isophorone diisocyanate and methanol. Included. Reaction products of other carbamate functional vinyl monomers such as isocyanic acid (HNCO) with hydroxyl functional acrylic or methacryl monomers such as hydroxyethyl acrylate, and are incorporated herein by reference Or those disclosed in US Pat. No. 3,479,328.

Carbamate functional groups can also be introduced into the acrylic polymer by reacting a hydroxyl functional acrylic polymer with a low molecular weight alkyl carbamate, such as methyl carbamate. Pendant carbamate groups can also be introduced into the acrylic polymer by a 'transcarbamoylation' reaction that reacts the hydroxyl functional acrylic polymer with a low molecular weight carbamate derived from an alcohol or glycol ether. The carbamate groups can be exchanged with hydroxyl groups to give the carbamate functional acrylic polymer and the original alcohol or glycol ether. The hydroxyl functional acrylic polymer can also be reacted with isocyanic acid to provide pendant carbamate groups. Likewise, the hydroxyl functional acrylic polymer can be reacted with urea to provide pendant carbamate groups.

Polymers prepared from polymerizable ethylenically unsaturated monomers are prepared by those skilled in the art in the presence of suitable catalysts such as organic peroxides or azo compounds such as benzoyl peroxide or N, N-azobis (isobutylonitrile). It can be prepared by a solution polymerization technique well known to the art. The polymerization can be carried out in an organic solution in which the monomers are dissolved by techniques conventional in the art. On the one hand, the polymers can be prepared by aqueous emulsion or dispersion polymerization techniques well known in the art. The ratio of reactants and reaction conditions are chosen such that an acrylic polymer with the desired pendant functionality is produced.

Polyester polymers are also useful as additional polymers in the coating compositions of the present invention. Useful polyester polymers may include condensation products of polyhydric alcohols with polycarboxylic acids. Non-limiting examples of suitable polyhydric alcohols include ethylene glycol, neopentyl glycol, trimethylol propane and pentaerythritol. Non-limiting examples of suitable polycarboxylic acids are adipic acid, 1,4-cyclohexyl dicarboxylic acid and hexahydrophthalic acid. In addition to the above-mentioned polycarboxylic acids, functional equivalents of acids such as anhydrides or lower alkyl esters of acids such as methyl esters can be used, if present. It is also possible to use small amounts of monocarboxylic acids, for example stearic acid. The ratio of the reactants and the reaction conditions are chosen such that a polyester polymer having the desired pendant functional groups, ie carboxyl or hydroxyl functional groups, is produced.

For example, hydroxyl group-containing polyesters can be prepared by reacting anhydrides of dicarboxylic acids, such as hexahydrophthalic anhydride, with a diol such as neopentyl glycol in a molar ratio of 1: 2. If for the purpose of improving air-drying, suitable dry oil fatty acids can be used, which may include those derived from linseed oil, soybean oil, tall oil, dehydrated castor oil or kerosene.

Carbamate functional polyesters can be prepared by first forming hydroxyalkyl carbamate that can react with the polyacids and polyols used in the preparation of the polyesters. On the other hand, terminal carbamate functional groups can be introduced into the polyester by reacting isocyanic acid with the hydroxy functional polyester. Carbamate functional groups can also be introduced into polyesters by reacting hydroxyl polyesters with urea. Carbamate groups can also be introduced into the polyesters by transcarbamoylation reactions. Suitable methods for preparing carbamate functional group-containing polyesters are disclosed in column 2, line 40 to column 4, line 9 of US Pat. No. 5,593,733, which is incorporated herein by reference.

Polyurethane polymers containing terminal isocyanates (which may be blocked) or hydroxyl groups can be used as additional polymers in the coating compositions of the invention. Polyurethane polyols or NCO-terminated polyurethanes that can be used are those prepared by reacting polyols, including polymeric polyols, with polyisocyanates. Terminal isocyanates or primary and / or secondary amine group-containing polyureas that may also be used may be those prepared by reacting polyamines such as, but not limited to, polymer polyamines with polyisocyanates.

The hydroxyl / isocyanate or amine / isocyanate equivalent ratio can be controlled and the reaction conditions can be chosen such that the desired end groups are obtained. Non-limiting examples of suitable polyisocyanates include those disclosed in column 5, line 26 to column 6, line 28 of US Pat. No. 4,046,729, which is incorporated herein by reference. Non-limiting examples of suitable polyols include those disclosed in column 7, line 52 to column 10, line 35 of US Pat. No. 4,046,729, which is incorporated herein by reference. Non-limiting examples of suitable polyamines include those disclosed in column 6, line 61 to column 7, line 32, and column 3, line 13 to 50, US Pat. No. 4,046,729, which are incorporated herein by reference.

Carbamate functional groups can be introduced into the polyurethane polymer by reacting the polyisocyanates with polyesters containing hydroxyl functional groups and pendant carbamate groups. On the other hand, the polyurethane can be prepared by reacting the polyisocyanate with the polyester polyol and hydroxyalkyl carbamate or isocyanic acid as separate reactants. Non-limiting examples of suitable polyisocyanates include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate and toluene diisocyanate, and aliphatic polyisocyanates such as 1,4 -Tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate. Alicyclic diisocyanates such as 1,4-cyclohexyl diisocyanate and isophorone diisocyanate can be used.

Non-limiting examples of suitable polyether polyols include polyalkylene ether polyols, for example compounds of formula VII or VIII:

In the above formulas,

Substituent R is a lower alkyl group of 1 to 5 carbon atoms including hydrogen or mixed substituents,

n has a value ranging from 2 to 6,

m has a value ranging from 8 to 100 or more.

Non-limiting examples of polyalkylene ether polyols include poly (oxytetramethylene) glycol, poly (oxytetraethylene) glycol, poly (oxy-1,2-propylene) glycol and poly (oxy-1,2-butylene) Glycols.

Various polyols such as but not limited to glycols such as ethylene glycol, 1,6-hexanediol, bisphenol A and the like, or other higher polyols such as trimethylolpropane, pentaerythritol and the like oxyalkylation Polyether polyols formed from these may also be useful. Polyols of higher functional groups which can be used above can be prepared by oxyalkylation of compounds such as, for example, sucrose or sorbitol. One oxyalkylation method that can be used is the reaction of a polyol in the presence of an acidic or basic catalyst with an alkylene oxide, for example but not limited to propylene or ethylene oxide. Examples of specific and non-limiting polyethers are those sold under the trade names TERATHANE and TERACOL, available from E.I. Du Pont de Nemours and Company, Inc.

In one embodiment, the second material may comprise one or more polysiloxanes having one or more thermosetting groups. At least one polysiloxane has at least one structural unit of formula (I):

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each substituent R ¹ is the same or different and is a group selected from H, OH, a monovalent hydrocarbon group and a monovalent siloxane group; Each substituent R ² is the same or different and comprises one or more reactive functional groups.

'At least one polysiloxane comprising at least one unit of formula I' is to be understood as a polymer containing at least two Si atoms per molecule. The term 'polymer' as used herein includes oligomers, including without limitation both homopolymers and copolymers. It should also be understood to include one or more of the polysiloxane linear, branched, dendritic or cyclic polysiloxanes.

The term 'reactive' as used herein also refers to a functional group that forms a covalent bond with another functional group under conditions sufficient to cure the composition.

M and n shown in at least one of the above formulas I satisfy 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4, respectively. When (m + n) is 3, the value represented by n may be 2 and the value represented by m is 1. Similarly, when (m + n) is 2, the values represented by n and m are each 1.

As used herein, “monovalent hydrocarbon group” means a monovalent group having a backbone repeating unit based only on carbon. As used herein, 'monovalent' refers to a substituent that forms only one single covalent bond as a substituent. For example, monovalent groups on one or more polysiloxanes will form one single covalent bond to the silicon atoms in the backbone of the one or more polysiloxane polymers. As used herein, a 'hydrocarbon group' is intended to include both branched and unbranched hydrocarbon groups.

Thus, when referring to 'monovalent hydrocarbon groups', the hydrocarbon groups can be branched or unbranched, acyclic or cyclic, saturated or unsaturated, or aromatic, and 1 to 24 (or 3 to 24 for aromatic groups). May contain a carbon atom. Non-limiting examples of such hydrocarbon groups include alkyl, alkoxy, aryl, alkaryl and alkoxyaryl groups. Non-limiting examples of lower alkyl groups include methyl, ethyl, propyl and butyl groups. As used herein, 'lower alkyl' refers to an alkyl group having 1 to 6 carbon atoms. One or more of the hydrogen atoms of the hydrocarbon may be substituted with heteroatoms. As used herein, “heteroatom” means elements other than carbon, such as oxygen, nitrogen and halogen atoms.

As used herein, "siloxane" means a group comprising a backbone comprising two or more -SiO- groups. For example, the siloxane groups represented by R ¹ discussed above and R discussed below may be branched or unbranched linear or cyclic. The siloxane groups can be substituted with pendant organic substituents such as alkyl, aryl and alkaryl groups. The organic substituents may be substituted with heteroatoms such as oxygen, nitrogen and halogen atoms, reactive functional groups such as the reactive functional groups discussed above in connection with R ² and any mixture of the groups.

In another embodiment, each substituent R ² may be the same or different and includes hydroxyl groups, carboxyl groups, isocyanate groups, blocked polyisocyanate groups, primary amine groups, secondary amine groups, amide groups, carbamate Groups, urea groups, urethane groups, vinyl groups, unsaturated ester groups such as acrylate groups and methacrylate groups, maleimide groups, fumarate groups, onium salt groups such as sulfonium groups and ammonium groups, Group comprising at least one reactive functional group selected from anhydride groups, hydroxy alkylamide groups and epoxy groups, wherein m and n are represented by 0 <n <4, 0 <m <4 and 2≤ (m + n) <4. Meet the requirements.

In one embodiment, the present invention relates to the aforementioned cured composition, wherein at least one polysiloxane comprises at least two reactive functional groups. The at least one polysiloxane may have a reactive group equivalent in the range of 50 to 1000 mg per gram of the at least one polysiloxane. In one embodiment, the at least one polysiloxane has a hydroxyl group equivalent of 50-1000 mg KOH per gram of said at least one polysiloxane. In another embodiment, the at least one polysiloxane has a hydroxyl group equivalent of 100 to 300 mg KOH per gram of the at least one polysiloxane, and in another embodiment, the hydroxyl group equivalent ranges from 100 to 500 mg KOH per gram. to be. The hydroxyl equivalent of one or more polysiloxanes may range from any combination therein, including both ends of the numerical values.

In another embodiment, the present invention relates to the aforementioned cured composition, wherein the at least one R ² group represents a group comprising at least one reactive functional group selected from hydroxyl groups and carbamate groups. In another embodiment, the present invention relates to the aforementioned coating composition, wherein the at least one R ² group represents a group comprising at least two reactive functional groups selected from hydroxyl groups and carbamate groups. In another embodiment, the present invention relates to the aforementioned coating composition, wherein the at least one R ² group represents a group comprising an oxyalkylene group and at least two hydroxyl groups.

In one embodiment, the invention relates to any of the cured compositions described above, wherein the one or more polysiloxanes have Formula II or III:

In the above formulas,

m has a value of 1 or more,

m 'ranges from 0 to 75,

n ranges from 0 to 75,

n 'ranges from 0 to 75,

Each R may be the same or different and is selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and any mixture of these groups,

-R ^a includes the structure of Formula IV:

-R ³ -X

Where

-R ³ is selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group and an alkenylene aryl group,

X is hydroxyl group, carboxyl group, isocyanate group, blocked polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group, urea group, urethane group, vinyl group, unsaturated ester group, eg For example at least one reactive functional group selected from acrylate groups and methacrylate groups, maleimide groups, fumarate groups, onium salt groups, such as sulfonium groups and ammonium groups, anhydride groups, hydroxy alkylamide groups and epoxy groups It represents group containing.

As used herein, 'alkylene' refers to an acyclic or cyclic saturated hydrocarbon group having a carbon chain length of C ₂ to C ₂₅ . Non-limiting examples of suitable alkylene groups include propenyl, 1-butenyl, 1-pentenyl, 1-decenyl and 1-heneicosenyl, for example (CH ₂ ) ₃ , (CH ₂ ) _{4, respectively.} , Isoprene and myrcene, as well as those derived from (CH ₂ ) ₅ , (CH ₂ ) ₁₀ and (CH ₂ ) ₂₃ .

As used herein, 'oxyalkylene' refers to an alkylene group containing one or more oxygen atoms bonded to two carbon atoms and inserted therebetween and having an alkylene carbon chain length of C ₂ to C ₂₅ . Non-limiting examples of suitable oxyalkylene groups are derived from trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol monoallyl ether, polyethoxylated allyl alcohol and polypropoxylated allyl alcohol And others such as — (CH ₂ ) ₃ OCH ₂ C (CH ₂ OH) ₂ (CH ₂ CH ₂ —).

'Alkylene aryl' as used herein refers to an acyclic alkylene group substituted with one or more aryl groups, for example phenyl and having an alkylene carbon chain length of C ₂ to C ₂₅ . The aryl group may optionally be further substituted. Non-limiting examples of suitable substituents for aryl groups include hydroxyl groups, benzyl groups, carboxylic acid groups and aliphatic hydrocarbon groups. Non-limiting examples of suitable alkylene aryl groups include those derived from styrene and 3-isopropenyl-VII, VIII-dimethylbenzyl isocyanate, for example-(CH ₂ ) ₂ C ₆ H ₄ -and -CH ₂ CH (CH ₃ ) C ₆ H ₃ (C (CH ₃ ) ₂ (NCO). As used herein 'alkenylene' is an acyclic having at least one double bond and an alkenylene carbon chain length of C ₂ to C ₂₅ . Or non-limiting examples of suitable alkenylene groups include those derived from propargyl alcohol and acetylene diol, for example 2,4,7,9-tetramethyl-5-decine-4,7- Dior (commercially available as SURFYNOL 104 from Air Products and Chemicals, Inc., Allentown, PA).

Formulas (II) and (III) are schematic and blocks may be used in some cases, but parentheses do not necessarily mean blocks. In some cases, the polysiloxane may include various siloxane units. This is even more so as the number of siloxane units used increases, especially when using a mixture of a number of different siloxane units. If it is desired to use a large number of siloxane units and this forms a block, oligomers can be formed that can combine to form a block compound. By wisely selecting the reactants, compounds with alternating structures or blocks of alternating structures can be used.

In one embodiment, the present invention relates to a coating composition comprising polysiloxane wherein substituent R ³ represents an oxyalkylene group. In another embodiment, R ³ represents an oxyalkylene group and X represents a group comprising two or more reactive functional groups.

In another embodiment, the present invention relates to any coating composition prepared from the above-mentioned components comprising at least one polysiloxane of formula II or III above, wherein (n + m) is in the range of 2-9. In another embodiment, the components may include one or more polysiloxanes having Formula II or III above, wherein (n + m) is in the range of 2-3. In another embodiment, the components can include one or more polysiloxanes having Formula II or III described above, wherein (n '+ m') is in the range of 2-9. In another embodiment, the components may include one or more polysiloxanes having Formula II or III above, wherein (n '+ m') is in the range of 2-3.

In one embodiment, the invention relates to any of the aforementioned coating compositions wherein the components comprise one or more polysiloxanes wherein X represents a group comprising at least one reactive functional group selected from hydroxyl groups and carbamate groups. In another embodiment, the present invention relates to a polysiloxane as a component as described above wherein X represents a group comprising two or more hydroxyl groups. In another embodiment, the above-mentioned components, wherein X represents a group comprising at least one group selected from H, a monohydroxy substituted organic group and a group of formula (V) and at least a portion of X represents a group having formula (V) Polysiloxanes as:

R ⁴ -(-CH ₂ -OH) _p

Where

When p is 2, the substituent R ⁴ is Substituent R ₃ represents a C ₁ to C ₄ alkylene group, or

When p is 3, the substituent R ⁴ is Indicates.

In another embodiment, the present invention relates to any of the aforementioned cured compositions, wherein m is 2 and p is 2.

In an embodiment of the invention, the one or more polysiloxanes are unreactive with the particles. In another embodiment, the invention relates to any of the coating compositions described above, wherein the particles are different from the one or more polysiloxanes. In another embodiment, the invention relates to any of the coating compositions described above, wherein the particles have an average particle diameter of less than 100 nm prior to incorporation into the cured composition. Methods known to those skilled in the art for measuring the average particle diameter are described below.

In one embodiment, the present invention relates to formula II or formula III wherein less than 70% by weight of the partial condensate is formed from CH ₃ Si (OH) ₃ when no curing agent is present and at least one polysiloxane is a partial condensate of silanol. It relates to any of the coating compositions described above comprising one or more polysiloxanes having. The components used in these various embodiments can be selected from the coating components discussed above, and additional components can also be selected from those described above.

In another embodiment, the invention relates to any of the coating compositions described above, wherein the components forming the composition comprise one or more polysiloxanes that are at least reaction products of the following reactants:

(i) at least one polysiloxane of formula VI:

Where

Each substituent R may be the same or different and represents a group selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and any mixture of these groups;

At least one of the groups represented by R is H;

n 'may be in the range of 0 to 100, 0 to 10, and also 0 to 5 so that the SiH content (%) in the polysiloxane is 2 to 50%, and ranges from 5 to 25%; And

(ii) hydroxyl groups, carboxyl groups, isocyanate groups, blocked polyisocyanate groups, primary amine groups, secondary amine groups, amide groups, carbamate groups, urea groups, urethane groups, vinyl groups, unsaturated ester groups, For example acrylate and methacrylate groups, maleimide groups, fumarate groups, onium salt groups such as sulfonium groups and ammonium groups, anhydride groups, hydroxy alkylamide groups and epoxy groups and hydrosilylation reactions One or more molecules comprising one or more functional groups selected from one or more unsaturated bonds that may undergo.

In another embodiment, the one or more functional groups are selected from hydroxyl groups.

It should be appreciated that the various R groups may be the same or different, and in some embodiments the R groups may be entirely monovalent hydrocarbon groups or a mixture of various groups, for example monovalent hydrocarbon groups and hydroxyl groups.

In another embodiment, the reaction product is not gelated. As used herein, “ungelled” refers to a reaction product that is substantially free of crosslinks and has an intrinsic viscosity when dissolved in a suitable solvent, for example as measured according to ASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the reaction product indicates its molecular weight. On the other hand, the gelled reaction product will have an intrinsic viscosity that is too high to measure because it has a very high molecular weight. As used herein, a 'substantially free of crosslinking' reaction product refers to a reaction product having a weight average molecular weight (Mw) of less than 1,000,000 as measured by gel permeation chromatography.

In addition, it should be appreciated that the unsaturation level comprised in reactant (ii) can be selected so that an ungelled reaction product is obtained. That is, when using silicon hydride containing polysiloxane (i) having higher average Si-H functionality, the reactant (ii) may have a lower level of unsaturation. For example, the silicon hydride containing polysiloxane (i) may be a low molecular weight material with n 'in the range of 0 to 5 and an average Si—H functional value of 2 or less. In this case, the reactant (ii) may contain two or more unsaturated bonds which may undergo a hydrosilylation reaction without the occurrence of gelation.

Non-limiting examples of silicon hydride-containing polysiloxanes (i) include 1,1,3,3-tetramethyl disiloxane where n 'is 0 and an average Si-H functional group is 2, and n' ranges from 4 to 5 and averages Silicon hydride containing polymethyl polysiloxanes having approximately Si—H functional groups (for example, commercially available as MASILWAX BASE® from BASF Corporation).

Materials for use as the reactant (ii) include hydroxyl functional group-containing allyl ethers such as trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, trimethylolpropane diallyl ether, polyoxyalkylene alcohols, For example, it may include those selected from polyethoxylated alcohols, polypropoxylated alcohols and polybutoxylated alcohols, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylic acid adducts and mixtures thereof. . Also suitable are mixtures of hydroxyl functional polyallyl ethers with hydroxyl functional monoallyl ethers or allyl alcohols. In some cases, reactant (ii) may contain one or more unsaturated bonds at the terminal position. The reaction conditions and proportions of reactants (i) and (ii) are chosen such that the desired functional groups are formed.

Hydroxyl functional group-containing polysiloxanes are prepared by reacting hydroxyl functional group-containing polysiloxanes with anhydrides to form only semi-ester acid groups under reaction conditions that promote only the reaction of the anhydride and hydroxyl functional groups and prevent further esterification from occurring. Can be. Non-limiting examples of suitable anhydrides include hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, chloric anhydride, alkenyl succinic anhydride and substituted alkenyl anhydrides such as jade Tenyl succinic anhydrides and mixtures thereof.

The semi-ester group-containing reaction product prepared as described above may be further reacted with monoepoxide to form a polysiloxane containing secondary hydroxyl group (s). Non-limiting examples of suitable monoepoxides include phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, glycidyl versatate, for example shell chemicals. CARDURA E, available from Campani, and mixtures thereof.

In another embodiment, the present invention relates to the aforementioned coating composition, wherein the components forming the coating composition comprise at least one polysiloxane which is a carbamate functional group-containing polysiloxane comprising at least the reaction product of the following reactants:

(i) at least one polysiloxane in which R and n 'contain silicon hydride of formula VI as disclosed for Formula VI above;

(ii) at least one hydroxyl functional group-containing material having at least one unsaturated bond capable of undergoing a hydrosilylation reaction as described above; And

(iii) at least one low molecular weight carbamate functional material comprising the reaction product of an alcohol or glycol ether with urea.

Examples of such 'low molecular weight carbamate functional materials' include, but are not limited to, alkyl carbamate and hexyl carbamate, and glycol ether carbamate (see US Pat. Nos. 5,922,475 and 5,976,701, incorporated herein by reference). There is).

The carbamate functional group can be introduced into the polysiloxane by reacting the hydroxyl functional group-containing polysiloxane with the low molecular weight carbamate functional material through a 'transcarbamoylation' process. The low molecular weight carbamate functional material, which may be derived from an alcohol or glycol ether, is reacted with the free hydroxyl groups of a polysiloxane polyol, i.e., a substance having an average of at least two hydroxyl groups per molecule, to give the carbamate functional polysiloxane and the original alcohol or glycol Ether can be obtained. The reaction conditions and ratios of reactants (i), (ii) and (iii) are chosen to form the desired groups.

The low molecular weight carbamate functional material can be prepared by reacting an alcohol or glycol ether with urea in the presence of a catalyst such as butyl tartaric acid. Non-limiting examples of suitable alcohols include low molecular weight aliphatic, cycloaliphatic and aromatic alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexanol and 3-methylbutanol. Non-limiting examples of suitable glycol ethers are ethylene glycol methyl ether and propylene glycol methyl ether. The introduction of carbamate functional groups into the polysiloxane can also be accomplished by reacting isocyanic acid with the free hydroxyl groups of the polysiloxane.

As mentioned above, in addition to or instead of hydroxyl or carbamate functional groups, the one or more polysiloxanes may be selected from one or more other reactive functional groups such as carboxyl groups, isocyanate groups, blocked isocyanate groups, carboxylate groups, primary And / or secondary amine groups, amide groups, urea groups, urethane groups, epoxy groups and any mixtures of these groups.

If the one or more polysiloxanes contain carboxyl functional groups, the one or more polysiloxanes may be prepared by reacting a hydroxyl functional group-containing one or more polysiloxanes as described above with a polycarboxylic acid or anhydride. Non-limiting examples of suitable polycarboxylic acids for use include adipic acid, succinic acid and dodecanedioic acid. Non-limiting examples of suitable anhydrides include those described above. The reaction conditions and ratios of the reactants are chosen such that the desired functional groups are formed.

Where at least one polysiloxane contains at least one isocyanate functional group, the at least one polysiloxane may be prepared by reacting at least one polysiloxane containing hydroxyl functional groups as described above with a polyisocyanate, for example diisocyanate. Non-limiting examples of suitable polyisocyanates include aliphatic polyisocyanates such as aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate; Alicyclic polyisocyanates such as 1,4-cyclohexyl diisocyanate, isophorone diisocyanate and α, α-xylylene diisocyanate; And aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate and tolylene diisocyanate. These and other suitable polyisocyanates are disclosed in more detail in column 5, lines 26 to 6, line 28 of US Pat. No. 4,046,729, which is incorporated herein by reference. The reaction conditions and ratios of the reactants are chosen such that the desired functional groups are formed.

Substituent X in the structure of Formula IV may comprise a polymeric urethane or urea containing material terminated with an isocyanate, hydroxyl, primary or secondary amine functional group or any mixture of these materials. If substituent X comprises such functional groups, the one or more polysiloxanes are two per molecule, selected from one or more of the aforementioned polysiloxane polyols, one or more polyisocyanates and optionally hydroxyl groups, primary amine groups and secondary amine groups It may be a reaction product of one or more compounds having at least active hydrogen atoms.

Non-limiting examples of suitable polyisocyanates include those described above. Non-limiting examples of compounds having two or more active hydrogen atoms per molecule include polyols and polyamines containing primary and / or secondary amine groups.

Non-limiting examples of suitable polyols include polyalkylene ether polyols such as thio ethers; Polyester polyols such as polyhydroxy polyesteramides; And hydroxyl containing polycaprolactone and hydroxy-containing acrylic copolymers. Various polyols, for example glycols, for example ethylene glycol, 1,6-hexanediol, bisphenol A and the like, or higher polyols, for example polyether polyols formed from oxyalkylation such as trimethylolpropane, pentaerythritol This is also useful. Polyester polyols may also be used. Column 7, lines 52 to column 8, line 9 of US Pat. No. 4,046,729, which is recited herein by reference and other suitable polyols; Column 8, lines 29 to column 9, line 66; And column 2, line 64 to column 3, line 33 of US Pat. No. 3,919,315.

Non-limiting examples of suitable polyamines are primary or secondary diamines wherein the groups bonded to the nitrogen atom may be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted aliphatic, aliphatic-substituted aromatic and heterocyclic. Or polyamines. Typical suitable aliphatic and cycloaliphatic diamines include 1,2-ethylene diamine, 1,2-propylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine and the like. Suitable aromatic diamines are phenylene diamine and toluene diamines such as o-phenylene diamine and p-tolylene diamine. These and other suitable polyamines are disclosed in detail in column 6, line 61 to column 7, line 26, of US Pat. No. 4,046,729, which is incorporated herein by reference.

In one embodiment substituent X of Formula IV may comprise a polymer ester containing group terminated with a hydroxyl or carboxylic acid functional group. When X is such a group, the one or more polysiloxanes may be the reaction product of one or more polysiloxane polyols, one or more materials comprising one or more carboxylic acid functional groups, as described above, and one or more organic polyols. Non-limiting suitable examples of materials comprising at least one carboxylic acid functional group include carboxylic acid group-containing polymers well known in the art, such as carboxylic acid group-containing acrylic polymers, polyester polymers and polyurethane polymers, for example US patents. There are those disclosed in US Pat. No. 4,681,811. Non-limiting examples of suitable organic polyols include those described above.

To prepare one or more polysiloxanes containing epoxy groups, one or more polysiloxanes containing hydroxyl functional groups as described above may be further reacted with the polyepoxide. The polyepoxide may be an aliphatic or alicyclic polyepoxide or a mixture thereof. Non-limiting examples of suitable polyepoxides for use include one or more ethylenically unsaturated monomers comprising one or more epoxy groups, such as glycidyl (meth) acrylate and allyl glycidyl ether, and one without epoxy functional groups. And epoxy functional acrylic copolymers prepared from the above ethylenically unsaturated monomers. Methods for preparing such epoxy functional acrylic copolymers are disclosed in detail in column 4, line 52 to column 5, line 50 of US Pat. No. 4,681,811, which is incorporated herein by reference. The reaction conditions and ratios of the reactants are chosen such that the desired functional groups are formed.

In one embodiment, the present invention relates to the aforementioned coating composition, wherein the at least one polysiloxane comprises a reactive functional group that is a thermally curable functional group. In alternative embodiments, one or more of the reactive functional groups of the polysiloxane may be cured by ionizing radiation or actinic radiation. In yet another alternative embodiment, the polysiloxane may comprise one or more functional groups that can be cured by thermal energy and one or more functional groups that can be cured by ionizing or actinic radiation. Suitable radiation curable groups are discussed in detail above.

The second material, when added to the other components forming the coating composition, is generally present in the coating composition in an amount of from 0.5 to 98.5 weight percent based on the total weight of the resin solids of the components forming the coating composition. In one embodiment of the present invention, the second material is generally present in an amount of at least 25% by weight when added to other components forming the coating composition. The second material is present in an amount of at least 5% by weight and is generally present in an amount of at least 50% by weight based on the total weight of the resin solids in the components forming the coating composition. In addition, the second material is generally present in an amount of less than 98.5 weight percent when added to other components in the coating composition. It may be present in an amount of less than 95 weight percent, generally less than 90 weight percent, based on the total weight of the resin solids of the components forming the coating composition. The amount of second material present in the coating composition can range from any combination therein, including both ends of the numerical value.

In another embodiment, one or more functional groups curable by thermal energy and one or more functional groups curable by ionizing radiation or actinic radiation, using one or more dual curing materials instead of or in addition to the first and second materials A coating composition can be prepared. Examples of such materials are disclosed in European Patent Application No. 940 422, described above and incorporated herein by reference. If a dual cured material is present, it may generally be present in the coating composition at 0.5 to 99% by weight, based on the total weight of the resin solids of the other components forming the coating composition, when added to the other components forming the coating composition. It can be a range of any combination therein, including both ends of the numerical value.

In one embodiment, the components that form the coating composition include one or more curing agents that are reactive with the thermosetting groups of the second material. One or more curing agents may be selected from aminoplast resins, polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols and mixtures thereof.

In another embodiment in which a dual curable material is present, the components forming the coating composition are at least one selected from polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols and mixtures thereof Hardener.

In another embodiment, the curing agent is aminoplast. Aminoplast resins, including phenolplasts, are well known in the art as curing agents for hydroxyl, carboxylic acid, and carbamate functional group-containing materials. Suitable aminoplasts, such as those discussed above, are known to those skilled in the art. Aminoplasts can be obtained from condensation reactions of formaldehyde with amines or amides. Non-limiting examples of amines or amides are melamine, urea or benzoguanamine. Condensates with other amines or amides may be used, for example aldehyde condensates of glycoluril which provide high melt crystalline products useful for powder coatings. Formaldehyde is the most frequently used aldehyde, but other aldehydes such as acetaldehyde, crotonaldehyde and benzaldehyde can also be used.

Aminoplasts contain imino and methylol groups and in certain cases at least some of the methylol groups are etherified with alcohols to modify the curing reaction. For this purpose monohydric alcohols including methanol, ethanol, n-butyl alcohol, isobutanol and hexanol can be used.

Non-limiting examples of aminoplasts include melamine-, urea- or benzoguanamine-formaldehyde condensates, which in certain cases are in monomeric form or at least partially etherified with one or more alcohols of 1 to 4 carbon atoms. Exists in the form of Non-limiting examples of suitable aminoplast resins are products such as the trademark CYMEL from Cytec Industries, Inc. and the trademark RESIMENE from Solutia, Inc.

In another embodiment, the present invention provides that, when the aminoplast curing agent is added to other components forming the coating composition, the curing agent generally is from 0.5 to 65 based on the total weight of the resin solids forming the coating composition. To the cured composition described above, which is present in an amount by weight.

Non-limiting examples of other curing agents suitable for use include polyisocyanate curing agents. The term "polyisocyanate" as used herein is to be understood to include blocked (or capped) polyisocyanates as well as unblocked polyisocyanates. The polyisocyanate may be aliphatic polyisocyanate or aromatic polyisocyanate, or mixtures thereof. Often higher polyisocyanates such as isocyanurates of diisocyanates are used but diisocyanates may be used. Higher polyisocyanates can also be used with diisocyanates. Isocyanate prepolymers can also be used, for example reaction products of polyisocyanates with polyols. Mixtures of polyisocyanate curing agents can also be used.

When the polyisocyanate is blocked or capped, suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohols known to those skilled in the art can be used as the capping agent for the polyisocyanate. Other suitable capping agents include oximes and lactams. In use, when the polyisocyanate curing agent is added to other components in the coating composition, the curing agent is typically present in an amount of from 5 to 65% by weight, based on the total weight of the resin solids of the components forming the coating composition. It may range from weight percent, and is often present in an amount from 15 to 40 weight percent.

Other useful curing agents include triazine derived isocyanates, for example tricarbamoyl triazine compounds specifically described in US Pat. No. 5,084,541, which is incorporated herein by reference. In use, when triazine derived isocyanate is added to other components in the coating composition, it is typically present in an amount of up to 20 weight percent, based on the total weight of the resin solids of the components forming the coating composition, from 1 to 20 weight It may be in the range of%.

Anhydrides as curing agents for hydroxyl functional group-containing materials are known in the art and can be used in the present invention. Non-limiting examples of suitable anhydrides for use as curing agents in the coating compositions of the present invention include mixtures of monomers comprising ethylenically unsaturated carboxylic anhydrides and one or more vinyl comonomers such as styrene, alpha-methylstyrene, vinyl toluene and the like. Derived from include having two or more carboxylic acid anhydride groups per molecule. Suitable ethylenically unsaturated carboxylic anhydrides include, but are not limited to, maleic anhydride, citraconic anhydride and itaconic anhydride. Anhydrides may also be anhydrous adducts of diene polymers such as maleated polybutadiene or maleated copolymers of butadiene such as butadiene / styrene copolymers. Such anhydride curing agents and other anhydride curing agents are described in lines 16-50 of column 10 of US Pat. No. 4,798,746 and lines 41-57 of column 3 of US Pat. No. 4,732,790.

Polyepoxides as curing agents for carboxylic acid functional group-containing materials are known in the art. Suitable polyepoxides for use in the coating compositions of the present invention include, but are not limited to, polyglycidyl ethers of polyhydric phenols and aliphatic alcohols, such as epichlorohydrin in the presence of alkalis. It can be prepared by etherification with epihalohydrin. These polyepoxides and other suitable polyepoxides are described in column 5, lines 33-58 of US Pat. No. 4,681,811, which is incorporated herein by reference.

Suitable curing agents for epoxy functional group-containing materials are acid group-containing acrylic polymers prepared from polyacid curing agents such as ethylenically unsaturated monomers containing at least one carboxylic acid-group and at least one ethylenically unsaturated monomer without carboxylic acid groups. It includes. The acid functional acrylic polymer may have an acid value of 30 to 150. Acid functional group-containing polyesters may also be used. Such polyacid curing agents are described in column 6, line 45 to column 9, line 54 of US Pat. No. 4,681,811, which is incorporated herein by reference.

In addition, polyols, i.e. materials having two or more hydroxyl groups per molecule, are well known in the art as curing agents for isocyanate functional group-containing materials. Suitable materials for use in the coating compositions of the present invention include, but are not limited to, polyalkylene ether polyols including thio ethers; Polyester polyols including polyhydroxy polyesteramides; And hydroxyl-containing polycaprolactone and hydroxy-containing acrylic acid copolymers. In addition, polyether polyols formed by oxyalkylating various polyols such as ethylene glycol, glycols such as 1,6-hexanediol, bisphenol A, or higher polyols such as trimethylolpropane and pentaerythritol are useful. Polyester polyols may also be used. Such polyol curing agents and other suitable polyol curing agents include, but are not limited to, column 7, lines 52 to 8, line 9 and column 8, lines 29 to column 9, line 66 of US Pat. No. 4,046,729; And column 2, line 64 to column 3, line 33, US Pat. No. 3,919,315, both of which are incorporated herein by reference.

In addition, polyamines can be used as curing agents for isocyanate functional group-containing materials. Suitable polyamine curing agents include, but are not limited to, primary or secondary diamines or polyamines in which the radicals attached to nitrogen atoms may be unsaturated or saturated, aliphatic, cycloaliphatic, aromatic, aromatic substituted aliphatic, aliphatic substituted aromatics, hetero Cyclic matter can be illustrated. Suitable aliphatic and cycloaliphatic diamines include, but are not limited to, 1,2-ethylene diamine, 1,2-propylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like. Can be. Suitable aromatic diamines include, but are not limited to, phenylene diamines and toluene diamines such as o-phenylene diamine and p-tolylene diamine. Such polyamines and other suitable polyamines are described in detail in column 6, line 61 to column 7, of US Pat. No. 4,046,729, which is incorporated herein by reference.

In some cases, mixtures of suitable curing agents may be used. It is to be understood that the coating composition may be formulated as a one-component coating composition in which a curing agent, such as an aminoplast resin and / or a triazine compound described above, is additionally mixed with other coating composition components. The one-component coating composition may have storage stability when formulated. The coating composition may also be formulated as a bicomponent coating composition in which the polyisocyanate curing agent described above may be added to a preformed addition mixture of other coating composition components immediately prior to application. The preformed addition mixture may comprise a curing agent such as an aminoplast resin and / or a triazine compound described above.

Generally, the curing agent is present in the coating composition in an amount of 0.5 to 65% by weight, based on the total weight of the resin solids of the components forming the coating composition when added to the other components forming the coating composition, and from 1 to 20% by weight. It may be present in an amount of% and may also be present in an amount of 5 to 15% by weight.

The components that form the coating composition include the first and second materials of the coating composition, the dual curable material (if present) and a plurality of particles different from the curing agent. The particles can be formed from materials selected from polymeric and non-polymeric inorganics, polymeric and non-polymeric organics, composites, and mixtures thereof. As used herein, the expression "formed from" is an open expression, for example, the expression "comprising" is used in the claims. For example, the term "formed from" a composition in the list of components mentioned refers to a composition comprising at least the components mentioned and may further include other components not mentioned during formation of the composition.

As used herein, the term “polymeric inorganic material” means a polymeric material having a repeating backbone unit based on element (s) other than carbon. For more detailed information, see James Mark et al., Inorganic Polymers , Prentice Hall Polymer Science and Engineering Series, (1992) at page 5, which is incorporated herein by reference. The term "polymer organic material" as used herein also means synthetic polymeric materials, semisynthetic polymeric materials and natural polymeric materials, all of which are repeatable backbone units based on carbon.

As used herein, the term "organic" refers to a carbon containing compound in which carbon is typically combined with carbon itself and hydrogen, often with other elements, among which two-component compounds such as carbon oxides, carbides, carbon disulfides, etc. ; 3-component compounds, such as metallic cyanide, metallic carbonyl, phosgene, and carbonyl sulfide; And carbon-containing ionic compounds such as metallic carbonates such as calcium carbonate and sodium carbonate. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary , (12th Ed. 1993), pages 761-762, and M. Silberberg, Chemistry The Molecular Nature of Materials and Change (1996), page 586, which is herein incorporated by reference. Specifically cited by reference.]

As used herein, the term "inorganic material" refers to any material that is not an organic material.

As used herein, the term “composite” means a combination of two or more different materials. In general, the hardness at the particle surface of the particles formed from the composite material is different from the internal hardness below the particle surface. More specifically, the particle surface can be modified in a well known manner including, but not limited to, changing the surface properties chemically or physically using techniques known in the art.

For example, the particles can be formed from a first material that is coated, cladding or encapsulated with one or more second materials to form composite particles having a soft surface. In another embodiment, the particles formed from the composite material may be formed from a first material that is coated, cladding or encapsulated with a different type of first material. More specific information regarding the particles useful in the present invention can be found in G. Wypych, Handbook of Fillers , 2nd Ed. (1999), pages 15-202.

Particles suitable for use in the coating compositions of the present invention may include inorganic elements or compounds known in the art. Suitable particles can be formed from ceramic materials, metallic materials and mixtures thereof. Suitable ceramic materials include metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates and mixtures thereof. Particularly suitable metal nitrides include, but are not limited to, boron nitride, zinc oxide as metal oxide, molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide as metal sulfide, aluminum silicate and magnesium silicate as metal silicate (e.g. : Vermiculite) can be illustrated respectively.

The particles are for example colloidal fumed or amorphous forms of silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, for example colloidal or amorphous zirconia, and Single inorganic oxides such as mixtures thereof; Or another type of organic oxide may comprise a core consisting essentially of an inorganic oxide of the deposited type. When the cured composition of the present invention is used as a clear top coat, for example as a clear coat in a multicomponent composite coating composition, the particles should not be significantly interfered with the optical properties of the cured composition. As used herein, the term “transparent” means that the cured coating has a BYK haze index of less than 50 when measured using the BYK / Haze Gloss instrument.

Non-polymeric inorganic materials useful for forming the particles of the present invention include inorganic materials selected from graphite, metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates and hydroxides. Useful inorganic oxides include, but are not limited to, zinc oxide. Suitable inorganic sulfides include, but are not limited to, molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide. Useful inorganic silicates include, but are not limited to, aluminum silicates and magnesium silicates (eg vermiculates). Suitable metals include, but are not limited to, molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys and mixtures thereof.

In one embodiment, the invention relates to a cured composition as described above wherein the particles in the composition comprise fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide , Colloidal yttria, zirconia, colloidal zirconia and mixtures thereof. In another embodiment, the present invention relates to a cured composition as described above wherein the particles in the composition comprise colloidal silica. As disclosed above, the materials may be untreated or surface treated.

The coating composition may comprise precursors suitable for forming silica particles in situ by a sol-gel process. The coating composition according to the invention may comprise an alkoxy silane which can be hydrolyzed to form silica particles in situ. For example, tetraethylortho silicate can be hydrolyzed and condensed with an acid such as hydrochloric acid to form silica particles. Other useful particles can be exemplified by the surface modified silica described in column 6, line 51 to column 8, line 43 of US Pat. No. 5,853,809, which is incorporated herein by reference.

In one embodiment of the invention, the particles have a hardness value that is greater than the hardness value of the material capable of polishing the polymer coating or polymer substrate. Non-limiting examples of materials that can polish the polymer coating or polymer substrate include mud, sand, rock, glass, car wash brushes, and the like. Hardness values of particles and materials capable of polishing the polymer coating or polymer substrate can be measured by conventional hardness measurements such as Vickers or Brinell hardness, but the relative scratch resistance of the material surface is 1 to 10 It may also be measured according to the original Moh's hardness scale, which is expressed as a value of. Some non-limiting MOS hardness values of particles formed from inorganic materials suitable for use in the present invention are illustrated in Table A below.

Particulate matter Morse Hardness (Aid Scale) Boron nitride 2 in ¹ black smoke 0.5 to 1 ² Molybdenum disulfide 1 ³ talc 1 to 1.5 ⁴ mica 2.8 to 3.2 ⁵ Kaolinite 2.0 to 2.56 gypsum 1.6 to 2 ⁷ Calcite (Calcium Carbonate) 3 ⁸ Calcium fluoride 4 ⁹ Zinc oxide 4.5 ¹⁰ aluminum 2.5 ¹¹ Copper 2.5 to 3 ¹² iron 4 to 5 ¹³ gold 2.5 to 3 ¹⁴ nickel 5 ¹⁵ Palladium 4.8 ¹⁶ platinum 4.3 ¹⁷ silver 2.5 to 4 ¹⁸ Zinc sulfide 3.5 to 4 ¹⁹

* Note: 1: K., incorporated herein by reference. Ludema, Friction, Wear, Lubrication , (1996), page 27].

2: See R. Weast (Ed.), Handbook of Chemistry and Physics , CRC Press (1975), page F-22.

3: literature, which is incorporated herein by reference. Lewis, Sr., Hawley's Condensed Chemical Dictionary , (12th Ed. 1993), page 793.

4: See Hawley's Condensed Chemical Dictionary , (12th Ed. 1993), page 1113, which is incorporated herein by reference.

5: See Hawley's Condensed Chemical Dictionary , (12th Ed. 1993), page 784, which is incorporated herein by reference.

6: See Handbook of Chemistry and Physics, page F-22.

7: See Handbook of Chemistry and Physics, page F-22.

8: See Friction, Wear, Lubrication, page 27.

9: See Friction, Wear, Lubrication, page 27.

10: See Friction, Wear, Lubrication, page 27.

11: See Friction, Wear, Lubrication, page 27.

12: See Handbook of Chemistry and Physics, page F-22.

13: See Handbook of Chemistry and Physics, page F-22.

14: See Handbook of Chemistry and Physics, page F-22.

15: See Handbook of Chemistry and Physics, page F-22.

16: See Handbook of Chemistry and Physics, page F-22.

17: See Handbook of Chemistry and Physics, page F-22.

18: See Handbook of Chemistry and Physics, page F-22.

19: R. Weast (Ed.), Handbook of Chemistry and Physics , CRC Press (71 ^st Ed. 1990), page 4-158.

In one embodiment, the particle hardness value of the particles is greater than five. In certain embodiments, the MOS hardness value of the particles, such as silica, is greater than six.

As mentioned above, the Mohs hardness measure relates to the scratch resistance of a material. Thus, the present invention further relates to particles having a surface hardness different from the particle internal hardness below the particle surface. More specifically, as discussed above, the particle surface can be modified in a manner well known in the art, including, but not limited to, the surface hardness of the particles being greater than the hardness of the material capable of polishing the polymer coating or polymer substrate. The surface properties of the particles can be chemically changed using techniques known in the art such that the hardness of the particles below is less than the hardness of the polymer material or the material capable of polishing the polymer substrate.

As another alternative, the particles can be formed from a first material that is coated, clad or encapsulated with one or more second materials to form a composite with a hard surface. In addition, the particles may be formed from a first material that is coated, clad or encapsulated with a different material of the first material to form a composite material having a hard surface.

As a non-limiting example, inorganic particles formed from inorganic materials such as silicon carbide or aluminum nitride can be provided with silica, carbonate or nanoclay coatings to form useful multiparticulates. In another non-limiting example, silane coupling agents with alkyl side chains interact with the surface of inorganic particles formed from inorganic oxides to provide useful composite particles having a "soft" surface. Other examples include cladding, encapsulating or coating particles formed from nonpolymeric or polymeric materials with different nonpolymeric or polymeric materials. A particular non-limiting example of such composite particles is DUALITE®, a synthetic polymer particle coated with calcium carbonate commercially available from Pierce and Stevens Corporation, Buffalo, NY.

In one non-limiting embodiment of the invention, the particles are formed from a solid lubricant material. As used herein, the term “solid lubricant” means a solid that is used between two surfaces that provide protection against damage during relative movement and / or reduce friction and wear. In one embodiment, the solid lubricant is a solid inorganic lubricant. The term "inorganic solid lubricant" as used herein means that the solid lubricant has a characteristic crystal behavior that causes shear to a thin plate and thus easily slides into another, resulting in an antiwear lubricating effect. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary , (12th Ed. 1993), page 712, which is specifically incorporated herein by reference. Friction represents resistance to sliding one solid from another. F., incorporated herein by reference. Clauss, Solid Lubricants and Self-Lubricating Solids (1972), page 1].

In one non-limiting embodiment of the invention, the particles have a lamellar structure. The lamellar particles consist of a hexagonal array of sheets or plates of atoms, strongly bound within the sheet, weakly bound by van der Waals forces between the sheets, and providing low shear strength between the sheets. Non-limiting examples of lamellar structures include hexagonal crystal structures. Inorganic solid particles having a lamellar fullerene (ie, buckball) structure are also useful in the present invention.

Non-limiting examples of suitable materials having a lamellar structure useful for forming the particles of the present invention include boron nitride, graphite, metal dichalcogenide, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, And mixtures of the foregoing materials. Suitable metal dichalcogenides include molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures of the foregoing materials.

The particles can be formed from nonpolymeric organic materials. Non-limiting examples of nonpolymeric organic materials useful in the present invention include, but are not limited to, stearates (eg zinc stearate and aluminum stearate), diamond, carbon black and stearamide.

The particles can be made of an inorganic polymeric material. Non-limiting examples of useful inorganic polymeric materials include polyphosphazenes, polysilanes, polysiloxanes, polygeremann, polymeric sulfur, polymeric selenium, silicone, and mixtures of these materials. Non-limiting examples of particles formed from inorganic polymeric materials useful in the present invention include TOSPEARL (R), commercially available from Toshiba Silicones Company, Ltd., Japan, as particles made of crosslinked siloxanes. RJPerry "Applications for Cross-Linked Siloxane Particles: Chemtech , February 1999, page 39-44".

The particles can be made from synthetic organic polymeric materials. Non-limiting examples of suitable organic polymeric materials include, but are not limited to, thermosets and thermoplastics. As used herein, "thermoplastic" materials are materials that soften when exposed to heat and return to their original state when cooled to room temperature. Non-limiting examples of suitable thermoplastics include thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonates, polyolefins such as polyethylene, polypropylene, and polyisobutene, acrylics. Polymers such as copolymers of styrene and acrylic acid monomers, polymers containing methacrylates, polyamides, thermoplastic polyurethanes, vinyl polymers, and mixtures of the foregoing materials.

Non-limiting examples of suitable thermosetting materials include thermosetting polyesters, vinyl esters, epoxy materials, phenolic materials, aminoplasts, thermosetting polyurethanes, and mixtures of the foregoing materials. Specific non-limiting examples of synthetic polymer particles formed from epoxy materials are epoxy microgel particles. As used herein, a "thermoset" material is a material that, when heated, becomes irreversibly solidified or "cured". Thermosets form crosslinked networks. As used herein, when at least partially forming a polymer network, the polymeric material is said to be "crosslinked." Those skilled in the art will recognize that the presence and extent of crosslinking (crosslink density) can be varied in various ways, for example, dynamic mechanical thermal analysis using a TA Instruments DMA 2980 DMTA analyzer performed under nitrogen as described above. It can be measured by DMTA). This method measures the glass transition temperature and crosslink density of the glass film of the coating or polymer. This physical property of the cured material is related to the structure of the crosslinked network.

The particles may also be hollow particles formed from materials selected from polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composite materials, and mixtures described above. Non-limiting examples of suitable materials capable of forming hollow particles are as described above. In one embodiment, the hollow particles are hollow glass spheres.

For example, but not limited to, the particles according to the invention to be applied to polymer substrates or polymer coatings, such as electrodeposition coatings, undercoats or topcoats, may be present in the form of dispersions, suspensions or emulsions in the carrier. Non-limiting examples of suitable carriers include, but are not limited to, water, solvents, surfactants, or mixtures of the foregoing materials. Non-limiting examples of suitable solvents include mineral oils, alcohols such as methanol or butanol, ketones such as methyl amyl ketone, aromatic hydrocarbons such as xylene, glycol ethers such as ethylene glycol monobutyl ether, esters, aliphatic materials, and the foregoing Although a compound is mentioned, It is not limited to this.

Prior to introduction, one class of particles that can be used according to the present invention includes sols such as organic sol of the particles. Such sol can be a wide range of fine particles, colloidal silica of average particle diameter in the range as described above.

Colloidal silica can be surface modified after or during the initial formation of the particles. These surface modified silicas have carbon-containing moieties that are chemically bonded on their surfaces, depending on the properties of the particular silica required, and anhydrous SiO ₂ and SiOH groups, various ions physically associated or chemically bonded to the silica surface. And groups such as groups, adsorbed organic groups or combinations of the foregoing groups. Such surface modified silica is disclosed in detail in US Pat. No. 4,680,204, which is incorporated herein by reference.

Such materials can be prepared in various forms and by various techniques. Non-limiting examples include organic sol and mixed sol. As used herein, the term “mixed sol” is intended to include dispersions of colloidal silica in which the dispersion medium comprises both organic liquids and water. Colloidal silicas of such particulates are readily available, inherently colorless, and capable of forming colorless transparent coatings without additional pigments or ingredients known to those skilled in the art for reducing the transparency and / or coloring of such compositions. It has a refractive index that makes it possible to introduce the material into it.

Suitable non-limiting examples of particles are commercially available from Nissan Chemical Company under the trade name ORGANOSILICASOLS® such as ORGANOSILICASOL® MT-ST, or Clariant Corporation as HIGHLINK®. Colloidal silica such as commercially available from; Colloidal alumina commercially available from Nalco Chemical under the tradename NALCO 8676®; The colloidal zirconia commercially available from Nissan Chemical Company is mentioned as brand name HIT-32M (trademark).

The particles can be introduced into the compositions of the present invention in the form of stable dispersions. If the particles are in colloidal form, the dispersion can be prepared by dispersing the particles in the carrier while shaking, and the solvent present can be removed under vacuum at ambient temperature. In certain embodiments, the carrier may be a material other than a solvent such as a surface active agent, which will be described in detail below, and non-limiting examples thereof include polysiloxanes containing but not limited to one or more polysiloxanes (a). It can be mentioned).

Alternatively, dispersions may be prepared as disclosed in US Pat. No. 4,522,958 or US Pat. No. 4,526,910, which is incorporated herein by reference. The particles may be “cold-blended” with one or more polysiloxanes before they are introduced into the compositions of the present invention. Optionally, the particles can be post-added to a mixture of any remaining composition components (including but not limited to one or more polysiloxanes (a)) and dispersed using dispersion techniques known in the art.

If the particles are in a form other than colloidal form, such as, but not in the form of agglomerates, the dispersion disperses one or more polysiloxanes (a), but not limited thereto, in a carrier to stably disperse the particles. It can be manufactured by. Dispersion techniques known in the art of coating formulations can be used, such as polishing, grinding, microfluidization, sonication, or any other pigment dispersion technique. Optionally, the particles can be dispersed by any dispersion technique known in the art. If desired, particles other than colloidal forms may be subsequently added to the mixture of other composition components and dispersed using any dispersion technique known in the art.

In one embodiment, the invention relates to a composition comprising a plurality of particles, wherein the first portion of the particles is at a concentration higher than the concentration of the second region of particles present in the bulk region of the cured composition. Exists in the surface area of the.

As used herein, the “surface region” of the cured composition is generally parallel to the exposed air-surface of the coated substrate and from the surface of the cured coating to a depth of at least 20 nm to 150 nm below the exposed surface. By vertically generally meant an area having an extended depth. In certain embodiments, the thickness of this surface area may be at least 20 nm to 100 nm, and may range from at least 20 nm to 50 nm (including the above values). As used herein, “bulk region” of the cured composition means an area that extends below the surface area and is generally parallel to the surface of the coated substrate. The bulk region has a thickness that extends from the interface with the surface region to the substrate or coating layer under the cured composition through the cured coating.

In embodiments of the invention where the average particle diameter of the particles is greater than 50 nm, the thickness of the surface area generally extends vertically from the surface of the cured coating to a thickness corresponding to three times the average particle diameter of the particles, the surface of the particles It can extend to a depth corresponding to twice the average particle diameter of.

The concentration of particles in the cured composition can be characterized in a variety of ways. For example, the average number density of particles dispersed in the surface area (ie, the average number or number of particles per unit volume) is greater than the average number density dispersed in the bulk area. Optionally, the average volume fraction of particles dispersed in the surface area (i.e., volume / total volume occupied by the particles) or average weight percent per unit volume (i.e., ((weight of particles in unit volume of the cured coating) / (Total weight of unit volume of the cured coating)) × 100%) is greater than the average weight percent or average volume fraction of particles dispersed in the bulk region.

The concentration of particles (characterized as described above) present in the surface area of the cured coating can be determined by various surface analysis techniques known in the art, such as electron transmission microscopy (TEM), surface scanning electron microscopy (if required). X-SEM), atomic force microscopy (AFM), and X-ray photoelectron spectrophotometry.

For example, the particle concentration present in the surface area of the cured coating can be measured by cross-sectional electron transmission microscopy techniques. Useful electron transmission microscopy methods are generally described below. The coating composition is applied to a substrate and cured under conditions suitable for the composition and the substrate. A sample of the cured coating is then recovered or peeled from the substrate and embedded in the cured epoxy resin using techniques as known in the art. The embedded sample can then be microtome at room temperature by techniques known in the art, such as block surface formation. This zone can be cut using a 45 ° diamond knife mounted in a holder in a "boat-shaped cavity" to capture water. During the cutting process, the zone rises to the surface of the water in the boat-like cavity. Once several cuts reach the interference color from light gold to dark gold (ie, between about 100 and 150 nm thick), individual samples are typically collected on a formvar-carbon coated grating and glass Dry at room temperature on a slide. The samples were then placed in a suitable electron transmission microscope, for example Philips CM12 TEM, and measured at various magnifications, for example 105,000 times, for examination of the particle concentration in the surface area via an electron microscope. The concentration of particles in the surface area of the cured coating can be investigated by visual observation of electron micrography.

It is to be understood that the particles may be present in the surface area such that a portion of the particles may at least partially protrude over the cured coating surface unprotected by the organic coating layer. Optionally, the particles may be present in the surface region such that the organic coating layer is between the particles and the exposed air-surface interface of the surface region.

In one embodiment, the present invention relates to a cured composition as described above, wherein the average particle diameter of the particles prior to introduction into the coating composition may be less than 100 μm, and the average particle diameter may be less than 50 μm prior to introduction into the coating composition. In another embodiment, the present invention relates to a cured composition as described above, wherein the average particle diameter of the particles is less than 1 to 1000 nm prior to introduction into the curable composition. In another embodiment, the present invention relates to a cured composition as described above, wherein the average particle diameter of the particles is 1 to 100 nm prior to introducing the curable composition.

In another embodiment, the present invention relates to a cured composition as described above, wherein the average particle diameter of the particles is 5 to 50 nm prior to introduction into the composition. In another embodiment, the present invention relates to a cured composition as described above, wherein the average particle diameter of the particles is 5-25 nm prior to introduction into the composition. The particle diameter can range between any combination of the above values, including the stated values.

In embodiments in which the average particle diameter of the particles is greater than 1 μm, the average particle diameter can be measured according to known laser scattering techniques. For example, the average particle diameter of such particles uses a helium-neon laser with a wavelength of 633 nm to measure the particle diameter, and a horiba, assuming that the particle is spherical, ie the particle diameter refers to the smallest sphere that completely encloses the particle. Measurements were made using a (Horiba) model LA 900 laser diffraction particle size instrument.

In embodiments of the invention wherein the particle diameter of the particles is 1 μm or less, the average particle diameter is visually observed by electron micrographing of an electron transmission microscope (TEM) image, the diameter of the particles in the image is determined, and based on the magnification of the TEM image. It can measure by calculating an average particle diameter. Those skilled in the art will understand how to prepare such TEM images, which are described in the Examples described below. In one non-limiting embodiment of the invention, a TEM image with a magnification of 105,000 times was produced and the conversion factor was obtained by dividing the magnification by 1000. When visually observed, the diameter of the particles is measured in millimeters and the measurement is converted to nm using a conversion factor. The diameter of a particle is referred to as the smallest diameter sphere that completely surrounds the particle.

The shape (or tissue) of the particles can vary depending on the specific embodiment of the present invention and their intended use. For example, generally spherical tissue (eg, solid beads, microbeads or hollow spheres) may be used, or particles that are tetrahedral, plate-like, or needle-like (extended or fibrous) may be used. In addition, the particles can maintain a hollow internal structure, porous or empty voids, or have a combination of the aforementioned forms, for example porous or solid walls and hollow cores. For more detailed information on suitable particle characteristics, see Handbook of Fillers and Plastics (1987), page 9-10, specifically cited herein.

Those skilled in the art will recognize that mixtures of one or more particles having different average particle diameters are introduced into a composition according to the present invention to impart the desired properties and properties to the composition. For example, particles of various particle diameters can be used in the compositions according to the invention.

In one embodiment, the present invention provides that when the particles are added to other components that form the composition, the particles are present in the composition in an amount of 0.01 to 75% by weight based on the total weight of the resin solids of the components that form the composition. , To a composition as described above. In another embodiment, the invention provides that the particles are present in the composition in an amount of at least 0.1% by weight, based on the total weight of the resin solids of the components that form the composition, when the particles are added to the other components that form the composition. , The particles may be present in the composition in an amount of at least 0.5% by weight and may also be present in the composition in an amount of at least 5% by weight.

In another embodiment, the present invention relates to the above, wherein the particles are present in the composition in an amount of less than 75% by weight, based on the total weight of the resin solids of the components forming the composition, when the particles are added to the other components forming the composition. It relates to a cured composition as one. In a further embodiment, the present invention relates to the above, wherein the particles are present in the composition in an amount of less than 50% by weight, based on the total weight of the resin solids of the components that form the composition, when the particles are added to the other components that form the composition. It relates to a cured composition as one. In another embodiment, the invention relates to the aforementioned, wherein the particles are present in a composition of less than 20% by weight, based on the total weight of the resin solids of the components that form the composition, when the particles are added to other components that form the composition. To a cured composition as such. In another embodiment, the present invention relates to a method wherein the particles are present in the composition in an amount of less than 10% by weight, based on the total weight of the resin solids of the components that form the composition, when the particles are added to other components that form the composition. To a composition as described. The amount of particles present can range between any combination of these values, including the values mentioned.

Additionally, in another embodiment, the present invention relates to a composition, wherein one or more surface active agents may be present while forming the composition as described above. One or more surface active agents may be selected from anionic, nonionic and cationic surface active agents.

As used herein, "surfactant" means any material that tends to reduce the surface energy or solid surface tension of the cured composition or coating. That is, a cured composition or coating formed from a composition comprising a surface active agent has a lower solid surface tension or surface energy compared to a cured coating formed from a similar composition containing no surface active agent.

For the purposes of the present invention, the solid surface tension is determined according to the Owens Wendt method using distilled water and methylene iodide as reagents and using the Rame's-Hart Contact Angle Goniometer. It can be measured. In general, 0.02 cc drops of one reagent were placed on the cured coating surface and the contact angle and their excitation angle were measured using a standard microscope equipped with a goniometer. Contact angles and their angles were measured for 3 drops each. The procedure was then repeated using another reagent. The average value was calculated after six measurements for each reagent. The solid surface tension was then calculated using the Owen-Wenz formula of Equation 1 below:

Where

γ ^l is the surface tension of the liquid (methylene is 50.8, distilled water is 72.8),

γ ^d and γ ^p are dispersion components and polar components (γ ^d of methylene iodide is 49.5, γ ^p is 1.3; γ ^d of distilled water is 21.8, and γ ^p is 51.0),

The cos Φ value was determined by measuring the value of γ.

Next, we arranged two equations, one for methylene iodide and the other for water. Only unknowns are γ _s ^d and γ _s ^p . Then we solved two equations for two unknowns. The two components combined represent the total solid surface tension.

One or more surface active agents may be selected from amphiphilic reactive functional group-containing polysiloxanes, amphiphilic fluoropolymers and mixtures of the foregoing compounds. In water-soluble or water-dispersible amphiphilic materials, the term "amphoteric" refers to a polymer that retains a hydrophilic polar end and a generally hydrophobic end that is water insoluble. Non-limiting examples of suitable functional group-containing polysiloxanes useful as surface active agents include the polysiloxanes described below. Non-limiting examples of suitable amphiphilic fluoropolymers are the fluoroethylene-alkyl vinyl ether alternating copolymers available from Asahi Glass Company under the trade name LUMIFLON (US Pat. No. 4,345,057). As described); Fluorosurfactants, such as the fluoroaliphatic polymer esters available from 3M, St. Paul, Minn., USA, under the trade name FLUORAD; Functionalized perfluorinated materials such as 1H, 1H-perfluoro-nonanol available from FluoroChem USA; And perfluorinated (meth) acrylate resins.

Non-limiting examples of other surfactants suitable for use in the curing compositions or coatings of the present invention may include anionic, nonionic and cationic surfactants. Non-limiting examples of suitable anionic surfactants include sulfates or sulfonates. Specific non-limiting examples include higher alkyl mononuclear aromatic sulfonates such as alkyl groups and higher or lower alkyl benzene sulfonates having 10 to 16 carbon atoms, for example decyl, undecyl, dodecyl, tridecyl, tetradecyl, Pentadecyl or hexadecyl benzene sulfonate and sodium salts of higher alkyl toluene, xylene and phenol sulfonates; Alkyl naphthalene sulfonates and sodium dinonyl naphthalene sulfonates. Other non-limiting examples of suitable anionic surfactants include olefin sulfonates, including long chain alkenylene sulfonates, long chain hydroxyalkane sulfonates, and any mixtures thereof. Non-limiting examples of other sulfate or sulfonate detergents are paraffin sulfonates, such as the reaction product of alpha olefins and bisulfite (eg sodium bisulfite). Also, sulfates of higher alcohols (eg sodium lauryl sulfate, sodium tallow alcohol sulfate), or sulfates of mono- or di-glycerides of fatty acids (eg stearic acid monoglyceride monosulfate), ethylene oxide and Alkyl poly (ethoxy) ether sulfates including but not limited to sulfates of condensation products of lauryl alcohol (generally having 1 to 5 ethenoxy groups per molecule); Lauryl or other higher alkyl glyceryl ether sulfonates; Aromatic poly (ethenoxy) ether sulfates, including but not limited to, sulfates of condensation products of ethylene oxide and nonyl phenol (generally having 1 to 20 oxyethylene groups per molecule).

Further non-limiting examples include salts of sulfated aliphatic alcohols, alkyl ether sulfates and / or alkyl aryl ethoxy sulfates commercially available under the trade name ABEX from Rhone-Poulenc. Phosphate mono- or di-ester type anionic surfactants may also be used. Such anionic surfactants are well known in the art and are commercially available from GAF Corporation under the trade name GATON and under the trade name Triton under the Rohm & Haas Company.

Non-limiting examples of suitable nonionic surfactants for use in the curable compositions or coatings of the present invention include the formula RO (R'O) _n H containing ether bonds, wherein substituent R is a hydrocarbon group having 6 to 60 carbon atoms. Substituent R 'is an alkylene group having 2 or 3 carbon atoms, n is an integer of 2 to 100; and any mixture thereof.

Such nonionic surfactants can be prepared by treating fatty alcohols or alkyl substituted phenols with excess ethylene or propylene oxide. The alkyl carbon chain may have 14 to 40 carbon atoms and may be derived from long chain fatty alcohols such as oleyl alcohol or stearyl alcohol. Nonionic polyoxyethylene surfactants of the type of the formula include SURFYNOL under the tradename SURFYNOL from Air Products Chemicals, Inc .; PLURONIC or TETRONIC from BASF Corporation; Tergitol on Union Carbide; And HURTSMAN Corporation, available as SURFONIC. Non-limiting examples of other suitable nonionic surfactants include, but are not limited to, block copolymers of glycol-based ethylene oxide and propylene oxide such as ethylene glycol or propylene glycol, including but not limited to those sold by BASF Corporation under the tradename Pluronic. do.

As mentioned above, cationic surfactants may also be used. Non-limiting examples of cationic surfactants suitable for use in the curable compositions or coatings of the present invention include ARMAC HT, an acetic acid salt of n-alkyl amines available from Akzo Nobel Chemicals. Acid salts of alkyl amines such as; Imidazoline derivatives such as CALGENE C-100 available from Calgene Chemicals Inc .; Ethoxylated amines or amides such as DETHOX Amine C-5, a commercially available cocoamine ethoxylate from Deforest Enterprises; Ethoxylated fatty acid amines such as ETHOX TAM available from Ethox Chemicals Inc .; And glyceryl esters such as LEXEMUL AR, a glyceryl stearate / stearaidoethyl diethylamine available from Inolex Chemical Co.

Examples of other suitable surfactants may include polyacrylates. Non-limiting examples of suitable polyacrylates include homopolymers and copolymers of acrylate monomers, such as acrylate monomers such as ethyl (meth) acrylate, 2-ethylhexyl acrylate, butyl (meth) acrylate and Isobutyl acrylate) and polybutylacrylates and copolymers derived from hydroxy ethyl (meth) acrylate and (meth) acrylic acid monomers. In one embodiment, the polyacrylates can have amino and hydroxy functional groups. Suitable amino and hydroxyl functional acrylates are disclosed in Example 26 below and US Pat. No. 6,013,733, which is incorporated herein by reference. Examples of other useful amino and hydroxyl functional copolymers are copolymers of hydroxy ethyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate and dimethylamino ethyl methacrylate. In another embodiment, the polyacrylate may have an acid functional group which may be provided by preparing an polyacrylate by incorporating an acid functional monomer such as, for example, (meth) acrylic acid into the component used. In another embodiment, the polyacrylate is a polyacrylate comprising, for example, an acid functional monomer such as (meth) acrylic acid and a hydroxyl functional monomer such as hydroxy ethyl (meth) acrylate in the component used. It can have an acid functional group and a hydroxyl functional group which can be provided by preparing.

In other embodiments, the reactants may include one or more materials with one or more reactive functional groups that are reversibly blocked with silyl groups. This silyl-blocked material is different from the first material, second material, dual curing material (if present) and curing agent of the composition. Hydrolysis of the silyl groups regenerates reactive functional groups on the material that can be used for further reaction with the curing agent.

Suitable silyl blockers are compounds of formula (IX):

Where

R ₁ , R ₂ and R ₃ are the same or different and each is an alkyl group having 1 to 18 carbon atoms, a phenyl group or an allyl group.

Non-limiting examples of suitable functional groups that can be blocked by silyl groups include hydroxyl groups, carbamate groups, carboxyl groups, amide groups and mixtures thereof. In one embodiment, the functional group is a hydroxyl group.

Non-limiting examples of suitable compounds that can react with functional groups to form silyl groups include hexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine, t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride, hexamethyl di Silylazide, hexamethyl disiloxane, trimethylsilyl triflate, hexamethyldissilyl acetamide, N, N'-bis [trimethylsilyl] -urea and mixtures of any of these.

Further examples of compounds suitable for the silylation reaction, and reaction conditions and reagents suitable for the trimethylsilylation reaction, are described in T. Greene et al., Protective Groups in Organic Synthesis , (2d. Ed. 1991), pages 68-86 and 261-263.

The backbones of these materials are compounds or polyesters comprising at least one bond selected from ester bonds, urethane bonds, urea bonds, amide bonds, siloxane bonds and ether bonds, acrylic acid polymers, polyurethanes, polyethers, polyureas, polyamides and It may be a polymer such as any of these copolymers.

Suitable compounds or polymers having ester groups and one or more reactive functional groups include half-esters formed from the reaction of one or more polyols with one or more 1,2-anhydrides. Semi-esters are preferred because they are relatively low molecular weight and highly reactive with epoxy functional groups.

The semi-esters are obtained by reacting a polyol with 1,2-anhydrides under conditions sufficient to open the anhydride to form a semi-ester which is substantially free of polyesteration. This reaction product has a narrow molecular weight distribution and relatively low molecular weight of low viscosity. By "substantially no esterification occurs" is meant that the carboxyl groups formed by the reaction of anhydride are not further esterified by the polyol in a cyclic manner. This means that less than 10% or less than 5% by weight of high molecular weight polyester is formed.

1,2-anhydrides and polyols are generally mixed together and the reaction is carried out in an inert atmosphere such as nitrogen, in the presence of a solvent such as a ketone or an aromatic hydrocarbon to dissolve the solid components and / or to lower the viscosity of the reaction mixture. do.

In the desired ring-opening reaction and semi-ester formation, 1,2-dicarboxylic anhydride is used. Reaction with polyols using carboxylic acids instead of anhydrides requires esterification by condensation and removal, and water must be removed by distillation. Under these conditions, the reaction promotes undesirable polyesteration. In addition, the reaction temperature may be low. That is, it may be less than 135 ℃ or 70 to 135 ℃. The reaction time may vary somewhat depending on the reaction temperature and is generally 10 minutes to 24 hours.

The equivalent ratio of anhydride to hydroxyl on the polyol may be at least 0.8: 1 to achieve the maximum conversion to the desired semi-ester (anhydrides are considered to be monofunctional). A ratio of less than 0.8: 1 can be used but this ratio increases the formation of lower functional semi-esters.

Useful anhydrides include aliphatic, cycloaliphatic, olefinic, cycloolefinic and aromatic anhydrides. Substituted aliphatic and aromatic anhydrides are also useful as long as the substituents do not adversely affect the reactivity of the anhydride or the properties of the resulting polyester. Examples of substituents include chloro, alkyl and alkoxy. Examples of anhydrides include succinic anhydride, methyl succinic anhydride, dodecenyl succinic anhydride, octadecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkyl hexahydrophthalic anhydride (e.g. methyl Hexahydrophthalic anhydride), tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, chloric acid anhydride, itaconic anhydride, citraconic anhydride and maleic anhydride.

Among the polyols that can be used are simple polyols (ie simple polyols having 2 to 20 carbon atoms), as well as polymeric polyols such as polyester polyols, polyurethane polyols and acrylic acid polyols.

Among the simple polyols are diols, triols, tetrols and mixtures thereof. Non-limiting examples of polyols include polyols having 2 to 10 carbon atoms, such as aliphatic polyols. Specific examples include, but are not limited to, the following compositions: di-trimethylol propane (bis (2,2-dimethylol) dibutylether); Pentaerythritol; 1,2,3,4-butanetetrol; Sorbitol; Trimethylolpropane; Trimethylolethane; 1,2,6-hexanetriol; glycerin; Trishydroxyethyl isocyanurate; Dimethylol propionic acid; 1,2,4-butanetriol; TMP / epsilon-caprolactone triol; Ethylene glycol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 2-ethyl-1,3-hexanediol, neopentyl glycol; Diethylene glycol; Dipropylene glycol; 1,4-cyclohexanedimethanol and 2,2,4-trimethylpentane-1,3-diol. In one embodiment, the polyol is trimethylolpropane.

For oligomeric polyols, suitable polyols are polyols prepared from the reaction of triols with diacids such as trimethylol propane / cyclohexane diacid and trimethylol propane / adipic acid.

For polymeric polyols, polyester polyols are prepared by esterifying organic polycarboxylic acids or their anhydrides using organic polyols and / or epoxides. Generally, polycarboxylic acids and polyols are aliphatic or aromatic diacids or acid anhydrides and diols.

Polyols commonly used to prepare polyesters include trimethylol propane, di-trimethylol propane, alkylene glycols such as ethylene glycol, neopentyl glycol and other glycols such as hydrogenated bisphenol A, cyclohexanediol Cyclohexanedimethanol, reaction products of lactones with diols (e.g., reaction products of epsilon-caprolactone and ethylene glycol), hydroxy-alkylated bisphenols, polyester glycols (e.g. poly (oxytetramethylene ) Glycol) and the like.

The acid component of the polyester consists mainly of monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule. Among the useful acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chloric acid, tetrachlorophthalic acid and various other Form of dicarboxylic acid. In addition, higher polycarboxylic acids such as trimellitic acid and tricavallylic acid can be used. However, the use of such higher functional polycarboxylic acids is undesirable due to the resulting high viscosity.

In addition to polyester polyols formed from polyacids and polyols, polylactone polyesters can also be used. These products are formed from the reaction of lactones such as epsilon-caprolactone with polyols such as ethylene glycol, diethylene glycol and trimethylolpropane.

In addition to the polyester polyols, polyurethane polyols can be used, such as polyester-urethane polyols formed from the reaction of organic polyisocyanates with polyester polyols as described above. The organic polyisocyanate allows the product resulting from the reaction with the polyol to contain free hydroxyl groups such that the OH / NCO equivalent ratio is greater than 1: 1. The organic polyisocyanate used to prepare the polyurethane polyols may be aliphatic or aromatic polyisocyanates or mixtures. Diisocyanates can be used and higher polyisocyanates such as triisocyanates can also be used, but this can lead to high viscosity.

Examples of suitable diisocyanates are 4,4'-diphenylmethane diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate). Examples of suitable higher functional polyisocyanates are polymethylene polyphenol isocyanates.

Some or more or all of the acid functionalities may be silylated. Alternatively, some or more or all of the acid functional groups can be converted to hydroxyl groups by reacting with an epoxy functional material or aliphatic diol as described above to provide an alcoholic hydroxyl group for silylation.

Useful epoxy functional materials include glycidyl methacrylate, ethylene oxide, butylene oxide, propylene oxide, cyclohexene oxide, glycidyl ethers (e.g. phenyl glycidyl ether, n-butyl glycidyl ether, cress) Silglycidyl ether and isopropyl glycidyl ether), glycidyl esters such as glycidyl vercetate, such as CARDURA E available from Shell Chemical Co. Epoxy functional monomers), and mixtures of any of these. The equivalent ratio of acid groups on epoxy groups to esters can generally be from 0.1: 1 to 2: 1, 0.5: 1 to 1: 1, typically from 0.8: 1 to 1: 1.

Useful aliphatic diols include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,2-hexane Diol, 1,5-hexanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentane Diols containing primary hydroxyls such as diols and 3,3-dimethyl-1,2-butanediol.

Non-limiting examples of silylated compounds containing ester groups for use in the coating compositions of the present invention are compounds of formula X:

Other useful materials having ester, urethane, urea, amide and / or ether groups and one or more reactive functional groups suitable for silylation have been disclosed above in the discussion of suitable further polymers.

Alternatively, useful reagents are described in I. I. Azuma et al., Containing hydroxyl groups blocked with hydrolyzable siloxy groups as disclosed in "Acrylic Oligomer for High Solid Automotive Top Coating System Having Excellent Acid Resistance", Progress in Organic Coatings 32 (1997) 1-7. Acrylic polymers (eg, polymerized from vinyl monomers and trimethyl siloxy methylmethacrylate).

In one embodiment, the invention is present in a composition in an amount of 0.1 to 90 weight percent based on the total weight of the resin solids of the components forming the composition when the silyl-blocked reactant is added to the other components forming the composition. It relates to a composition as described above. In another embodiment, the present invention provides a coating composition in an amount of at least 0.1% by weight based on the total weight of the resin solids of the components forming the coating composition when the silyl-blocked reactant is added to the other components forming the coating composition. It relates to a composition as described above, present. In another embodiment, the present invention provides a coating composition in an amount of at least 1% by weight based on the total weight of the resin solids of the components forming the coating composition when the silyl-blocked reactant is added to the other components forming the coating composition. Present in a composition as described above. In another embodiment, the present invention provides a coating composition in an amount of at least 5% by weight based on the total weight of the resin solids of the components forming the coating composition when the silyl-blocked reactant is added to the other components forming the coating composition. Present in a composition as described above.

In another embodiment, the present invention provides a coating composition in an amount of less than 60 weight percent based on the total weight of the resin solids of the components forming the coating composition when the silyl-blocked reactant is added to the other components forming the coating composition. Present in a composition as described above. In a further embodiment, the present invention provides a coating composition in an amount of less than 30% by weight based on the total weight of the resin solids of the components forming the coating composition when the silyl-blocked reactant is added to the other components forming the coating composition. Present in a composition as described above. In another embodiment, the present invention provides a coating in an amount of less than 10% by weight based on the total weight of the resin solids of the components forming the coating composition when the silyl-blocked reactant is added to the other components forming the coating composition. It relates to a composition as described above present in the composition. The amount of silyl-blocked reactant can range from any combination of these values, including those mentioned above.

The coating composition of the present invention may be a solvent-based coating composition or an aqueous coating composition in the form of a solid particulate (ie powder coating composition) or in the form of a powder slurry or an aqueous dispersion. The components of the invention used to form the curable compositions of the invention may be dissolved or dispersed in organic solvents. Non-limiting examples of suitable organic solvents include alcohols such as butanol; Ketones such as methyl amyl ketone; Aromatic hydrocarbons such as xylene; Glycol ethers such as ethylene glycol monobutyl ether; ester; Other solvents; And any mixtures thereof.

In the solvent-based composition, the organic solvent is generally present in an amount of 5 to 80% by weight based on the total weight of the resin solids of the components forming the composition, and an amount of 30 to 50% by weight including the above-mentioned values. May exist. The composition as described above may have a total solids content of 40 to 75% by weight, based on the total weight of the resin solids of the components forming the composition, with a total solids content of 50 to 70% by weight, including the stated values. Can have Alternatively, the compositions of the present invention may be in solid particulate form suitable for use as a powder coating or suitable for dispersion in a liquid medium such as water for use as a powder slurry.

In further embodiments, the catalyst may be present during the formation of the coating composition. Non-limiting examples of suitable catalysts include acidic materials such as acid phosphates such as phenyl acid phosphate, and substituted or unsubstituted sulfonic acids such as dodecylbenzene sulfonic acid or para-toluene sulfonic acid, and N, N'-dimethyl Other catalysts such as dodecyl amine catalysts and tin catalysts such as dibutyl tin dilaurate. When the catalyst is added to the other components forming the coating composition, the catalyst may be present in an amount of 0.1 to 5.0% by weight, including the quoted values, based on the total weight of the resin solids of the components forming the coating composition. .

In another embodiment, additional components may be present during the formation of the coating composition as described above. As such additional components, softeners, plasticizers, surface active agents (e.g., polysiloxanes), thixotropic agents, anti-gassing agents, organic cosolvents, flow control agents, hindered amines as defined herein Light stabilizers, antioxidants, UV light absorbers, colorants or tints, and similar conventional additives in the art, as well as any mixture of these materials may be included in the coating composition. When such additional components are added to other components forming the coating composition, the additional components may be present in an amount of up to 40% by weight, based on the total weight of the resin solids of the components forming the coating composition.

The amount of coating composition applied to the substrate can vary depending on factors such as the type of substrate and the use of the substrate, ie the environment in which the substrate is placed and the nature of the material being contacted.

In another embodiment, the invention relates to a coated substrate comprising a substrate and a coating composition coated on at least a portion of the substrate, wherein the coating composition is selected from any of the coating compositions described above. In another embodiment, the invention relates to a method of coating a substrate, comprising applying a coating composition selected from any of the coating compositions onto at least a portion of the substrate.

In another embodiment, the invention relates to a method of coating a substrate, further comprising curing the coating composition after applying the coating composition to the substrate. The components used to form the coating composition in this embodiment may be selected from the above-mentioned components, and further components may also be selected from the materials recited above.

As used herein, a composition "on at least a portion of a substrate" refers to a composition that is applied directly to at least a portion of the substrate, as well as a composition applied to any coating material previously applied onto at least a portion of the substrate.

The coating composition of the present invention may be applied over virtually any substrate, including wood, metal, glass, cloth, plastics, polymeric substrates such as foams and elastomeric substrates, and the like. In one embodiment, the coated substrate of the present invention is a soft substrate. In another embodiment, the coated substrate of the present invention is a rigid substrate.

In a further embodiment, the coated substrate of the present invention is a ceramic substrate. In another embodiment, the coated substrate of the present invention is a polymeric substrate. In another embodiment, the invention relates to a coated metallic substrate comprising a metallic substrate and a cured composition coated on at least a portion of the metallic substrate, wherein the cured composition is selected from any of the foregoing compositions do. The components used to form the cured composition in this embodiment may be selected from the aforementioned components, and further components may also be selected from those recited above.

A further embodiment of the invention relates to a coated automotive substrate comprising an automotive substrate and a cured composition coated on at least a portion of the automotive substrate, wherein the curable composition is selected from any of the foregoing compositions. In another embodiment, the present invention includes providing an automotive substrate, and applying a coating composition selected from any of the foregoing compositions onto at least a portion of the automotive substrate. It is about a method. Likewise, the components used to form the cured composition in this embodiment may be selected from those described above, and additional components may also be selected from those cited above.

Suitable flexible elastomeric substrates may include any thermoplastic or thermoset synthetic material well known in the art. Non-limiting examples of suitable soft elastomeric base materials include polyethylene, polypropylene, thermoplastic polyolefin ("TPO"), reactive injection molded polyurethane ("RIM"), and thermoplastic polyurethane ("TPU").

Non-limiting examples of thermoset materials useful as substrates in connection with the present invention include polyesters, epoxides, phenols, polyurethanes such as "RIM" thermosets, and any mixtures thereof. Non-limiting examples of suitable thermoplastics include thermoplastic polyolefins such as polyethylene, polypropylene, polyamides (e.g. nylon), thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonates, acrylonitrile-butadiene -Styrene ("ABS") copolymers, ethylene propylene diene terpolymer ("EPDM") rubbers, copolymers and any mixtures thereof.

Non-limiting examples of suitable metal substrates include ferrous metals (eg, iron, steel, and alloys thereof), nonferrous metals (eg, aluminum, zinc, magnesium, and alloys thereof), and any mixtures thereof. It includes. In specific applications of automotive parts, the substrate may be formed from cold rolled steels, galvanicized steels, such as hot dip steels, galvanic electro-zinc steels, aluminum and magnesium.

When the substrate is used as a part for manufacturing automatic vehicles (including but not limited to cars, trucks and tractors), the substrate can have any shape and is selected from the metallic and soft substrates described above. Can be. Typical shapes of the vehicle body may include the body (frame), hood, door, fender, bumper and trim of the vehicle.

In another embodiment, the coated automotive substrate of the present invention is a hood. In another embodiment, the coated automotive substrate of the present invention is a door. In another embodiment, the coated automotive substrate of the present invention is a fender. In another embodiment, the coated automotive substrate of the present invention is a quarterpanel. In this embodiment, the components used to form the cured composition used to coat the automotive substrate may be selected from the aforementioned components.

In embodiments of the present invention relating to automotive applications, the cured composition may be, for example, an electrodeposition coating, an undercoat, an undercoat and / or a topcoat. Suitable top coats include monolayers and undercoat / transparent coat complexes. The monolayer is formed from one or more layers of colored coating composition. The undercoat / transparent coating composite includes at least one layer of colored undercoat compositions, and at least one layer of coating composition for a clearcoat, wherein the undercoat composition includes at least one component different from the clearcoat coating composition. In embodiments of the present invention relating to automotive applications, the clearcoat can be transparent after application.

In another embodiment, the present invention is directed to a multicomponent composite curing composition comprising a undercoat deposited from a colored coating composition, and a topcoat coating composition applied over the undercoat, wherein the topcoat coating composition is described above. Selected from any of the compositions.

In one embodiment, the present invention is directed to a multicomponent composite curing composition as described above, wherein said top coat composition is transparent after curing and selected from any of the foregoing curing compositions. The components used to form the top coat composition in this embodiment may be selected from the coating components described above, and additional components may also be selected from those cited above.

The undercoat and the transparent topcoat (for example, the clearcoat) composition used in the multicomponent composite curing composition of the present invention are formulated into a liquid composition containing a high solids content, i.e., at least 40% by weight, or at least 50% by weight of resin solids. Can be. Samples of the curable composition may be heated at 105 ° C. to 110 ° C. for 1-2 hours to remove volatiles, and then the relative content may be determined by calculating the relative weight loss. As mentioned above, the curing composition may be formed from a liquid coating composition, but may also be formed from a coating composition formulated as a powder coating composition.

The coating composition of the undercoat of the color-plus-clear system can be any composition useful for coating applications, especially automotive applications. The coating composition of the undercoat can be formed from a component comprising a dendritic binder and a pigment that acts as a colorant. Non-limiting examples of dendritic binders are acrylic polymers, polyesters, alkyds and polyurethanes.

The dendritic binder of the undercoat can be an organic solvent-based material such as the material described in US Pat. No. 4,220,679, column 2, lines 24 to 4, line 40 (incorporated herein by reference). As a binder of the undercoat composition, it is also possible to use waterborne coating compositions such as those described in US Pat. Nos. 4,403,003, 4,147,679 and 5,071,904. This US patent is incorporated herein by reference.

The undercoat composition may include one or more pigments as colorants. Non-limiting examples of suitable metallic pigments include aluminum flakes, copper bronze flakes and metal oxide coated mica.

In addition to metallic pigments, the undercoat compositions may be selected from nonmetallic colored pigments commonly used in surface coatings, such as inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate and carbon black; And organic pigments such as phthalocyanine blue and phthalocyanine green.

Optional components of the undercoat composition may include materials that are well known in the art of formulating surface coatings, and include surface active agents, flow control agents, thixotropes, fillers, antigasing agents, organic cosolvents, catalysts, and other conventional Auxiliary may be included. Non-limiting examples of such materials and appropriate amounts thereof are described in US Pat. No. 4,220,679; No. 4,403,003; No. 4,147,769; And 5,071,904, which are incorporated by reference herein.

The undercoat composition may be applied to the substrate by any conventional coating technique such as brushing, spraying, dipping or flowing. Spray techniques, known in the art, and manual or automated methods of air spray, vacuum spray, and electrostatic spray apparatus can be used.

During the application of the undercoat to the substrate, the film thickness of the undercoat formed on the substrate is 0.1 to 5 mils. In another embodiment, the film thickness of the undercoat formed on the substrate may be 0.1 to 1 mil, 0.4 mil.

After forming the film of the undercoat on the substrate, a drying step may be performed to cure the undercoat before applying the transparent coat, or alternatively, remove the solvent of the undercoat through a heating or air drying period. Appropriate drying conditions may depend on the particular undercoat composition and may depend on ambient humidity if the composition is aqueous, but a drying time of 1 to 15 minutes may be appropriate at temperatures between 75 ° F and 200 ° F.

The clear or clear topcoat coating composition may be applied to the undercoat by any conventional coating technique, including but not limited to compressed air spray, electrostatic spray, and manual or automated methods. The transparent top coat may be applied to the cured undercoat, or may be applied to the dried undercoat before curing the undercoat. In the latter case, the two coatings can be heated to cure both coating layers simultaneously. The clear coating thickness may be 1 to 6 mil.

The coating composition can be cured by ionization or a combination of actinic radiation and thermal energy as described in detail above. Typical radiation energy curing conditions are the same as described in detail above. Typical thermal energy curing conditions may be 50 ° F. to 475 ° F. (10 ° C. to 246 ° C.) for 1 to 30 minutes.

The second top coat composition may be applied to the first top coat to form a "clear-on-clear" top coat. The first top coat coating composition may be applied on the undercoat as described above. The second top coat coating composition may be applied to the cured first top coat, or may be applied to the dried first top coat before curing the bottom coat and the first top coat. Subsequently, the undercoat, the first top coat and the second top coat may be heated to simultaneously cure three coatings.

When the second transparent top coat and the first transparent top coat composition are applied in a wet-on-wet manner, the second transparent top coat and the first transparent top coat composition may be the same or different, and one top coat may be For example, by inhibiting evaporation of the solvent / water from the lower layer, it should not substantially interfere with the curing of the other top coat. In addition, the first top coat, the second top coat, or both may be the cured composition of the present invention. The first clear top coat composition may be substantially any clear top coat composition, well known in the art. The first transparent coating composition for coating may be water-based or solvent-based, or may be in the form of solid particulates (eg, powder coating).

Non-limiting examples of suitable first coat coating compositions include crosslinkable coating compositions that include one or more thermosetting coating materials and one or more curing agents. Suitable aqueous transparent coatings are disclosed in US Pat. No. 5,098,947, incorporated herein by reference, and based on water soluble acrylic resins. Useful solvent-based clearcoats are disclosed in US Pat. Nos. 5,196,485 and 5,814,410, incorporated herein by reference, and include polyepoxides and polyacid curing agents. Suitable powder clearcoats are disclosed in US Pat. No. 5,663,240, which is incorporated herein by reference, and includes epoxy functional acrylic copolymers and polycarboxylic acid curing agents.

Typically, after the first top coat is formed on the undercoat, a drying step is performed in which the solvent is removed by heating the first top coat or alternatively by air drying period or curing step before applying the second top coat. Appropriate drying conditions will depend on the particular first coat coating composition and, if the composition is aqueous, will depend on ambient humidity, but generally a drying time of 1 to 15 minutes will be appropriate at temperatures between 75 ° and 200 ° F. .

The polysiloxane-containing second top coat coating composition of the present invention may be applied using any conventional coating technique as described for the first top coat. Curing conditions are the same as described for the top coat. The second phase dry film thickness may be 0.1 to 3 mils (7.5 μm to 75 μm).

When the polysiloxane-containing coating composition is applied to a substrate, it may be advantageous to be formulated as a "single coating" which is essentially a coating that forms one coating layer. The single layer coating composition may be colored. Non-limiting examples of suitable pigments include the aforementioned materials. When used as a single membrane, the polysiloxane-containing coating compositions of the present invention may be applied as two or more continuous coats (by any conventional application technique described above), and in certain cases may be applied with an ambient flashing period between the coats. Can be. The multiple coats can form essentially one coating layer upon curing.

In another embodiment, the present invention provides a method for preparing a coating film comprising the steps of (a) applying a colored composition to a substrate to form a undercoat; (b) applying to at least a portion of the undercoating film, a coating composition for top coat selected from any of the above-mentioned compositions, to form a top coat. The components used to form the topcoating composition in this embodiment may be selected from the coating compositions described above, and additional components may also be selected from those described above.

In accordance with the present invention, a coating formed from the cured composition may have outstanding appearance properties and initial mar resistance, and post-weathering or “hold” scratch resistance (mar). It can be evaluated by measuring the gloss of the coated substrate before and after abrasion of the coated substrate.

The initial 20 ° gloss of the coated substrate according to the invention can be measured using a 20 ° NOVO-GLOSS 20 statistical glossmeter, available from Gardner Instrument Company, Inc. . Straighten the coating or substrate with a weighted abrasive paper of 10 rubbers using the Atlas AATCC Scratch Tester, Model CM-5, available from Atlas Electrical Devices Company, Chicago, Illinois. The scratch test of the coating substrate can be performed by scratching. The abrasive paper is a sheet of 3M 281Q WETORDRY ^™ PRODUCTION ^™ 9 μm commercially available from 3M Company, St. Paul, Minn. The panels are then rinsed with tap water and carefully pated with a paper towel to dry. The 20 ° gloss is measured in the scratch area of each test panel. The reported value is the percentage of initial gloss retained after the scratch test, calculated as 100% x scratched gloss / initial gloss. The test method is described in detail in the Examples below.

In one embodiment, the present invention is directed to a curing composition having at least 40 initial 20 ° gloss (measured using a 20 ° NOVO-GLOSS 20 statistical glossmeter commercially available from the Gardner Instrument Company described above). The composition is any of the compositions according to the invention. In another embodiment, the present invention provides a curing with an initial 20 ° gloss of at least 50, or at least 70 (measured using a 20 ° NOVO-GLOSS 20 statistical glossmeter commercially available from the Gardner Instrument Company described above). With regard to the composition, the composition is any of the aforementioned compositions according to the invention.

In another embodiment, the present invention also relates to a cured composition having a post-weathering or "hold" scratch resistance value so that at least 40% of the initial 20 ° gloss is maintained after the scratch test. In addition, the cured composition of the present invention may have a post-weathering scratch value so that at least 50%, or at least 60% of the initial 20 ° gloss is retained after weathering (a test panel that is not scratched, a Q Panel) And simulated weathering by QUV exposure to UVA-340 bulbs of weathering cabinets available from the company), and then measured by the scratch test method described above).

In one embodiment, the present invention is directed to a method of improving a scratch resistance value of a substrate comprising applying to the substrate any of the compositions of the invention described for the substrate. In another embodiment, the invention relates to a method of improving the dirt repellency of a substrate, comprising applying any of the compositions of the invention described with respect to the substrate.

In another embodiment, the invention relates to a method of maintaining the gloss of a substrate over a period of time, comprising applying to the substrate any of the compositions described herein for the substrate. In another embodiment, the invention relates to a method of restoring the gloss of a substrate comprising applying to the substrate any of the compositions of the invention described for the substrate.

In another embodiment, the cured compositions of the invention may be useful as decorative or protective coatings of colored calcined (elastomeric) substrates, such as mold-in-color ("MIC") calcined substrates as described above. . In such applications, the composition may be applied directly to the fired substrate or incorporated into the mold matrix. Optionally, the adhesion promoter can first be applied directly to the fired or elastomeric substrate and the composition applied as a top coat thereon. It may also be advantageous for the compositions of the present invention to be formulated as colored coating compositions for use as undercoats, undercoats of multicomponent composite coatings, and as a single top coat comprising pigments or colorants. The components used to form the composition in this embodiment may be selected from the coating compositions described above, and additional components may also be selected from those cited above.

In another embodiment of the present invention, the cured composition is provided to include particles dispersed in the cured composition comprising one or more thermoplastics. As described above, the particle concentration in the surface region is greater than the particle concentration in the bulk region. The cured composition may be derived from a thermoplastic dendritic coating composition. Non-limiting examples of suitable thermoplastics include acrylic polymers, polyolefin polymers, polyamide polymers, and polyester polymers suitable for use in lacquer anhydrous systems of high molecular weight (eg, at least 20,000, at least 40,000, or at least 60,000 Mw). do. Non-limiting examples of the class of thermoplastics from which the curable composition can be derived include materials made from fluoropolymer-acrylic copolymers (e.g., polyvinyridine fluoride (e.g., KYNAR 500 manufactured by Ossimmont). Ausimont USA, Inc., a thermoplastic acrylic copolymer (e.g., ACRYLOID B44 (65% methyl methacrylate and 35% ethyl acrylate) (Doc: resin resin, Dock) Resin, Inc.).

In another embodiment, the present invention includes applying any of the compositions described herein to a substrate to a substrate, the method comprising maintaining the gloss of the polymeric substrate or polymeric coated substrate after a predetermined time. It is about. The predetermined time is generally six months or more and may be one year or more. In another embodiment, the present invention includes applying any of the compositions of the present invention to a substrate, and relates to a method for restoring the gloss of a polymeric substrate or a polymer coated substrate, as described above.

The present invention is explained through the following examples, which are not intended to limit the present invention to the details of the examples. Unless otherwise indicated, all parts and percentages in the following examples and specification are based on weight.

Dual curing (ultraviolet and thermal curing) coating compositions were prepared and evaluated as follows.

Each component was added while stirring in the order listed in Table 1 to prepare a coating composition. Acrylic polyols and isocyanurates were previously blended before the other ingredients were added.

ingredient Kinds Solids weight SR355 ¹ DiTMP Tetraacrylate 27.3 27.3 Clariant HIGHLINK OG108-32 Colloidal Silica in Tripropylene Glycol Diacrylate 41.9 41.9 DAROCURE 4265 ³ Photoinitiator 2.0 2.0 TINUVIN 400 ³ UV absorbers 3.0 3.0 TINUVIN 292 ³ Hindered amine light stabilizer 0.8 0.8 RC-68-1497 ² Acrylic Polyol Resin 15.6 23.3 DESMODUR N-3300 ⁴ Isocyanurate of HDI 9.4 9.4 Sum 100.0 107.7 ¹ Sartomer Co., Inc. Needle (Sartomer Company, Inc.) commercially available di-trimethylolpropane tetraacrylate ² 14.5% butyl acrylate, 14.5% butyl methacrylate, isobornyl methacrylate 27.5%, in the hydro-propyl Acrylic polyol prepared from 22.6% methacrylate, 20.4% hydroxyethyl methacrylate, 0.4% acrylic acid, having the following properties: 67% solids in aromatic 100 solvent, Mw 2336, Mn 1236 and OH value 116.8 ³ 2- 50:50 blend of hydroxy-2-methyl-1-phenyl propane-1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (eg, DAROCURE 4265 commercially available from Ciba-Geigy Corporation) Phosphine oxide as. ⁴ Isocyanurate of hexamethylene diisocyanate commercially available from Bayer Corporation.

The coating composition was applied onto the pretreated and underlaid panels as follows. The panels used were cold rolled steel panels (size: 4 inches x 12 inches (10.16 cm x 30.48 cm) coated with ED5000 electrocoat (commercially available from PPG Industries, Inc.). )) Test panels are commercially available from ACT Laboratories, Inc., Hillsdale, Michigan. The undercoat (Black Aqueous Undercoat BWB-8555, available from Fiji Industries, Inc.) was spray applied to a dry film thickness of 0.6 mils and thoroughly baked at 285 ° F. (141 ° C.) for 30 minutes. The coating composition of the present invention was applied to a dry film thickness of about 1.0 to 1.2 mils (26 to 31 μm) on the undercoat using a drawdown bar of 7 mils (179 μm). The clearcoat was flashed at ambient temperature (25 ° C.) for 5 minutes, followed by curing at line speeds of 70 feet per minute using ultraviolet light at 576 mJ / cm 2, followed by thermal curing at 285 ° F. (141 ° C.) for 30 minutes.

The scratch resistance value of the coating on the panel was evaluated as follows. 20 ° gloss was measured using a NOVO-GLOSS 20 ° statistical glossmeter available from Paul N. Gardner Company. Using the Atlas AATCC Scratch Tester, Model CM-5, available from Atlas Electrical Devices Company, Chicago, Illinois, the surface was scratched in a straight line with weighted abrasive paper of 10 rubbers. The scratch test of the coating panel was performed. The abrasive paper is a sheet of 3M 281Q WETORDRY ^™ PRODUCTION ^™ 9 μm commercially available from 3M Company, St. Paul, Minn. The panels were then rinsed with tap water and dried by carefully patting with paper towels. The 20 ° gloss was measured in the scratch area of each test panel (using the same glossmeter as used for the initial 20 ° gloss). With the lowest 20 ° gloss read from the scratch area, the scratch results after the scratch test are reported as% of initial gloss retained, calculated as follows: 100% × scratch gloss + initial gloss. The higher the gloss retained, the better.

The test results are shown in Table 2.

Transparent film Initial 20 ° Gloss 20 ° gloss after scratch test Gloss retention UV / heat dual curing 82 79 96

It will be apparent to those skilled in the art that the foregoing embodiments may be modified without departing from the broad inventive concept of the invention. Accordingly, it is to be understood that the invention is not limited to the specific embodiments disclosed and includes modifications that fall within the spirit and scope of the invention as defined in the appended claims.

The compositions of the present invention have a number of advantages in coating applications, such as good initial scratch resistance and good retention thereof, good appearance properties such as gloss and clear phase, and physical properties such as good flexibility and weather resistance. Not limited).

Claims (87)

(a) at least one first material comprising at least one radiation curable reactive functional group; (b) at least one second material comprising at least one thermally curable reactive functional group; (c) reactive to said at least one thermally curable reactive functional group, in aminoplast resins, polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols and mixtures thereof At least one curing agent selected; (d) a coating composition prepared from components comprising a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof, wherein each of the components is different. The method of claim 1, Wherein said at least one radiation curable reactive functional group is selected from a vinyl group, a vinyl ether group, an unsaturated ester group, an epoxy group, a maleimide group and a fumarate group. The method of claim 2, Wherein said at least one radiation curable reactive functional group is an unsaturated ester group selected from an acrylate group, a methacrylate group, and an acrylate group. The method of claim 3, wherein Coating composition wherein said unsaturated ester group is an acrylate group. The method of claim 1, The coating composition wherein the first material comprises polysiloxane. The method of claim 1, When the first material is added to the other components forming the coating composition, the coating composition is present in the coating composition at 1 to 99% by weight based on the total weight of the resin solids of the components forming the coating composition. The method of claim 1, Wherein said at least one radiation curable reactive functional group is curable by ionizing radiation. The method of claim 1, Wherein said at least one radiation curable reactive functional group is curable by actinic radiation. The method of claim 1, Wherein said at least one radiation curable reactive functional group is curable by ultraviolet radiation. The method of claim 1, The at least one heat curable reactive functional group is hydroxyl group, vinyl group, urethane group, urea group, amide group, carbamate group, isocyanate group, blocked isocyanate group, epoxy group, carbonyl group, amine group, anhydride group, hydroxy Coating composition selected from the group consisting of alkyl amide groups and aziridine groups. The method of claim 1, Blocked poly, wherein the second material is a polyisocyanate different from the hydroxyl functional polymer, polyester, acrylic polymer, polyurethane, polyurea, polyamide, carbamate functional polymer, curing agent (c), curing agent (c) A coating composition which is a film-forming polymer selected from isocyanates, polyepoxides different from the curing agent (c), polyethers, polyacids different from the curing agent (c), polyamines, polyanhydrides and copolymers and mixtures thereof. The method of claim 11, Coating composition, wherein the second material comprises one or more polysiloxanes. The method of claim 12, A coating composition wherein said at least one polysiloxane comprises at least one structural unit of formula Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} Where Each substituent R ¹ is the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each substituent R ² is the same or different and comprises at least one reactive functional group; m and n are numbers satisfying the conditions of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4, respectively. The method of claim 13, Each R ² is the same or different and is hydroxyl group, carboxyl group, isocyanate group, blocked polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group, urea group, urethane group, vinyl A coating composition exhibiting a group comprising at least one reactive functional group selected from among groups, unsaturated ester groups, maleimide groups, fumarate groups, anhydride groups, hydroxy alkylamide groups and epoxy groups. The method of claim 12, Coating composition wherein at least one polysiloxane has the structure of Formula II or III: Formula II Formula III Where m has a value of 1 or more, m 'is 0 to 75, n is from 0 to 75, n 'is 0 to 75, Each R is the same or different and is selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and any mixture of said groups, -R ^a includes the structure of Formula IV: Formula IV -R ³ -X Where -R ³ is selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group and an alkenylene aryl group, X is hydroxyl group, carboxyl group, isocyanate group, blocked polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group, urea group, urethane group, vinyl group, unsaturated ester group, Malay A group comprising at least one reactive functional group selected from a mid group, a fumarate group, an anhydride group, a hydroxy alkylamide group and an epoxy group. The method of claim 12, Wherein the at least one polysiloxane is present in an amount of from 0.5 to 75% by weight based on the total weight of the resin solids of the components forming the coating composition. The method of claim 1, When the second material is added to the other components forming the coating composition, the coating composition is present in the coating composition in an amount of 0.5 to 98.5% by weight based on the total weight of the resin solids of the components forming the coating composition. The method of claim 1, The coating composition wherein the curing agent is selected from aminoplast resins, polyisocyanates and blocked polyisocyanates. The method of claim 18, The coating composition wherein the curing agent is a polyisocyanate. The method of claim 1, When the curing agent is added to the other components forming the coating composition, the coating composition is present in the coating composition in an amount of 0.5 to 65% by weight based on the total weight of the resin solids of the components forming the coating composition. The method of claim 1, And wherein the particles are selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia, and mixtures thereof. The method of claim 1, A coating composition wherein the particles are surface treated. The method of claim 21, The coating composition wherein the particles comprise colloidal silica. The method of claim 1, A coating composition having an average particle size of less than 100 μm before the particles are introduced into the composition. The method of claim 24, A coating composition having an average particle size of less than 50 μm before the particles are introduced into the composition. The method of claim 1, Coating composition having an average particle size of less than 1 to 1000nm before the particles are introduced into the composition. The method of claim 26, Coating composition having an average particle size of 1 to 100nm before the particles are introduced into the composition. The method of claim 27, Coating composition having an average particle size of 5 to 50nm before the particles are introduced into the composition. The method of claim 1, When the particles are added to the other components forming the coating composition, the coating composition is present in the coating composition in an amount of 0.01 to 75% by weight based on the total weight of the resin solids of the components forming the coating composition. The method of claim 29, The coating composition wherein the particles are present in an amount of at least 0.1% by weight. The method of claim 30, The coating composition wherein the particles are present in an amount of at least 0.5% by weight. The method of claim 31, wherein Wherein the particles are present in an amount of at least 5% by weight. The method of claim 1, A coating composition wherein the components forming the coating composition comprise one or more surface active agents. The method of claim 33, wherein At least one surface active agent is selected from anionic surface active agents, nonionic surface active agents and cationic surface active agents. The method of claim 1, A coating composition, wherein the components forming the coating composition comprise one or more photoinitiators. 36. The method of claim 35 wherein Said at least one photoinitiator is a substituted benzoin such as benzoin, benzophenone, hydroxy benzophenone, anthraquinone, thioxanthone, butyl isomer of benzoin ether, α, α-diethoxyacetophenone, α, α-dimeth Coating composition selected from oxy-a-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl propane 1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and mixtures thereof. 36. The method of claim 35 wherein Wherein said at least one photoinitiator is a 50:50 blend of 2-hydroxy-2-methyl-1-phenyl propane-1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide. The method of claim 1, A coating composition wherein the components forming the composition comprise one or more materials having one or more reactive functional groups blocked with a silyl group. The method of claim 38, Coating compositions wherein the silyl blocker has the formula IX: Formula IX Where Each of R ₁ , R ₂ and R ₃ is the same or different and represents an alkyl group, phenyl group or allyl group having 1 to 18 carbon atoms. The method of claim 1 The coating composition, when cured, has an initial scratch resistance value such that at least 40% of the initial 20 ° gloss is maintained after the scratch test. The method of claim 1, The coating composition, when cured, has a retention scratch value that maintains at least 30% of the initial 20 ° gloss after the scratch test. A cured coating formed from the composition of claim 1. The method of claim 42, A cured composition cured by exposure to (1) ionizing radiation or actinic radiation and (2) thermal energy. The method of claim 42, A cured composition, cured by exposure to (1) ultraviolet light and (2) thermal energy. A coated substrate comprising a substrate and a composition according to claim 1 deposited on at least a portion of the substrate. A method of forming a cured coating on a substrate, comprising applying the coating composition of claim 1 onto at least a portion of the substrate. The method of claim 46, Exposing the coating composition to (1) ionizing radiation or actinic radiation and (2) thermal energy. The method of claim 46, Wherein said substrate is an automotive substrate. A coated automotive substrate comprising an automotive substrate and a composition according to claim 1 deposited on at least a portion of said automotive substrate. The method of claim 49, Coated automotive substrate, which is a bumper. The method of claim 49, Coated automotive substrate, which is a hood. The method of claim 49, Coated automotive substrate, which is a door. The method of claim 49, Coated automotive substrate, which is a fender. A multicomponent composite coating composition comprising a undercoat deposited from a colored coating composition and a composition according to claim 1 applied on at least a portion of the undercoat. The method of claim 54, wherein Multi-component composite in which the composition is a top coat. The method of claim 55, Transparent multicomponent composite when the composition is cured. (a) applying a colored coating composition to a substrate to form a undercoat; (b) applying the coating composition of claim 1 as a top coat composition on at least a portion of the undercoat; (c) preparing a cured coating by curing the top coat composition. The method of claim 57, And wherein said top coat composition is applied to said substrate and cured by exposure to (1) ionizing radiation or actinic radiation and (2) thermal energy. A method for improving the scratch resistance of a substrate, comprising forming a composition according to claim 1 on at least a portion of a polymeric substrate or a polymeric coated substrate. A method of maintaining the gloss of a substrate over a period of time, comprising forming a composition according to claim 1 on the surface of the polymeric substrate or polymeric coated substrate. A method of restoring the gloss of a substrate comprising forming a composition according to claim 1 on the surface of a polymeric substrate or a polymer coated substrate. (a) a first material comprising at least one radiation curable reactive functional group; (b) a second material comprising at least one thermally curable reactive functional group; (c) reactive to said at least one thermally curable reactive functional group, in aminoplast resins, polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols and mixtures thereof At least one curing agent selected; And (d) components comprising a plurality of particles, wherein each component is different. 63. The method of claim 62, The coating composition, when cured, has an initial scratch resistance value such that at least 40% of the initial 20 ° gloss is maintained after the scratch test. 63. The method of claim 62, The coating composition, when cured, has a retention scratch value that maintains at least 30% of the initial 20 ° gloss after the scratch test. A cured coating prepared from the composition of claim 62. A coated substrate comprising a substrate and a composition according to claim 62 deposited on at least a portion of the substrate. 63. A method of forming a cured coating on a substrate comprising applying the coating composition of claim 62 onto at least a portion of the substrate. The method of claim 67 wherein The coating composition is applied to the substrate and then cured by exposure to (1) actinic or ionizing radiation and (2) thermal energy. The method of claim 67 wherein Wherein said substrate is an automotive substrate. A coated automotive substrate comprising an automotive substrate and a composition according to claim 62 deposited on at least a portion of said automotive substrate. A multicomponent composite coating composition comprising a undercoat deposited from a colored coating composition and a composition according to claim 62 applied on at least a portion of the undercoat. (a) applying a colored composition to a substrate to form a undercoat; (b) applying the coating composition according to claim 62 on at least a portion of the undercoat as a top coat composition; (c) preparing a cured coating by curing the top coat composition. 63. A method for improving the scratch resistance of a substrate comprising forming a composition according to claim 62 on at least a portion of a polymeric substrate or a polymeric coated substrate. A method of maintaining the gloss of a substrate over a period of time, comprising forming a composition according to claim 62 on the surface of the polymeric substrate or polymeric coated substrate. 63. A method for restoring gloss of a substrate comprising forming a composition according to claim 62 on the surface of a polymeric substrate or a polymeric coated substrate. (a) at least one material comprising at least one ultraviolet curable reactive functional group and at least one thermally curable reactive functional group; (b) one or more curing agents reactive to one or more thermally curable reactive functional groups and selected from polyisocyanates, blocked polyisocyanates, triazine derived isocyanates, polyepoxides, polyacids, polyols, and mixtures thereof; And (c) components comprising a plurality of particles, wherein each component is different. 77. The method of claim 76, The coating composition, when cured, has an initial scratch resistance value such that at least 40% of the initial 20 ° gloss is maintained after the scratch test. 77. The method of claim 76, The coating composition, when cured, has a retention scratch value that maintains at least 30% of the initial 20 ° gloss after the scratch test. The cured coating formed from the composition of claim 76. 77. A coated substrate comprising a substrate and a composition according to claim 76 deposited on at least a portion of said substrate. 76. A method of forming a cured coating on a substrate comprising applying the coating composition according to claim 76 on at least a portion of the substrate and then curing the coating composition. A coated automotive substrate comprising an automotive substrate and a composition according to claim 76 deposited on at least a portion of said automotive substrate. A multicomponent composite coating composition comprising a coating film deposited from a colored coating composition, the composition according to claim 76 applied on at least a portion of the coating film. (a) applying a colored composition to a substrate to form a undercoat; (b) applying the coating composition of claim 76 as a top coat composition on at least a portion of the undercoat; (c) preparing a cured coating by curing the top coat composition. 77. A method of improving the scratch resistance of a substrate comprising forming a composition according to claim 76 on at least a portion of a polymer substrate or a polymer coated substrate. 77. A method of maintaining the gloss of a substrate over a period of time, comprising forming a composition according to claim 76 on the surface of the polymeric substrate or polymeric coated substrate. 77. A method of restoring gloss of a substrate comprising forming a composition according to claim 76 on the surface of a polymeric substrate or a polymeric coated substrate.