KR20020053802A - Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto - Google Patents

Abstract

Coating compositions are provided which include a polysiloxane comprising at least one reactive functional group and at least one material comprising at least one reactive functional group. Also provided are multi-layer composite coatings formed from a basecoat deposited from a pigmented coating composition and a topcoat applied over the basecoat, the topcoat deposited from the aforementioned coating composition. A method for improving the scratch resistance of a coated substrate, as well as coated substrates also are provided. The compositions of the invention provide highly scratch resistant coatings, particularly highly scratch resistant color-plus-clearcoatings.

Description

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

This application is part of US Patent Application Serial Nos. 09 / 489,042 and 09 / 489,043, filed Jan. 21, 2000, the applications of which are filed July 30, 1999, US Patent Application No. 09 / 365,069 Part of the issue is pending application. US Patent Application Nos. 09 / 489,042 and 09 / 489,043 take precedence over US Patent Application No. 60 / 171,899, filed December 23, 1999.

Color + transparent coating systems, including the application of colored undercoats to substrates followed by the application of a clear coat over the undercoats, have become increasingly popular as original finishes 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 coating compositions, particularly compositions used in the manufacture of transparent coatings in automotive color + transparent coating systems, are susceptible to damage from a number of environmental factors as well as defects that occur 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. Softer, 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 body side moldings, are typically "separately" coated and shipped to an automobile assembly plant. Coating compositions applied to such elastomeric substrates are typically very flexible so that the coating can be blended with the substrate without cracking. In order to achieve this essential flexibility, coating compositions used in elastomeric substrates often employ flexible aids 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.

Many patents disclose colloidal silica dispersions in alcohol-aqueous solutions of partial condensates of silanol of formula RSi (OH) ₃ , wherein at least 70% by weight of the partial condensates are partial condensates of CH ₃ Si (OH) ₃ . Teaches the use of a coating composition comprising a. Representative, non-limiting examples include US Pat. No. 3,986,997; 4,027,073; 4,239,738; 4,310,600; And 4,410,594.

U.S. Patent No. 4,822,828 discloses (a) 50 to 85 weight percent vinyl functional silanes based on the total weight of the dispersion, (b) 15 to 50 weight percent multifunctional acrylate based on the total weight of the dispersion, and ( c) optionally the use of vinyl functional silanes in aqueous irradiated 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 formula (R) _a Si (R ′) _b (R ″) _c where R is allyl or vinyl functional alkyl R 'is hydrolyzable alkoxy or methoxy; R''is non-hydrolyzable saturated alkyl, phenyl or siloxy, a + b + c is 4, 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 substrate and exposing it to an ultraviolet or electron beam to form a substantially transparent wear resistant layer.

U. S. Patent No. 5,154, 759 teaches polishing formulations comprising reactive amine functional silicone polymers and one or more other components commonly used in polishing formulations. One such constituent disclosed in the patent is an abrasive and teaches aluminum silicate, diatomaceous earth, pumice, clay, kaolin, silica, tripoly, hydrated calcium silicate, chalk, colloidal clay, magnesium oxide red iron oxide or tin oxide It is.

U. S. Patent No. 5,686, 012 discloses modified particles comprising, as core particles, inorganic colored or magnetic particles, and one or more polysiloxanes modified with one or more organic groups coated on the surface of the core particles. The patent also discloses a method of making the modified particles as well as an aqueous paint comprising the modified particles as a paint base material and pigment.

U. S. Patent No. 5,853, 809 discloses a transparent coating in a color + transparency system with improved scratch resistance due to the incorporation of inorganic particles, such as colloidal silica, surface modified by reactive coupling agents via covalent bonds into the coating composition.

U. S. Patent No. 5,709, 950 discloses flexible aminoplast-curable coating compositions comprising polyether polymers having terminal or pendant carbamate groups along with other hydroxyl or carbamate functional film forming polymers. The composition is useful as a top coat composition in multilayer composite coating compositions for plastic automotive parts.

Despite recent improvements to color + transparent coating systems, automotive coatings have improved initial post-weather ("owned") scratch resistance as well as good initial scratch resistance without the film's smoothness due to high crosslink density. There is still a need for a top coat. Furthermore, it may be advantageous to provide a topcoat for elastomeric substrates for use in the automotive industry that is flexible and scratch resistant.

Summary of the Invention

In one embodiment, the invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I); (b) one or more polyols having hydroxyl numbers ranging from 100 to 200; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one functional group of at least one polyol (b). Wherein the respective components are different, and the coating material prepared from the coating composition has a flexibility rating of at least 6 according to the flexibility test method at a temperature of 70 ° F. upon curing:

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In another embodiment, the present invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I); (b) one or more substances comprising one or more reactive functional groups; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one reactive functional group of at least one substance (b). To a coating composition prepared, wherein each of said components is different and the coating material prepared from said coating composition has a flexibility rating of at least 6 depending on the flexibility test method at a temperature of 70 ° F. upon curing:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In yet another embodiment, (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I); And (b) at least one reactant comprising at least one functional group reactive with at least one reactive functional group of at least one polysiloxane (a), wherein the coating material prepared from the coating composition is Have a flexibility rating of at least 6 depending on the flexibility test method at a temperature of 70 ° F. upon curing, wherein each of the components is different and the coating material prepared from the coating composition is at least 40% of the initial 20 ° gloss after the scratch test at curing. It has an initial scratch resistance value that allows it to be retained:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In another embodiment, the present invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I); (b) at least one polyol having a hydroxyl value of 100 to 200, less than 30% by weight, based on the total resin solids of the components forming the coating composition; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one functional group of at least one polyol (b). To a coating composition wherein the respective components are different and the coating material prepared from the coating composition has a glass transition temperature in the range of 20 to 100 ° C. upon curing:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In another embodiment, (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I); (b) at least one polyol having a hydroxyl number ranging from 100 to 200 and selected from polyether polyols and polyester polyols; (c) one or more aminoplast resins; And (d) a coating composition made from components comprising at least one polyisocyanate, wherein each of said components is different and the coating material prepared from said coating composition is flexible at a temperature of 70 ° F. upon curing. Has a flexibility rating of 6 or more depending on:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In another embodiment, the present invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I); (b) one or more polyols having a hydroxyl value of 100 to 200, less than 30% by weight, based on the total resin solids of the components forming the coating composition, selected from polyether polyols and polyester polyols; (c) one or more aminoplast resins; And (d) a coating composition made from components comprising at least one polyisocyanate, wherein each of said components is different and the coating material prepared from said coating composition has a glass transition in the range of -20 to 100 ° C. upon curing. Has temperature:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In yet another embodiment, the present invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and comprising at least one unit of formula (I); And (b) a coating composition prepared from the components comprising (a) and other carbamate functional materials:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

The present invention also provides a cured coating material prepared from any of the above coating compositions. In addition, there is provided a multi-component composite coating material prepared from a coating film deposited from a colored coating composition and a coating film applied over the coating film and made from any of the coating compositions.

The present invention also provides a coated substrate comprising a substrate and any of the coating compositions coated on at least a portion of the substrate. The invention also provides a method of coating a substrate, comprising coating any of the coating compositions on at least a portion of the substrate.

Another aspect of the invention is a method of improving the scratch resistance of a substrate by applying any of the coating compositions to at least a portion of a polymeric substrate or a polymer coated substrate. Other methods provided include a method of maintaining the gloss of the substrate after a period of time, including coating any of the coating compositions on a polymer coated surface of a polymer coated substrate, and a polymer coated substrate of the polymer coated substrate. A method of revitalizing the gloss of the substrate after a predetermined time, comprising coating any of the coating compositions on the surface.

In addition to the examples, or when otherwise indicated, all numbers representing the amounts of ingredients, reaction conditions, and the like used in the specification and claims are to be understood as being limited to the term "about" in all of the above cases. Accordingly, unless indicated to the contrary, the numerical variables set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. In any case, to avoid limiting the application of the equivalence principle to the claims, each numerical variable should be construed by applying the conventional approximation technique at least in light of the reported numbers of significance.

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, certain 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 provide one or more materials comprising one or more reactive functional group-containing polysiloxanes, one or more polyol groups, and one or more carbamate groups, and one or more functional groups of the polysiloxane and one of the one or more materials. A coating composition comprising at least one reactant comprising at least one functional group reactive with at least one functional group selected from the above functional groups. Other embodiments of the present invention relate to cured coatings made from the coating compositions. Further embodiments relate to substrates coated with the aforementioned compositions. Embodiments of the present invention also relate to a method of improving the scratch resistance of a polymeric substrate or a polymer coated substrate.

In one embodiment, the present invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and comprising at least one unit of formula (I); (b) one or more polyols having hydroxyl numbers ranging from 100 to 200; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one functional group of at least one polyol (b) . Wherein the respective components are different, and the coating material prepared from the coating composition has a flexibility rating of at least 6 according to the flexibility test method at a temperature of 70 ° F. upon curing:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

Of course, "at least one polysiloxane comprising at least one unit of formula (I)" is 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 is of course also possible that the one or more polysiloxanes may comprise linear, branched, dendritic or cyclic polysiloxanes.

Moreover, as used herein, “prepared from” refers to the term claiming without limitation, for example, “comprising”. As such, a composition prepared from “list of recited components” is a composition comprising at least these recited components, and is intended to further include other, non-cited components during the preparation of the composition.

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.

As used herein, the phrase "each component is different" refers to components in the composition that do not have the same chemical formula as the other components.

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, the term “curing” as used in connection with a “composition upon curing” will mean that any crosslinkable components of 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. 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.

In a further embodiment, the present invention relates to the aforementioned cured composition, wherein one or more reactants are present during the preparation of the coating composition. As used herein, "one or more reactants" refers to any substance comprising a functional group that is reactive with one or more functional groups selected from one or more functional groups of one or more polysiloxanes and one or more functional groups of the substance. In one embodiment, the one or more reactants may be selected from one or more curing agents.

In another embodiment, the present invention provides a composition comprising (a) at least one polysiloxane comprising at least one reactive functional group and comprising at least one unit of formula (I); (b) one or more substances comprising one or more reactive functional groups; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one reactive functional group of at least one substance (b). To a coating composition prepared, wherein each of said components is different and the coating material prepared from said coating composition has a flexibility rating of at least 6 depending on the flexibility test method at a temperature of 70 ° F. upon curing:

Formula I

R ¹ _n R ² _m SiO _{(4-nm) / 2}

Where

Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

Each R ² may be the same or different and represents a group comprising one or more reactive functional groups;

m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2≤ (m + n) <4.

In another embodiment, the invention provides that R ² may be the same or different and that hydroxyl groups, carboxyl groups, isocyanate groups, protected 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, It relates to any of the compositions described above, which represents a group comprising at least one reactive functional group selected from anhydride groups, hydroxy alkylamide groups and epoxy groups.

As used herein, “monovalent hydrocarbon group” means a monovalent group having only carbon-based backbone repeat units. 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 silicon atoms in the main chain of one or more polysiloxane polymers. As used herein, "hydrocarbon group" is intended to include both branched and unbranched hydrocarbon groups.

Thus, when referring to "monovalent hydrocarbon groups", the hydrocarbon groups may be branched or unbranched, acyclic or cyclic, saturated or unsaturated, or aromatic, and 1 to 24 (or 3 to 24 for aromatic groups). C) may contain carbon atoms. 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 a heteroatom. 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 can be linear 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 can 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 mixtures of any of the above groups.

In another embodiment, the present invention relates to any of the aforementioned compositions, wherein one or more reactants (c) are selected from one or more curing agents.

In one embodiment, the present invention relates to any of the compositions described above, wherein at least one polysiloxane comprises at least two reactive functional groups. The at least one polysiloxane may have a reactive group equivalent weight 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 weight 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 weight of 100 to 300 mg KOH per gram of the at least one polysiloxane, and in another embodiment, the hydroxyl group equivalent weight ranges from 100 KOH per gram to 500 mg.

In another embodiment, the invention relates to any of the compositions described above, wherein the at least one R ² group represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In yet another embodiment, the invention relates to any composition described above, 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 invention relates to any of the compositions described above, 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 present invention relates to any of the compositions described above, wherein the at least one polysiloxane has the formula II or III:

In the above formulas,

m has a value of at least 1;

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 a mixture of any of the above groups;

-R ^a comprises formula IV:

-R ³ -X

Where

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

X is hydroxyl group, carboxyl group, isocyanate group, protected polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group, urea group, urethane group, vinyl group, unsaturated ester group, e.g. 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 Represents a group containing.

As used herein, "alkylene" refers to a non-cyclic or cyclic saturated hydrocarbon group having a carbon chain length of C ₂ to C ₂₅ . Non-limiting examples of suitable alkylene groups include those derived from propenyl, 1-butenyl, 1-pentenyl, 1-decenyl and 1-heneisenenyl, for example (CH ₂ ) ₃ , (CH ₂ ) ₄ , (CH ₂ ) ₅ , (CH ₂ ) ₁₀ and (CH ₂ ) ₂₃ as well as isoprene and myrcene.

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 include 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 —).

As used herein, "alkylene aryl" refers to a non-cyclic 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 be further substituted as the case may be. Non-limiting examples of suitable substituents for the aryl group 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” refers to a ratio having at least one double bond and an alkenylene carbon chain length of C ₂ to C ₂₅ . Non-limiting examples of suitable alkenylene groups include those derived from propargyl alcohol and acetylene diols, for example 2,4,7,9-tetramethyl-5-decine-4, 7-diol (commercially available as SURFYNOL 104 from Air Products and Chemicals, Inc. of Allentown, Pennsylvania).

Formulas (II) and (III) are schematic and parts in parentheses may be used as appropriate, but are not meant to be essential blocks. In some cases the polysiloxane may include various siloxane units. This is even more true when the number of siloxane units used increases, especially when using mixtures of many 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 any of the aforementioned compositions wherein the 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 of the aforementioned compositions comprising one or more polysiloxanes of Formula II or III above, wherein (n + m) is in the range of 2-9. In yet another embodiment, (n + m) in the composition comprising at least one polysiloxane having Formula II or III described above is in the range of 2-3. In another embodiment, (n '+ m') in the composition comprising at least one polysiloxane having Formula II or III described above is in the range of 2-9. In another embodiment, (n '+ m') in the composition comprising at least one polysiloxane having Formula II or III described above is in the range of 2-3.

In one embodiment, the invention relates to any of the compositions described above, wherein X represents a group comprising one or more reactive functional groups selected from hydroxyl groups and carbamate groups. In another embodiment, the present invention relates to the aforementioned composition, wherein X represents a group comprising two or more hydroxyl groups. In yet another embodiment, the invention represents a group wherein X comprises H, a monohydroxy substituted organic group and at least one group selected from the group of formula V and at least a portion of X represents a group having formula V It relates to any of the compositions described above:

R ⁴ -(-CH ₂ -OH) _p

Where

Substituent R ⁴ is Indicates,

when p is 2, the 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 invention relates to any of the aforementioned compositions, wherein m is 2 and p is 2.

In one embodiment, the present invention relates to formula II or formula II, wherein when no curing agent is present and at least one polysiloxane is a partial condensate of silanol, less than 70% by weight of the partial condensate is a partial condensate of CH ₃ Si (OH) ₃ . It relates to any of the compositions described above comprising one or more polysiloxanes having III. 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 cited above.

In another embodiment, the present invention relates to a compound of formula (I) wherein at least one polysiloxane (a) has at least the following reactants: (i) at least one polysiloxane of formula VI; And (ii) hydroxyl groups, carboxyl groups, isocyanate groups, protected polyisocyanate groups, primary amine groups, secondary amine groups, amide groups, carbamate groups, urea groups, urethane groups, vinyl groups, unsaturated ester groups 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 and hydrosilylation It relates to any of the compositions described above, which is the reaction product of one or more molecules comprising one or more functional groups selected from one or more unsaturated bonds which may undergo a reaction:

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 a mixture of any of the above groups;

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

n 'is in the range of 0 to 100, and may also be in the range of 0 to 10, more still 0 to 5;

SiH content% of the polysiloxane is in the range of 2 to 50%, and may be in the range of 5 to 25%.

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

It is to be understood that the various R groups may be the same or different and in some embodiments the R groups will be wholly 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, “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 level of unsaturation included in reactant (ii) can be selected so that an ungelled reaction product is obtained. In other words, 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, silicon hydride-containing polysiloxane (i) may be a low molecular weight material when n 'ranges from 0 to 5 and the average Si—H functionality is 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 the average Si-H functional group is 2; And silicon hydride containing polymethyl polysiloxanes with n 'in the range of 4 to 5 and an average Si—H functionality of approximately 2 (for example, commercially available as MASILWAX BASE® from BASF Corporation).

Materials for use as the reactant (ii) include allyl ethers containing hydroxyl functional groups, such as trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, trimethylolpropane diallyl ether, polyoxyalkylene alcohols, for example For example polyethoxylated alcohols, polypropoxylated alcohols and polybutoxylated alcohols, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylic acid adducts and mixtures of any of the above compounds may be included. Can be. 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.

The hydroxyl functional group-containing polysiloxane (a) reacts the hydroxyl functional group-containing polysiloxane with an anhydride to promote only the reaction of the anhydride with the hydroxyl functional group and prevents the formation of further esterification under the reaction conditions of the semi-ester acid group. By forming. 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 anhydride and mixtures of any of the above compounds.

The semi-ester group containing reaction product prepared as described above may be further reacted with a 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, such as shell chemicals CARDURA E, available from Campani, and mixtures of any of the above compounds.

In another embodiment, the invention relates to any of the compositions described above, wherein the at least one polysiloxane 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 bound to the polysiloxane via a "transcarbamoylation" process by reacting the hydroxyl functional group containing polysiloxane with the low molecular weight carbamate functional material. Low molecular weight carbamate functional materials, which can be derived from alcohols or glycol ethers, are reacted with free hydroxyl groups of polysiloxane polyols, i.e. materials having an average of at least two hydroxyl groups per molecule, to react with carbamate functional polysiloxanes (a) and The original alcohol or glycol ether can be obtained. The reaction conditions and proportions of reactants (i), (ii) and (iii) are chosen to form the desired group.

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. Coupling the carbamate functional group to the polysiloxane can also be accomplished by reacting isocyanic acid with the free hydroxyl group of the polysiloxane.

As mentioned above, the one or more polysiloxanes may, in addition to or instead of hydroxyl or carbamate functional groups, include one or more other reactive functional groups, for example carboxyl groups, isocyanate groups, protected isocyanate groups, carboxylate groups, primary Or secondary amine groups, amide groups, urea groups, urethane groups, anhydride groups, hydroxy alkylamide groups, epoxy groups and mixtures of any of the foregoing groups.

If the one or more polysiloxanes (a) contain carboxyl functional groups, the one or more polysiloxanes (a) may be prepared by reacting one or more polysiloxanes containing hydroxyl functional groups as described above with polycarboxylic acids or anhydrides. 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 selected to form the desired functional group.

Where at least one polysiloxane (a) 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. have. 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, line 26 to column 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 selected to form the desired functional groups.

Substituents of the formula IV X may include an oligomeric or polymeric urethane or urea-containing material which is terminated with a mixture of isocyanate, hydroxyl, primary or secondary amine functional group, or any of the materials. If substituent X comprises such functional groups, the one or more polysiloxanes are two per molecule, selected from one or more of the above-mentioned 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 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 are mentioned above and other suitable polyols; Column 8, line 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 can be saturated or unsaturated, aliphatic, cycloaliphatic, 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 polymeric ester containing group terminated with a hydroxyl or carboxylic acid functional group. When X is such a group, the at least one polysiloxane may be the reaction product of at least one polysiloxane polyol as described above, at least one substance comprising at least one carboxylic acid functional group, and at least one organic polyol. 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 Pat. No. 4,681,811 There are those disclosed in the call. Non-limiting examples of suitable organic polyols include those described above.

To prepare one or more polysiloxanes (a) 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 cycloaliphatic polyepoxide or a mixture of any of the above compounds. Non-limiting examples of suitable polyepoxides for use include one or more ethylenically unsaturated monomers including one or more epoxy groups, such as glycidyl (meth) acrylate and allyl glycidyl ether, and epoxy functional groups. There is an epoxy functional acrylic copolymer made from one or more ethylenically unsaturated monomers. Such methods of making 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 selected to form the desired functional groups.

In one embodiment, the present invention provides that the amount of one or more polysiloxanes (a), when added to other components forming the composition, in an amount ranging from 0.01 to 90% by weight, based on the total weight of resin solids present in the composition. It relates to the aforementioned coating composition present in the composition to be present in the composition. In another embodiment, the present invention provides that the at least one polysiloxane is present in the composition in an amount of at least 2% by weight, based on the total weight of resin solids present in the composition, when added to the other components forming the composition. It relates to the aforementioned coating composition present in the composition.

In another embodiment, the present invention provides that the at least one polysiloxane is present in the composition in an amount of at least 5% by weight, based on the total weight of resin solids present in the composition, when added to the other components forming the composition. It relates to the aforementioned coating composition present in the composition. In yet another embodiment, the invention provides that at least one polysiloxane is present in the composition in an amount of at least 10% by weight, based on the total weight of the resin solids present in the composition, when added to the other components forming the composition. It relates to the above-described coating composition present in the composition.

In one embodiment, the invention provides that at least one polysiloxane is present in the composition in an amount of less than 90% by weight, based on the total weight of resin solids present in the composition, when added to the other components forming the composition. It relates to the above-described coating composition present in the composition. In another embodiment, the invention provides that at least one polysiloxane is present in the composition in an amount of less than 80% by weight, based on the total weight of resin solids present in the composition, when added to the other components forming the composition. It relates to the above-described coating composition present in the composition.

In another embodiment, the invention provides that at least one polysiloxane is present in the composition in an amount of less than 65% by weight, based on the total weight of resin solids present in the composition, when added to the other components forming the composition. It relates to the above-described coating composition present in the composition. In yet another embodiment, the invention provides that at least one polysiloxane is present in the composition in an amount of less than 30% by weight, based on the total weight of resin solids present in the composition, when added to the other components that form the composition. To the aforementioned coating composition present in said composition.

As used herein, “based on the total weight of resin solids” of any of the compositions herein refers to any flexibility imparting agent comprising polysiloxane, one or more functional groups, wherein the amount of components added during the preparation of the composition is present during the preparation of the coating composition. , Any film forming component and any curing agent (but particles, any solvent or any additive solid, such as hindered amine stabilizers, UV light absorbers, catalysts, pigments such as pigment extenders and fillers, and flow control agents) Is based on the total weight of resin solids (non-volatile).

As mentioned above, the components forming the coating composition may be, in addition to the one or more polysiloxanes (a), one or more polyols or carbamate functional materials other than those different from the polysiloxane components (a) and reactants (c). Component (b).

The component (b) may be present as a main component in the composition, ie as a film forming material in an amount in the range of 30 to 80% by weight, based on the total weight of resin solids present in the composition, b) may be present in an auxiliary amount, ie in an amount of less than 30% by weight based on the total weight of resin solids present in the composition, for example as a flexibility imparting agent in a composition suitable for application to an elastomeric substrate. Of course.

In one embodiment, the invention relates to coating compositions in which component (b) is present in an amount of less than 30% by weight based on the total weight of resin solids in the composition.

Component (b) comprises functional groups as disclosed in connection with the polysiloxane which can react with the functional groups of the polysiloxane and / or with the functional group of one or more reactants (c) as described below. In one embodiment of the invention, component (b) comprises at least one reactive functional group selected from polyol groups and carbamate groups. In addition, component (b) may contain one or more other reactive functional groups selected from epoxy groups, isocyanate groups, protected isocyanate groups, carboxylic acid groups, and mixtures of any of the above groups. The functional groups of component (b) are of course selected to form a coating having a flexibility rating of at least 6 according to the flexibility test method described below upon curing of the coating composition of the present invention.

Non-limiting examples of hydroxyl group containing polymers or polyols suitable for use as component (b) include acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and mixtures of any of the foregoing compounds. In one embodiment of the invention, the polyol is selected from polyester polyols and polyether polyols.

Suitable hydroxy or carbamate group-containing acrylic polymers can be prepared from polymerizable ethylenically unsaturated monomers, and include hydroxyalkyl esters of (meth) acrylic acid or (meth) acrylic acid and one or more other polymerizable ethylenically unsaturated monomers, eg Alkyl esters and vinyl aromatic compounds of (meth) acrylic acid including, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethyl hexyl acrylate, for example styrene, alpha- May be a copolymer of methyl styrene and vinyl toluene, wherein at least one of the reactant monomers has a polyhydroxy functional group to form a hydroxy functional acrylic polymer or a carbamate functional group to form a carbamate functional acrylic polymer do. 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 ethylenically unsaturated 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 bound to polymers made from monomers. Such methods of making 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 bonded to 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 a reaction product of hydroxyalkyl carbamate, for example ammonia with ethylene carbonate or propylene carbonate, with methacrylic anhydride. Other useful carbamate functional vinyl monomers include, for example, reaction products of hydroxyethyl methacrylate, isophorone diisocyanate and hydroxypropyl carbamate; Or reaction products of hydroxypropyl methacrylate, isophorone diisocyanate and methanol. 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 bonded to the acrylic polymer by reacting the hydroxyl functional acrylic polymer with a low molecular weight alkyl carbamate, such as methyl carbamate. Pendant carbamate groups can also be bound to the acrylic polymer by "transcarbamoylation" which 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.

Hydroxy or carbamate functional polyester polymers are also useful as component (b) in the 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 functionality, ie carboxyl or hydroxyl functionality, 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, the terminal carbamate functional group can be bonded to the polyester by reacting isocyanic acid with the hydroxy functional polyester. Carbamate functional groups can also be bonded to polyesters by reacting hydroxyl polyesters with urea. Carbamate groups can also be bonded to the polyester by transcarbamoylation reactions. Suitable processes 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 or hydroxyl groups can be used as component (b) in the 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 or secondary amine group containing polyureas that may also be used may be those prepared by reacting polyamines, for example and without limitation, polymeric 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. 3,799,854, 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 may be used as shown above may 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, such as but not limited to propylene or ethylene oxide. Examples of specific and non-limiting polyethers include the trade names TERATHANE and TERACOL available from EI Du Pont de Nemours and Company, Inc., and Great Lakes Chemical Corporation. Commercially available under POLYMEG®, available from Qo Chemicals, Inc., a Lafayette subsidiary of Great Lakes Chemical Corporation of Lafayette, Indiana. POLYMEG® 1000 is the preferred polyether diol.

Carbamate functional groups can be introduced onto polyether polymers by reacting urea with polyether polyols as described above under reaction conditions well known in the art. Pendant or terminal carbamate functional groups can be bound to the polyether polymer by a transcarbamoylation reaction carried out as described above.

The polyether polymers generally have a number average molecular weight (Mn) of 500 to 5000, typically 1100 to 3200.

In one embodiment, component (b) may have a weight average molecular weight (Mw) in the range of 1000 to 20,000 as measured by gel permeation chromatography using polystyrene standards. In another embodiment, Mw of component (b) is in the range of 1500-15,000 and may range from 2000-12,000 as measured by gel permeation chromatography using polystyrene standards.

In one embodiment of the invention, the at least one material (b) is a polyol present in the components forming the coating composition in an amount of less than 30% by weight based on the total resin solids of the components and in ASTM-E222 It has a hydroxyl value of 100 to 200 mg KOH per gram of polyol as measured by acetic anhydride esterification according to the above. In this embodiment, the amount of polyol is generally in the range of 5 to 30% by weight and in the range of 12 to 30% by weight, based on the total weight of the resin solids of the components forming the composition.

In another embodiment of the invention, the at least one material comprising at least one functional group is a carbamate functional material. In one embodiment, the carbamate functional material is generally present in an amount of at least 2% by weight, based on the total weight of the resin solids present in the composition, when added to the other components forming the coating composition, 5% by weight. It may be present in an amount of at least%, typically in an amount of at least 10% by weight. In addition, the carbamate functional material is generally present in an amount of less than 80% by weight, based on the total weight of the resin solids present in the composition, when added to other components forming the coating composition, and in an amount less than 70% And typically present in an amount of less than 65% by weight. The amount of carbamate functional material present in the coating composition may range between any combination of the above values, including the values recited above.

As mentioned above, the components forming the coating composition of the present invention may comprise at least one reactive functional group of the at least one polysiloxane (a) and at least one functional group of the at least one component (b) in addition to the components (a) and (b). It may also include one or more reactants (c) comprising one or more functional groups reactive with one or more functional groups selected from, wherein each of the components is different.

In one embodiment, the at least one reactant (c) is selected from one or more curing agents. Depending on the reactive functional groups of component (a) or (b), the curing agent may be selected from aminoplast resins, polyisocyanates, protected polyisocyanate compounds , polyepoxides, polyacids, anhydrides, amines, the at least one polyol (b Polyols), and mixtures of any of the above compounds. In one embodiment, the at least one reactant (c) is selected from aminoplast resins and polyisocyanates.

In another embodiment, the present invention relates to any of the aforementioned compositions, wherein said curing agent is aminoplast. Aminoplast resins, including phenoplasts, 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, an aldehyde condensate of glycoluril may be used that provides a high melt crystalline product useful for powder coatings. Formaldehyde is the most frequently used aldehyde, but other aldehydes such as acetaldehyde, crotonaldehyde and benzaldehyde can also be used.

The aminoplast contains imino and methylol groups, and in some cases at least a portion of the methylol groups is etherified with alcohols to modify the curing reaction. Any monohydric alcohols such as methanol, ethanol, n-butyl alcohol, isobutanol and hexanol can be used for this purpose.

Non-limiting examples of aminoplasts include melamine-, urea- or benzoguanamine-formaldehyde condensates, which in some cases are monomeric and at least partially etherified with one or more alcohols having 1 to 4 carbon atoms. Non-limiting examples of suitable aminoplast resins include the tradename CYMEL® from Cytec Industries, Inc., and the tradename RESIMENE® from Solutia, Inc. Commercially available under registered trademarks).

In another embodiment, the present invention is present in an amount ranging from 2 to 65% by weight, based on the total weight of resin solids generally present in the composition when the curing agent is added to the other components that form the composition. It relates to the aforementioned coating composition comprising an aminoplast resin which may be present in an amount ranging from to 50% by weight, and typically present in an amount ranging from 5 to 40% by weight.

In yet another embodiment, the present invention relates to the aforementioned coating composition, wherein said at least one reactant (c) comprises a polyisocyanate curing agent. The term "polyisocyanate" as used herein is intended to include protected (or capped) polyisocyanates as well as unprotected polyisocyanates. The polyisocyanate may be an aliphatic or aromatic polyisocyanate, or a mixture of the two compounds. Although diisocyanates can be used, higher polyisocyanates such as isocyanurates of diisocyanates are often 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 be used.

If the polyisocyanate is protected or capped, any suitable aliphatic, cycloaliphatic or aromatic monoalcohol known to those skilled in the art can be used as the capping agent for the polyisocyanate. Other suitable capping agents are oximes and lactams. In use, the polyisocyanate curing agent is present in an amount ranging from 5 to 65% by weight, based on the total weight of the resin solids present in the composition, when added to the other components forming the coating composition, from 10 to 45% by weight. It may be present in an amount ranging from%, often in an amount ranging from 15 to 40% by weight.

Other useful curing agents include protected polyisocyanate compounds, for example tricarbamoyl triazine compounds disclosed in detail in US Pat. No. 5,084,541, which is incorporated herein by reference. The protected polyisocyanate curing agent, when used, is present in an amount ranging from 20% by weight or less based on the total weight of resin solids present in the composition when added to other components in the composition, in an amount ranging from 1 to 20% by weight. May exist.

In one embodiment, the present invention relates to the aforementioned film forming composition, wherein said at least one reactant (c) comprises both an aminoplast resin and a polyisocyanate as curing agent.

Anhydrides as curing agents for hydroxyl functional groups containing materials are also well known in the art and can be used in the present invention. Non-limiting examples of anhydrides suitable for use as curing agents in the compositions of the present invention include those derived from mixtures of ethylenically unsaturated carboxylic anhydrides and monomers comprising one or more vinyl co monomers such as styrene, alpha methyl styrene, vinyl toluene and the like. And those having two or more carboxylic anhydride groups per molecule. Non-limiting examples of suitable ethylenically unsaturated carboxylic anhydrides are maleic anhydride, citraconic anhydride and itaconic anhydride. On the one hand, the anhydride may be an anhydride adduct of a diene polymer, for example maleated polybutadiene or a maleated copolymer of butadiene, for example butadiene / styrene copolymer. Column 10, lines 16-50 of US Pat. No. 4,798,746, to which these and other suitable anhydride curing agents are incorporated by reference; And column 3, lines 41 to 57 of US Pat. No. 4,732,790.

Polyepoxides as curing agents for carboxylic acid functional groups containing materials are well known in the art. Non-limiting examples of suitable polyepoxides for use in the compositions of the present invention include polyglycidyl esters (e.g. acrylics from glycidyl methacrylate), polyglycidyl ethers of polyhydric phenols and aliphatic alcohols ( Polyhydric phenols or aliphatic alcohols, which may be prepared by etherifying an epihalohydrin such as epichlorohydrin in the presence of an alkali). These and other suitable polyepoxides are disclosed in US Pat. No. 4,681,811, column 5, lines 33-58, which is incorporated herein by reference.

Curing agents suitable for epoxy functional group containing materials include polyacid curing agents, for example ethylenically unsaturated monomers containing one or more carboxylic acid groups, and acid group-containing acrylic polymers prepared from one or more ethylenically unsaturated monomers without carboxylic acid groups. Such acid functional acrylic polymers may have an acid value in the range of 30 to 150. Acid functional group containing polyesters can also be used. The polyacid curing agents described above are disclosed in more detail in column 6, line 45 to column 9, line 54 of US Pat. No. 4,681,811, which is incorporated herein by reference.

Also well known in the art as hardeners for isocyanate functional groups containing materials are polyols, i.e. substances having at least two hydroxyl groups per molecule, different from component (b) when component (b) is a polyol. Non-limiting examples of such materials suitable for use in the compositions of the present invention include polyalkylene ether polyols such as thio ethers; Polyester polyols such as polyhydroxy polyesteramides; And hydroxyl containing polycaprolactone and hydroxy containing acrylic copolymers. Also useful are various polyols, for example glycols such as ethylene glycol, 1,6-hexanediol, bisphenol A and the like or higher polyols such as trimethylolpropane, pentaerythritol and the like formed from oxyalkylation Ether polyols. Polyester polyols may also be used. Column 7, lines 52 to 8, line 9 of US Pat. No. 4,046,729, to which such and other suitable polyol curing agents are incorporated by reference; Column 8, line 29 to column 9, line 66; And column 2, line 64 to column 3, line 33 of US Pat. No. 3,919,315.

Polyamines can also be used as curing agents for isocyanate functional groups containing materials. Non-limiting examples of suitable polyamine curing agents are primary or secondary diamines wherein the radicals bonded to the nitrogen atom may be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted aliphatic, aliphatic-substituted aromatic and heterocyclic. Or polyamines. Non-limiting examples of suitable aliphatic and cycloaliphatic diamines include 1,2-ethylene diamine, 1,2-porphylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like. do. Non-limiting examples of suitable aromatic diamines are phenylene diamines 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.

If desired, suitable mixtures of curing agents may be used. It should be mentioned that the composition can be formulated as a one-component composition that mixes a curing agent, such as an aminoplast resin and / or a protected polyisocyanate compound, such as those described above with other composition components. The one-component composition may be storage stable upon compounding. On the one hand, the composition can be formulated as a two-component composition, in which a polyisocyanate curing agent, such as those described above, can be added to the pre-formed mixture of other composition components just prior to application. The pre-formed mixture may comprise a curing agent such as an aminoplast resin and / or a protected polyisocyanate compound such as those described above.

In another embodiment where the coating material is cured by actinic radiation, or a combination of actinic radiation and thermal energy, the components forming the coating composition may include one or more photoinitiators or photosensitizers that provide free radicals or cations to initiate the polymerization process. It may further include. 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.

In another embodiment, the reactant may comprise one or more materials with one or more reactive functional groups protected by silyl groups. The silyl-protected material is different from the polysiloxane (a) discussed above. Hydrolysis of the silyl group regenerates reactive functional groups on the material that can be used for further reaction with the curing agent.

Preferred silyl protecting groups may have the following formula (IX):

Where

Each R ₁ , R ₂ and R ₃ may be the same or different and represent an alkyl group, a phenyl group or an allyl group having 1 to 18 carbon atoms.

Non-limiting examples of suitable functional groups that may be protected by such 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 the functional groups to form silyl groups include hexamethyldisilazane (preferably), trimethylchlorosilane, trimethylsilyldiethylamine, t-butyl dimethylsilyl chloride, diphenyl methyl Silyl chloride, hexamethyl disilylazide, hexamethyl dissiloxane, trimethylsilyl triflate, hexamethyldissilyl acetamide, N, N'-bis [trimethylsilyl] urea and mixtures of any of the above compounds.

Further examples of compounds suitable for the silylation reaction and reaction conditions and reagents suitable for the trimethylsilylation reaction can be found in Example 28, below, and in the references cited in the present invention. Greene et al., Protective Groups in Organic Synthesis, (2d. Ed. 1991), pp. 68-86 and 261-263.

The main chain of the material is at least one bond selected from ester bonds, urethane bonds, urea bonds, amide bonds, siloxane bonds and ether bonds, or polymers such as polyesters, acrylic polymers, polyurethanes, polyethers, polyureas, polyamides and It may be a compound comprising a copolymer of any of the above polymers.

Suitable compounds or polymers having at least one ester bond and at least one reactive functional group include semi-esters formed from the reaction of at least one polyol with at least one 1,2-anhydride, or acid functional polys derived from polyols and polyacids or anhydrides. Esters, which are disclosed in column 5, line 29 to column 8, line 6 of US Pat. No. 5,256,452, some of which are incorporated herein by reference. The semi-esters are suitable because they have a relatively low molecular weight and are very reactive with epoxy functional groups.

The semi-esters are obtained, for example, by reaction between the polyols and 1,2-anhydrides under conditions sufficient to ring-open the anhydrides forming the semi-esters substantially without the occurrence of polyesteration. Such reaction products have a relatively low molecular weight and low viscosity with a narrow molecular weight distribution. "Substantially without the occurrence of polyesterization" means that the carboxyl groups formed by the reaction of anhydride are not further esterified by said polyol in a recurrent manner. In addition to the above embodiments, less than 10% by weight, typically less than 5% by weight, of high molecular weight polyesters are formed based on the resin solids of the components forming the coating composition.

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

In one embodiment, 1,2-dicarboxylic anhydride can be used for the desired ring opening reaction and semi-ester formation. Reacting the polyol with carboxylic acid instead of anhydride will require esterification by condensation and water removal by distillation and such conditions may promote undesirable polyesteration. According to the present invention, the reaction temperature may be lower than 135 ° C., typically in the range of 70 to 135 ° C. The reaction time may vary somewhat depending on the reaction temperature and is generally in the range of 10 minutes to 24 hours.

The equivalent ratio of anhydride to hydroxyl on the polyol may be at least 0.8: 1 (the anhydride is considered monofunctional) to obtain the maximum conversion to the desired semi-ester. A ratio of less than 0.8: 1 may be used, but such ratios may increase the formation of less functional semi-esters.

Useful anhydrides include aliphatic, cycloaliphatic, olefin, cycloolefin 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 are 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, for example Methylhexahydrophthalic anhydride (preferably), tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, chloric anhydride, itaconic anhydride, citraconic anhydride and maleic anhydride.

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

Among the simple polyols that can be used are diols, triols, tetrols and mixtures thereof. Examples of suitable polyols include polyols having 2 to 10 carbon atoms, for example 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; 2-ethyl-1,3-hexanediol; TMP / epsilon-caprolactone triol; Ethylene glycol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; Neopentyl glycol; Diethylene glycol; Dipropylene glycol; 1,4-cyclohexanedimethanol and 2,2,4-trimethylpentane-1,3-diol.

For oligomeric polyols, suitable polyols that can be used are polyols prepared from the reaction of diacids with triols, for example trimethylol propane / cyclohexane diacid and trimethylol propane / adipic acid.

For polymeric polyols, polyester polyols can be prepared by esterification with organic polyols or their anhydrides with organic polyols and / or epoxides. Usually, the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids or acid anhydrides and diols.

Polyols that can be used in the preparation of 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 and diols, for example reaction products of epsilon-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyester glycols such as poly (oxytetramethylene) glycol, and the like. .

The acid component of the polyester includes monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule. Among the acids that can be used 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 types of other dicarboxylic acids. It is also possible to use higher polycarboxylic acids, for example trimellitic acid and tricavallylic acid.

In addition to polyester polyols formed from polybasic acids and polyols, polylactone-type polyesters can also be used. The product may be 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, it is possible to use polyurethane polyols such as polyester-urethane polyols which can be formed by reacting organic polyisocyanates with polyester polyols, for example those disclosed above. The organic polyisocyanate may be reacted with the polyol such that the OH / NOC equivalent ratio is at least 1: 1 so that the resulting product contains free hydroxyl groups. Organic polyisocyanates that can be used in the preparation of polyurethane polyols can be aliphatic or aromatic polyisocyanates or mixtures. Diisocyanates are preferred, but higher polyisocyanates such as triisocyanates can be used but these produce higher viscosities.

Examples of suitable diisocyanates include 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.

At least in part, all of the acid functionalities may be silylated. On the other hand, at least in part, in some cases all of the acid functionalities can be converted to hydroxyl groups by reaction with epoxides. In some embodiments, the epoxide is a monofunctional epoxide such as ethylene oxide, butylene oxide, propylene oxide, cyclohexane oxide, glycidyl ether and glycidyl ester, and is silylated. The equivalent ratio of epoxy groups to acid groups on esters is generally in the range of 0.1: 1 to 2: 1, can range from 0.5: 1 to 1: 1, and typically ranges from 0.8: 1 to 1: 1. . In another embodiment, aliphatic diols such as 1,2-propanediol may be used in place of the epoxide.

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

In one embodiment, the coating composition of the present invention comprises a compound of formula

Other useful materials having one or more reactive functional groups suitable for silylation and a bond selected from ester bonds, urethane bonds, urea bonds, amide bonds, siloxane bonds and ether bonds are disclosed in the discussion of such further suitable polymers.

Useful reactants, on the other hand, include hydroxyl group-containing acrylic polymers protected with hydrolyzable siloxy groups (eg polymerized from vinyl monomers and trimethyl siloxy methylmethacrylate), for example cited herein by reference. I. Azuma et al., "Acrylic Oligomer for High Solid Automotive Top Coating System Having Excellent Acid Resistance", Progress in Organic Coatings 32 (1997) 1-7.

In one embodiment, the present invention provides 0.1 to 90 weight percent of the coating composition based on the total weight of the resin solids of the components that form the composition when the silyl-protected reactant is added to the other components that form the coating composition. It relates to any of the aforementioned compositions present in an amount in the range of%. In another embodiment, the present invention provides at least 0.1% by weight of the silyl-protected reactant in the coating composition based on the total weight of the resin solids of the components forming the composition when added to other components forming the coating composition. Present in any amount, and may be present in an amount of at least 1% by weight, usually in an amount of at least 5% by weight.

In yet another embodiment, the present invention generally relates to the coating composition based on the total weight of the resin solids of the components forming the composition when the silyl-protected reactant is added to the other components forming the coating composition. It is directed to any of the compositions described above, which are present in an amount of less than, by weight, may be present in an amount of less than 30% by weight, and typically present in an amount of less than 10% by weight. The amount of silyl-protected reactant present in the coating composition can range between any combination of the above values, including the values recited above.

In a further embodiment, the present invention is directed to the aforementioned coating composition comprising one or more film forming materials. The film forming material may be a polymer other than the above and different from the at least one polysiloxane (a), the material (b) and the at least one reactant (c). The film forming polymer has at least one reactive functional group selected from at least one reactive functional group of the at least one polysiloxane (a), at least one functional group of the at least one component (b), and at least one functional group selected from the at least one functional group of the reactant (c). It may have a functional group. In one embodiment, the one or more additional polymers may have one or more reactive functional groups selected from hydroxyl groups, carbamate groups, epoxy groups, isocyanate groups, and carboxyl groups. In another embodiment, the polymer may have one or more reactive functional groups selected from hydroxyl groups and carbamate groups.

The film forming material may contain one or more reactive functional groups selected from hydroxyl groups, carbamate groups, epoxy groups, isocyanate groups, carboxylic acid groups and mixtures of any of the above groups.

Non-limiting examples of film forming polymers suitable for use as the at least one film forming material (c) include those described above in connection with the polyol or carbamate functional material (b).

The coating composition of the present invention may be in the form of a solvent based composition, an aqueous composition, solid particulate form, ie, a powder composition, a powder slurry or an aqueous dispersion. The components of the invention used to prepare the 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; And glycol ethers such as ethylene glycol monobutyl ether; ester; Other solvents; And any of the above mixtures.

In the solvent based composition, the organic solvent is generally present in an amount ranging from 5 to 80% by weight based on the total weight of the resin solids of the components forming the composition; It may be present in an amount ranging from 30 to 50% by weight. The above-described composition may have a total solids content in the range of 40 to 75 wt% based on the total weight of the resin solids of the components forming the composition, and may have a total solids content in the range of 50 to 70 wt%. On the one hand, the compositions of the present invention may be in the form of solid particulates 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 film forming compositions described above further comprise a catalyst present during the preparation of the composition. In one embodiment, the catalyst is present in an amount sufficient to promote a reaction between one or more reactive functional groups of the one or more reactants (c) and / or one or more reactive functional groups of the one or more polysiloxanes (a).

Non-limiting examples of suitable catalysts are acidic materials such as acid phosphates such as phenyl acid phosphate and substituted or unsubstituted sulfonic acids such as dodecylbenzene sulfonic acid or paratoluene sulfonic acid. Non-limiting examples of suitable catalysts for the reaction between isocyanate groups and hydroxyl groups include tin catalysts such as dibutyl tin dilaurate. Non-limiting examples of epoxy acid base catalysts are tertiary amines such as N, N'-dimethyldodecyl amine catalysts. In another embodiment, the catalyst may be phosphorylated polyester or phosphorylated epoxy. In this embodiment, the catalyst is a reaction product of, for example, phosphoric acid and bisphenol A diglycidyl ether having two hydrogenated phenol rings, for example DRH-151 (commercially available from Shell Chemical Company). Present). The catalyst is present in an amount ranging from 0.1 to 5.0 weight percent based on the total weight of the resin solids of the components forming the composition when added to the other components forming the composition, typically in the range from 0.5 to 1.5 weight percent. Present in quantities.

In another embodiment, additional ingredients may be present during the preparation of the compositions described above. These additional components include, but are not limited to, particles different from components (a), (b) and (c), flexibility granters, plasticizers, surface active agents, thixotropic agents, rheology control agents, gas evolution agents, organic cosolvents, Flow control agents, hindered amine light stabilizers, antioxidants, UV light absorbers, colorants or dyes, and similar additives customary in the art, as well as mixtures of any of the foregoing materials can be included in the composition. These additional components may be present in an amount of up to 40 weight percent based on the total weight of the resin solids of the components that form the composition when added to the other components that form the composition.

In one embodiment, the present invention relates to the aforementioned composition, further comprising a plurality of particles. In another embodiment, the present invention relates to any of the aforementioned compositions, wherein said particles have an average particle size of less than 100 μ prior to incorporation into the composition. In another embodiment, the present invention relates to any of the aforementioned compositions, wherein said particles have an average particle size in the range of 1 to 1000 nm prior to incorporation into the composition. In yet another embodiment, the present invention relates to any of the aforementioned compositions, wherein said particles have an average particle size in the range of 1 to 100 nm prior to incorporation into the composition.

In another embodiment, the present invention relates to any of the aforementioned compositions, wherein said particles have an average particle size in the range of 5-50 nm prior to incorporation into the composition. In another embodiment, the present invention relates to any of the aforementioned compositions, wherein said particles have an average particle size in the range of 5-25 nm prior to incorporation into the composition.

In embodiments in which the average particle size of the particles is at least 1 μ, the average particle size can be measured according to known laser scattering techniques. For example, the average particle size of such particles is determined by a Horiba model LA 900 laser diffraction particle size device (using a helium-neon laser with a wavelength of 633 nm to measure the particle size, The particle size is related to the smallest sphere that completely surrounds the particle.

In embodiments of the invention where the size of the particles is 1 μm or less, the average particle size can be determined by visually examining an electron micrograph on a transmission electron microscopy (“TEM”), where the test method determines the particle diameter in the phase. The average particle size is calculated based on the magnification of the TEM. Those skilled in the art will understand how to make such a TEM, and the description of such a method is disclosed in the examples shown below. In one non-limiting embodiment of the invention, a 105,000-fold magnified TEM phase is prepared, dividing the magnification by 1000 to obtain the conversion factor. Upon visual inspection, the diameter of the particles is measured in mm and the measurement is converted to nm using the conversion factor. The diameter of the particles relates to a sphere of smallest diameter that completely surrounds the particles.

The shape (or form) of the particles can vary depending on the particular embodiment of the invention and its intended use. For example, generally spherical forms (eg, solid beads, fine beads or hollow spheres) can be used, and particles can also be used in the form of cubes, plates or needles (stretched or fibrous). The particles can also have an internal structure that is hollow, porous or void free, or any combination of the above forms, for example a hollow center with a porous or solid wall. For more information on suitable particle characteristics, see H. Katz et al. (Ed.), Handbook of Fillers and Plastics (1987), p. 9-10].

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

Particles can be prepared from materials selected from polymeric and non polymeric inorganic materials, polymeric and non polymeric organic materials, composite materials, and mixtures of any of the foregoing materials. As used herein, the term "polymeric inorganic material" means a polymeric material having a backbone repeating unit based on an element or elements other than carbon. For more information, see James Mark et al., Inorganic Polymers, Prentice Hall Polymer Science and Engineering Series, (1992) p. 5] (incorporated herein by reference). As used herein, the term "polymeric organic material" refers to synthetic polymeric materials, semisynthetic polymeric materials, and natural polymeric materials, all of which have backbone repeating units based on carbon.

As used herein, "organic material" refers to a binary compound, such as carbon, which is typically bonded to itself and to hydrogen, and often to other elements, such as carbon oxides, carbides, carbon disulfides, and the like; Ternary compounds such as metal cyanide, metal carbonyl, phosgene, carbonyl sulfide and the like; And carbon-containing compounds other than carbon-containing ionic compounds such as metal carbonates such as calcium carbonate and sodium carbonate. R. Cited herein by reference. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) p. 761-762; And in M. Silberberg, Chemistry The Molecular Nature of Matter and Change (1996) p. 586.

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

As used herein, the term "composite material" means a combination of two or more different materials. Particles made from composite materials generally have a surface hardness that is different from the hardness of the inner portion of the particles just below the surface. More specifically, the surface of the particles may be prepared in any manner well known in the art, including, but not limited to, chemically or physically changing its surface properties using techniques known in the art. Can be modified.

For example, particles may be prepared from a first material that is coated, covered, or encapsulated with one or more second materials to form composite particles having a more flexible surface. In yet another embodiment, particles made from the composite material may be prepared from the first material that has been coated, covered, or encapsulated with a different type of first material. For more information on particles useful in the present invention, see G. Wypych, Handbook of Fillers, 2nd Ed. (1999) p. 15-202 (incorporated herein by reference).

Particles suitable for use in the compositions of the present invention may include inorganic elements or compounds known in the art. Suitable particles can be prepared from ceramic materials, metal materials and mixtures of any of the above materials. Suitable ceramic materials include metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates and mixtures of any of the foregoing materials. Specific non-limiting examples of metal nitrides are boron nitride; Specific non-limiting examples of metal oxides are zinc oxide; Non-limiting examples of suitable metal sulfides are molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide; Non-limiting suitable examples of metal silicates are aluminum silicates and magnesium silicates such as vermiculite.

The particles are for example essentially a single inorganic oxide such as silica, alumina or colloidal alumina in colloidal, fuming or amorphous form, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, for example colloid or Amorphous zirconia and mixtures of any of the above materials; Or another type of organic oxide may comprise a core of one type of inorganic oxide deposited on the surface. When the composition of the present invention is used as a transparent coating film in a transparent top coat, for example, a multicomponent composite coating composition, the particles must not severely interfere with the optical properties of the composition. As used herein, “transparent” means that the cured coating has a BYK haze index of less than 50 as measured using a BYK / blur gloss device.

Non-polymeric inorganic materials useful for preparing the particles of the present invention include inorganic materials selected from graphite, metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates and hydroxides. A non-limiting example of a useful inorganic oxide is zinc oxide. Non-limiting examples of suitable inorganic sulfides include molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide. Non-limiting examples of useful inorganic silicates include aluminum silicates and magnesium silicates such as vermiculite. Non-limiting examples of suitable metals include molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys and mixtures of any of the above metals.

In one embodiment, the present invention relates to a method in which the particles comprise fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the above materials It relates to any of the above-described compositions selected from. In another embodiment, the present invention relates to any of the aforementioned compositions, wherein said particles comprise colloidal silica. As disclosed above, these materials may be surface treated or untreated.

The composition may comprise a precursor suitable for forming silica particles in situ by a sol-gel process. The composition according to the invention may comprise alkoxy silanes which can be hydrolyzed to form silica particles in situ. For example, silica particles can be prepared by hydrolyzing and condensing tetraethylortho silicate with an acid such as hydrochloric acid. Other useful particles are surface modified silicas such as those disclosed in US Pat. No. 5,853,809, column 6, line 51 to column 8, line 43, incorporated herein by reference.

In one embodiment of the present invention, the particles have a hardness value that is greater than the hardness value of the material that may wear the polymeric coating or polymeric substrate. Examples of materials that can wear the polymeric coating or polymeric substrate include, but are not limited to, dust, sand, rock, glass, car wash brushes, and the like. Hardness values of particles and materials that may wear the polymeric coating or polymeric substrate can be measured by any conventional hardness measurement method, such as Vickers or Brinell hardness, but are preferred. Preferably the relative scratch resistance of the material surface is measured according to the original Mohs hardness, which is represented on a scale of 1 to 10. Morse hardness values for a number of non-limiting examples of particles made from inorganic materials suitable for use in the present invention are shown in Table A below.

In one embodiment, the MOS hardness value of the particles is at least 5. In some embodiments, the MOS hardness value of the particles, such as silica, is at least 6.

As mentioned above, the Morse hardness grade relates to the scratch resistance of the material. The present invention therefore also contemplates particles having a surface hardness that differs from that of the inner portion of the particles just below the surface. More specifically, as discussed above, the surface of the particles may be formed in any manner well known in the art, for example, but not limited to the surface hardness of the particles that may wear the polymeric coating or polymeric substrate. The hardness of the particles immediately below the surface while greater than the hardness is modified by chemically changing the surface properties of the particles using techniques known in the art such that the hardness of the polymeric coating or polymeric substrate is less than that of the material that may wear out. Can be.

As another alternative, the particles can be prepared from a first material that is coated, covered or encapsulated with one or more second materials to form composite particles with a more flexible surface. On the one hand, the particles can be prepared from a first material which is coated, covered or encapsulated with a different material of the first material to form a composite material with a more flexible surface.

In one example, useful composite particles can be prepared by providing silica, carbonate, or nanoclay coatings to inorganic particles made from inorganic materials such as silicon carbide or aluminum nitride without limiting the invention. In another non-limiting example, silane coupling agents with alkyl side chains can interact with the surface of inorganic particles made from inorganic oxides to provide useful composite particles having a "flexible" surface. Other examples include overlaying, encapsulating, or coating particles made from non-polymeric or polymeric materials with different non-polymeric or polymeric materials. A specific non-limiting example of such composite particles is DUALITE ^™ , which is a synthetic polymeric particle coated with calcium carbonate, commercially available from Pierce and Stevens Corporation of Buffalo, NY.

In one non-limiting embodiment of the invention, the particles are made from a solid lubricant material. As used herein, the term "solid lubricant" means any solid used between two surfaces to protect from damage during relative movement or to reduce friction and wear. In one embodiment, the solid lubricant is an inorganic solid lubricant. As used herein, "inorganic solid lubricant" means that the solid lubricant has a characteristic crystal behavior that causes it to shear into thin, flat plates that slide easily with each other to produce a gamma lubrication effect. See, R., incorporated herein by reference. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) p. 712. Friction is resistance to sliding of one solid onto another. F. incorporated herein by reference. Clauss, Solid Lubricants and Self-Lubricating Solids (1972) p. 1].

In one non-limiting embodiment of the invention, the particles have a lamellar structure. Particles with a lamellar structure consist of a sheet or plate of atoms in a hexagonal arrangement, having strong bonds inside the sheets and weak van der Waals bonds between the sites, providing low shear strength between the sheets. Non-limiting examples of lamellar structures are hexagonal crystal structures. Inorganic solid particles having a lamellar fullness (ie, buckyball) structure are also useful in the present invention.

Non-limiting examples of suitable materials having a lamellar structure useful for the preparation of the particles of the present invention include boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolin, calcite, cadmium iodide, silver sulfide and any of the above materials There is a mixture. Suitable metal dichalcogenides include molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures of any of the foregoing materials.

The particles can be prepared from non polymeric organic materials. Non-limiting examples of non-polymeric organic materials useful in the present invention are stearates (eg zinc stearate and aluminum stearate), diamond, carbon black and stearamide.

Particles can be prepared from inorganic polymeric materials. Non-limiting examples of useful inorganic polymeric materials include polyphosphazenes, polysilanes, polysiloxanes, polygeremann, polymeric sulfur, polymeric selenium, silicone, and mixtures of any of the foregoing materials. Specific and non-limiting examples of particles made from inorganic polymeric materials suitable for use in the present invention are TOSPEARL (RJ Perry, "Applications for Cross-Linked Siloxane Particles" Chemtech, February 1999, p. 39-44) Is a particle made from crosslinked siloxane and is commercially available from Toshiba Silicones Company, Ltd. of Japan.

The particles can be prepared from synthetic organic polymeric materials. Non-limiting examples of suitable organic polymeric materials include thermosets and thermoplastics. As used herein, a "thermoplastic" material is a material that softens upon exposure to heat and returns to its original state upon cooling 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, acrylic polymers. Such as copolymers of styrene and acrylic acid monomers, and methacrylate containing polymers, polyamides, thermoplastic polyurethanes, vinyl polymers, and mixtures of any of the foregoing compounds.

Non-limiting examples of suitable thermoset materials include thermoset polyesters, vinyl esters, epoxy materials, phenols, aminoplasts, thermoset polyurethanes, and mixtures of any of the foregoing materials. Specific and non-limiting examples of synthetic polymeric particles made from epoxy materials are epoxy microgel particles. As used herein, a "thermoset" material is a material that is irreversibly solidified or "cured" upon heating. The thermoset material forms a crosslinked network. The polymeric material used herein is “crosslinked” when it at least partially forms a polymeric network. One skilled in the art measures the presence and extent of crosslinking (crosslink density) by various methods, for example by dynamic thermal analysis (DMTA) using a TA device DMA 2980 analyzer performed under nitrogen as described above. I will understand. The method measures the glass transition temperature and the crosslink density of the glass film of the coating or polymer. These physical properties of the cured material correlate with the structure of the crosslinked network.

The particles may also be hollow particles made from materials selected from polymeric and non polymeric inorganic materials, polymeric and non polymeric organic materials, composite materials, and mixtures of any of these materials. Non-limiting examples of suitable materials from which the hollow particles can be made are disclosed above.

In an embodiment of the invention, at least one polysiloxane (a) does not react with the particles.

In one embodiment, the invention is present in the composition in an amount ranging from 0.01 to 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 any of the compositions described above. In another embodiment, the present invention is 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 forming the composition when the particles are added to the other components forming the composition, 0.5 It may be present in the composition in an amount of at least% by weight, and typically relates to any of the compositions described above present in the composition in an amount of at least 5% by weight.

In yet another embodiment, the invention is 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 that form the composition when the particles are added to the other components that form the composition. , May be present in the composition in an amount of less than 50% by weight, may be present in the composition in an amount of less than 20% by weight, and typically in any of the compositions described above present in the composition in an amount of less than 10% by weight. It is about. The amount of particles present in the composition can range between any combination of these values, including the values recited above.

One class of particles that can be used according to the invention includes a sol of the particles, for example an organic sol, before incorporation. The sol can be a wide variety of small particle colloidal silicas having an average particle size in the range as indicated above.

The colloidal silica can be surface modified during or after the initial formation of the particles. Such surface modified silicas are anhydrous SiO ₂ and SiOH groups, as well as carbon-containing moieties chemically bonded to their surface, depending on the properties of the particular silica desired, various ion groups physically or chemically bonded within the silica surface. , Adsorbed organic groups or mixtures of any of the above groups. Such surface modified silicas are disclosed in detail in US Pat. No. 4,680,204, which is incorporated herein by reference.

Such materials can be prepared in a variety of forms by various techniques, non-limiting examples of which are organic sol and mixed sol. The term "mixed sol" as used herein is intended to include dispersions of colloidal silica in which the dispersion medium comprises both organic liquids and water. Such small particle colloidal silicas are readily available and are essentially colorless, so as to produce a colorless transparent coating without additional pigments or ingredients known in the art to color the composition or reduce the transparency of the composition. It has a refractive index that is acceptable for incorporation in the composition.

Suitable non-limiting examples of such particles are commercially available as colloidal silicas such as the tradename ORGANOSILICASOLS ^™ from Nissan Chemical Company, for example ORGANOSILICASOL ^™ MT-ST, and HIGHLINK ^™ from Clariant Corporation. Available; Colloidal alumina, such as those commercially available from Nalco Chemical under the tradename NALCO 8676®; And colloidal zirconia, such as those commercially available under the trade name HIT-32M® from Nissan Chemical Company.

The particles can be incorporated into the compositions of the invention in the form of stable dispersions. When the particles are in colloidal form, the dispersion can be prepared by dispersing the particles in a carrier under stirring, and the solvent present can be removed under vacuum at ambient temperature. In some embodiments, the carrier is a solvent other than a solvent, for example polysiloxane containing surface active agents, such as, but not limited to, reactive functional groups, such as, but not limited to, the at least one polysiloxane (a) Can be.

On the other hand, such dispersions may be prepared as disclosed in US Pat. No. 4,522,958 or 4,526,910, which is incorporated herein by reference. The particles may be “cold-blended” with the one or more polysiloxanes (a) prior to incorporation into the composition of the present invention. On the one hand, the particles can be post-added to a mixture of any remaining composition components (including but not limited to the at least one polysiloxane (a)) and dispersed therein using dispersion techniques well known in the art.

When the particles are other than colloidal form, for example, but not limited to agglomerate form, the agglomerates are dispersed in a carrier, for example, but not limited to one or more polysiloxanes (a), thereby stably dispersing the particles therein. Dispersions can be prepared. Dispersion techniques such as milling, microfluidization, sonication, or any other pigment dispersion techniques well known in the art of coating formulations can be used. On the one hand, the particles can be dispersed by any other dispersion technique known in the art. If desired, particles other than the colloidal form may be post-added to a mixture of other composition components and dispersed therein using any dispersion technique known in the art.

The particles may be present as dispersions, suspensions or emulsions in a carrier. Non-limiting examples of suitable carriers are water, solvents, surfactants or any mixtures of the foregoing.

In yet another embodiment of the present invention, one or more auxiliary surface active agents may be present during the preparation of the composition as described above. Moreover, as used herein, "surfactant" means any material that tends to lower the surface energy of a solid surface tension or "cured" composition or coating. That is, a cured composition or coating made from a composition comprising a surface active agent has a lower solid surface tension or surface energy than a cured coating made from a similar composition containing no surface active agent.

For the purposes of the present invention, solid surface tension can be measured according to the Owens-Wendt method using a Rame'-Hart contact angle goniometer with distilled water and methylene iodide as reagents. Generally, 0.02 cc drops of one reagent are placed on the cured coating surface and the contact angle and its opening angle are measured using a standard microscope equipped with the goniometer. The contact angle and its complement angle are measured for 3 drops each. The process is then repeated using other reagents. Calculate the mean value for six measurements for each reagent. Solid surface tension is then calculated using the Owens-Went equation:

Where

γ│ is the surface tension of the liquid (methylene iodide = 50.8, distilled water = 72.8),

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

Φ and cosΦ are measured values.

Next, formulas for methylene iodide and two formulas for water are prepared. The only unknown is γ _s ^d and γ _s ^p . The two equations are then solved for the two unknown values. The two components combined represent the total solid surface tension.

The at least one auxiliary surface active agent may be selected from amphoteric reactive functional groups containing polysiloxanes, amphoteric fluoropolymers and mixtures of any of the foregoing compounds as described above. With respect to water soluble or water dispersible amphoteric materials, the term "amphoteric" means a polymer having a hydrophilic polar end and a hydrophobic end that is generally water insoluble. Non-limiting examples of functional group-containing polysiloxanes suitable for use as surface active agents include the aforementioned polysiloxanes. Non-limiting examples of suitable amphoteric fluoropolymers include, but are not limited to, fluoroethylene-alkyl vinyl ether alternating copolymers available from Asahi Glass Company under the trade name LUMIFLON (see, for example, US Pat. No. 4,345,057). those); Fluorosurfactants such as fluoroaliphatic polymeric esters commercially available under the trade name FLUORAD from St. Paul, MN; Functionalized perfluorinated materials, such as 1H, 1H-perfluoro-nonanol commercially available from FluoroChem USA; And perfluorinated (meth) acrylate resins.

Non-limiting examples of other auxiliary surface active agents suitable for use in the compositions or coatings of the present invention may include anionic, nonionic and cationic surface active agents.

Non-limiting examples of suitable anionic surfactants include sulfates or sulfonates. Specific non-limiting examples include higher alkyl mononuclear aromatic sulfonates, for example higher alkyl benzene sulfonates containing alkyl groups of 10 to 16 carbon atoms and straight or branched chains such as decyl, undecyl, dodecyl, tridecyl Sodium salts and higher alkyl toluene, xylene and phenol sulfonates of tetradecyl, pentadecyl or hexadecyl benzene sulfonates; Alkyl naphthalene sulfonates and sodium dinonyl naphthalene sulfonates. Other non-limiting examples of suitable anionic surfactants include olefin sulfonates such as long chain alkylene sulfonates, long chain hydroxyalkane sulfonates and mixtures of any of the foregoing compounds. Non-limiting examples of other sulfate or sulfonate detergents are the reaction products of paraffin sulfonates, such as alpha olefins and bisulfites, such as sodium bisulfite. Also sulfates of higher alcohols such as sodium lauryl sulfate, sodium tallow alcohol sulfate, or sulfates of mono- or di-glycerides of fatty acids such as stearic acid monoglyceride monosulfate, alkyl poly (ethoxy) Ether sulfates, such as but not limited to sulfates of condensation products of ethylene oxide and lauryl alcohol (usually containing 1 to 5 ethoxy groups per molecule); Lauryl or other higher alkyl glyceryl ether sulfonates; Also included are aromatic poly (ethenoxy) ether sulfates, such as, but not limited to, sulfates of condensation products of ethylene oxide and nonyl phenol, usually containing 1 to 20 oxyethylene groups per molecule. Further non-limiting examples include salts of alkyl aryl ethoxy sulfates available under the general brand name ABEX from sulfated aliphatic alcohols, alkyl ether sulfates or long-furans. Anionic surfactants of the phosphate mono- or di-ester type can also be used. These anionic surface active agents are well known in the art and are commercially available from GAF Corporation under the trade name GAFAC and under the trade name TRITON from Rohm and Haas Co., Ltd.

Non-limiting examples of non-ionic surface active agents suitable for use in the cured compositions or coatings of the present invention include the formula RO (R'O) _n H, where substituent R represents a hydrocarbon group having 6 to 60 carbon atoms, substituent R 'Represents an alkylene group having 2 or 3 carbon atoms and any of the above mixtures, n being an integer ranging from 2 to 100). Such nonionic surface active agents can be prepared by treating fatty alcohols or alkyl substituted phenols with excess ethylene or propylene oxide. The alkyl carbon chain may contain 14 to 40 carbon atoms and may be derived from long chain fatty alcohols such as oleyl alcohol or stearyl alcohol. Non-ionic polyoxyethylene surface active agents of the type represented by the above formula are manufactured under the trade name SURFYNOL (R) from Air Products Chemicals, Inc .; PLURONIC® or TETRONIC® from BASF Corporation; TERGITOL® from Union Carbide; And HURTSMAN Corporation, commercially available as SURFONIC®. Other non-limiting examples of suitable non-ionic surfactants include block copolymers of ethylene oxide and propylene oxide based on glycols such as ethylene glycol or propylene glycol, for example, but not limited to the trade name PLURONIC® from BASF Corporation. There are things that can be obtained.

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

Other examples of suitable surface active agents may include polyacrylates. Non-limiting examples of suitable polyacrylates include homopolymers and copolymers of acrylate monomers such as polybutylacrylate, and acrylate monomers (eg ethyl (meth) acrylate, 2-ethylhexylacrylate, Butyl (meth) acrylate and isobutyl acrylate), and copolymers derived from hydroxy ethyl (meth) acrylate and (meth) acrylic acid monomers. In one embodiment, the polyacrylate may have amino and hydroxy functional groups. Suitable amino and hydroxy functional acrylates are disclosed in Example 26 below and US Pat. No. 6,013,733, which is incorporated herein by reference. Another example of useful amino and hydroxyl functional copolymers is a copolymer of hydroxy ethyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate and dimethylamino ethyl methacrylate. In another embodiment, the polyacrylate may have an acid functional group that may be provided by incorporating an acid functional monomer, for example (meth) acrylic acid, into, for example, the components used to prepare the polyacrylate. have. In another embodiment, the polyacrylate is an acid functional monomer such as (meth) acrylic acid and a hydroxy functional monomer, such as hydroxy, for example in the components used in the preparation of the polyacrylate. It may have an acid functional group and a hydroxy functional group which may be provided by incorporating ethyl (meth) acrylate.

Suitable flow additives include silicones such as BYK310 or BYK307, which are commercially available from Byk-Chemie. Suitable flow control agents include cellulose acetate butyrate and fumed silica, such as R812, which is commercially available from Degussa Chemical.

In yet another embodiment, the present invention relates to a coated substrate comprising a substrate and a composition coated on at least a portion of the substrate, selected from any of the above compositions. In yet another embodiment, the invention relates to a method of coating a substrate, comprising coating a composition (selected from any of the above compositions) on at least a portion of the substrate. In another embodiment, the invention relates to a method of coating a substrate, further comprising curing the composition after application to the substrate. In these embodiments the components used in the preparation of the composition may be selected from those discussed above, and the additional components may also be selected from those cited.

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

The coating composition of the present invention can be applied on virtually any flexible substrate, including plastics, and polymeric substrates such as elastomeric substrates. In one embodiment, the present invention relates to the coated substrate described above, wherein the coated substrate is a flexible elastomeric substrate. In yet another embodiment, the present invention relates to the aforementioned coated substrate, wherein the coated substrate is a polymeric substrate. In these embodiments the components used in the preparation of the composition may be selected from those discussed above, and further components may be selected from those recited above.

A further embodiment of the present invention relates to a coated automotive substrate comprising an automotive substrate and a composition (selected from any of the above compositions) coated over at least a portion of the automotive substrate. In yet another embodiment, the present invention is directed to a method of making a coated automotive substrate comprising providing an automotive substrate and coating a composition selected from any of the above compositions on at least a portion of the automotive substrate. Again, in these embodiments the components used in the preparation of the composition may be selected from those discussed above, and further components may be selected from those cited above.

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

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

The polymeric substrate described above may have an adhesion promoter present on the surface of the substrate to which the coating composition of the present invention is applied. In order to promote adhesion of the organic coating to the polymeric substrate, the substrate can be pretreated using an adhesion promoter layer or connecting coating, for example a thin layer of 0.25 mil (6.35 μ) thick, or by flame or corona pretreatment. have.

Suitable adhesion promoters include chlorinated polyolefin adhesion promoters, eg, US Pat. No. 4,997,882, incorporated herein by reference; 5,319,032; And 5,397,602. Other useful adhesion promoting coatings are described in US Pat. No. 6,001,469 (coating compositions containing saturated polyhydroxylated polydiene polymers with terminal hydroxyl groups), 5,863,646 (saturated polyhydroxylated polydiene polymers and chlorinated). Coating compositions with blends of polyolefins) and 5,135,984 (chlorinated polyolefins, maleic anhydride, acrylic or methacrylic modified hydrogenated polybutadiene and organic furs containing one or more acryloyl groups or methacryloyl groups per unit molecule) Coating compositions having adhesion promoting materials obtained by reacting oxides), the patents of which are incorporated herein by reference.

When the substrate is used as a component for manufacturing vehicles (including but not limited to automobiles, trucks and tractors), the substrate can have any shape and can be selected from the flexible substrates described above. Typical shapes of automotive body components may include automotive body side moldings, fenders, bumpers and sheaths.

In a further embodiment, the present invention relates to the aforementioned coated automotive substrate, wherein the coated automotive substrate is a vehicle body side molding. In another embodiment, the present invention relates to the aforementioned coated automotive substrate, wherein the coated automotive substrate is a fender. In another embodiment, the present invention relates to the aforementioned coated automotive substrate, wherein the coated automotive substrate is a bumper. In another embodiment, the present invention relates to the aforementioned coated automotive substrate, wherein the coated automotive substrate is an exterior. In these embodiments, the components used in the preparation of the compositions used for coating of automotive substrates can be selected from those discussed above, and further components can also be selected from those cited above.

In another embodiment, the present invention is directed to a multicomponent composite coating composition comprising a undercoat deposited from a colored coating composition, and a topcoat deposited from any of the coating compositions of the present invention described above. In one embodiment, the present invention relates to a multicomponent composite coating composition as described above, wherein the topcoat composition is clear after curing and selected from any of the aforementioned compositions. In these embodiments the components used in the preparation of the topcoat composition may be selected from the coating components discussed above, and further components may be selected from those cited above.

In some cases, the undercoat and transparent topcoat (ie, clearcoat) compositions used in the multicomponent composite coating compositions of the present invention contain a liquid coating composition having a high solids content, i.e., at least 40 wt% or at least 50 wt% resin solids. It can be mix | blended with a composition. The solids content can be measured by heating a sample of the composition to 105-110 ° C. for 1-2 hours to expel volatiles and subsequently measure the relative weight loss. As mentioned above, the composition may be a liquid coating composition, but it may also be formulated as a powder coating composition.

The coating composition of the undercoat in color + transparent systems can be any composition useful for coating applications, in particular automotive applications. The coating composition of the undercoat can include a pigment that acts as a resinous binder and a colorant. Non-limiting examples of resinous binders are acrylic polymers, polyesters, alkyds and polyurethanes.

The resinous binder of the undercoat can be an organic solvent based material, for example those disclosed in column 2, line 24 to column 4, line 40 of US Pat. No. 4,220,679, which is incorporated by reference in its entirety. In addition, aqueous coating compositions, such as those disclosed in US Pat. Nos. 4,403,003, 4,147,679 and 5,071,904, can be used as binders in the undercoat compositions. These US patents are incorporated herein by reference.

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

In addition to the metal pigments, the undercoat compositions may include non-metal color 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.

Any of the components in the undercoat composition may include those well known in the art of surface coating formulations, and may include surface active agents, flow control agents, thixotropic agents, fillers, gas release agents, organic cosolvents, catalysts, and other conventional auxiliaries. It may include. Non-limiting examples of these materials and suitable amounts are described in U.S. Patent Nos. 4,220,679; 4,403,003; 4,147,769; And 5,071,904.

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

While applying the undercoat to the substrate, the film thickness of the undercoat formed on the substrate may range from 0.1 to 5 mils. In another embodiment, the film thickness of the undercoat formed on the substrate may range from 0.1 to 1 mil, and may be 0.4 mil.

After the film of the undercoat is formed on the substrate, a drying step may be added to cure the undercoat, or, on the other hand, to dissolve the solvent from the undercoat by heating or air drying prior to application of the transparent coat. Suitable drying conditions may vary depending on the particular undercoat composition, and when the composition is aqueous, but a drying time of 1-15 minutes at a temperature of 75-200 ° F. (21-93 ° C.) may be suitable.

The transparent top coat composition may be applied to the undercoat by any conventional coating technique, for example, but not limited to compressed air spray, electrostatic spray, and automatic or manual methods. The transparent top coat may be applied to the cured or dried undercoat before curing of the undercoat. In this case, the two coating layers can be heated to cure the two coating layers simultaneously. Typical curing conditions can be 1 to 30 minutes at 50 to 475 ° F. (10 to 246 ° C.). The thickness (dry film thickness) of the transparent coating film may be 1 to 6 mils.

A second top coat coating composition may be applied to the first top coat to produce a "transparent over transparency" top coat. The first top coat composition may be applied on the bottom coat as described above. The second top coat coating composition may be applied to the first top coat that is cured or dried before the bottom coat and the first top coat are cured. Subsequently, the three coat layers may be cured simultaneously by heating the undercoat, the first top coat and the second top coat.

The second transparent top coat and the first transparent top coat coating compositions may be the same or different, provided that, when wet-on-wet is applied, one top coat is, for example, a solvent from the underlying layer. Of course, by suppressing the water evaporation should not substantially interfere with the curing of the other top coat. Further, the first top coat, the second top coat or both may be the film forming composition of the present invention. The first transparent top coat coating composition may be substantially any top coat composition known to those skilled in the art. The first transparent top coat composition may be either aqueous or solvent based, or on the one hand in the form of solid particulates, ie powder coatings.

Non-limiting examples of suitable first topcoat 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 transparent coatings are disclosed in US Pat. Nos. 5,196,485 and 5,814,410, which are 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 of discharging the solvent from the film by heating or by air drying or curing step on the first top coat before application of the second top coat Add. Suitable drying conditions will vary depending on the particular first topcoat composition, and when the composition is aqueous, but a drying time of 1 to 15 minutes at a temperature of 75 to 200 ° F. (21 to 93 ° C.) may be suitable. have.

The film forming composition of the present invention may be applied as described above for the first top coat by any conventional coating application technique when used as the second top coat coating composition. Curing conditions may be as described for the top coat. The second top coat dry film thickness may range from 0.1 to 3 mils (7.5 to 75 μm).

It should be mentioned that it may be advantageous to combine the coating composition of the present invention to form a "single coating", ie essentially one coating layer when applied to a substrate. The single coat coating composition may be colored. Non-limiting examples of suitable pigments are as mentioned above. When used as a single coating, the coating composition of the present invention may be applied (by any conventional application technique discussed above) into two or more continuous coatings, and in some cases the coatings may only be applied in an instant. Upon curing, the various coatings may essentially form one coating layer.

In another embodiment, the coating compositions of the present invention are also useful as decorative or protective coatings on colored plastic (elastomeric) substrates, such as those described above or mold-in-color ("MIC") plastic substrates. can do. In this use, the composition can be applied directly to the plastic substrate or incorporated into the molding matrix. Optionally, an adhesion promoter can first be applied directly to the plastic or elastomeric substrate and the composition can be applied thereon as a top coat as discussed above. It may also be advantageous to formulate the compositions of the present invention as colored coating compositions for use as primer coatings, as undercoats of multicomponent composite coatings, and as single coat topcoats including pigments or colorants. In these embodiments the components used in the preparation of the composition may be selected from the coating components discussed above and further components may be selected from those cited above.

In embodiments of the present invention relating to automotive applications, the cured compositions can be, for example, electrodeposition coatings, primer coatings, undercoats and / or topcoats. Suitable top coats include single coats and undercoat / transparent coat composites. Single coatings are formed from one or more colored coating composition layers. The undercoat / transparent coat composite includes at least one colored undercoat composition layer and at least one transparent coat composition layer, wherein the undercoat composition has at least one component different from the transparent coat composition. In embodiments of the present invention relating to automotive applications, the clearcoat can be transparent after application.

In another embodiment, the present invention provides a coating composition comprising (a) applying a colored composition to a substrate to form a undercoat; (b) applying a top coat composition on at least a portion of the undercoat to form a top coat thereon, wherein the top coat is selected from any of the compositions described above. The components used in the preparation of the topcoat composition in this embodiment may be selected from the coating components discussed above and further components may be selected from those cited above.

Coatings made from the compositions according to the invention may have not only significant appearance properties and initial scratch resistance, but also weathering or "holding" scratch resistance, which may be before or after abrasion of the coated substrate. It can be evaluated by measuring the gloss of the coated substrate.

In one embodiment, the invention includes applying any of the compositions of the invention described above to at least a portion of a polymeric substrate or a polymer coated substrate and curing the composition to form a cured coating on the substrate. And a method for improving the scratch resistance of the substrate.

In another embodiment, the present invention is directed to a method of retaining the gloss of a substrate after a predetermined period of time, including coating the polymeric substrate or polymer coated substrate with any of the compositions of the present invention disclosed for the substrate. will be. The predetermined period of time may generally be six months or more and one year or more. In another embodiment, the present invention is directed to a method of revitalizing the gloss of a substrate comprising coating a polymeric substrate or a polymer coated substrate with any of the compositions of the invention described above.

Initial 20 ° gloss of the cured coated substrate according to the present invention can be measured using a 20 ° NOVO-GLOSS 20 statistical glossmeter available from Gardner Instrument Company, Inc. Can be. The coating or substrate was linearly rubbed 10 times in double with weighed sandpaper using the Atlas AATCC Scratch Tester Model CM-5, available from Atlas Electrical Devices Company, Chicago, Illinois. By scratching, a scratch test can be applied to the coated substrate. The sandpaper is a 3M 281Q WETORDRY ^™ PRODUCTION ^™ 9 micron abrasive paper sheet (available from 3M Company, St. Paul, MN). The panels are then rinsed with tap water and gently pated with a paper towel to dry. 20 ° gloss is measured on the scratched area of each test panel. The number recorded is the percentage of initial gloss retained after the scratch test, ie 100% x scratched gloss / initial gloss. The test method is fully described in the following examples.

In some embodiments, the cured compositions or coatings of the present invention may be at least 40, at least 50 and often at least 70 with an initial 20 ° gloss (using a 20 ° NOVO-GLOSS 20 statistical glossmeter available from Gardner Instrument Company). Measurement). The high gloss composition is curable under ambient or thermal conditions or by irradiation curing techniques, for example by actinic radiation. In one embodiment, the high gloss composition is curable by ambient or thermal conditions.

Moreover, cured top coats made from the compositions of the present invention may exhibit excellent initial scratch resistance as well as scratch resistance after weathering. The cured top coat retains at least 30% of the initial 20 ° gloss after a scratch test, in some cases at least 40% of the initial 20 ° gloss, and in other cases at least 60% of the initial 20 ° gloss. Initial scratch resistance value (i.e. 100% x scratched gloss / initial gloss) to ensure that it remains after abrasion of the coating surface (the initial 20 ° gloss is measured as described above first, and the hardened coating surface is atlas electrified. Using a Atlas AATCC Scratch Tester Model CM-5 available from Trial Devices Co., Ltd., CM-5, it was rubbed linearly 10 times with weighed sandpaper and measured 20 ° gloss as described above for the worn surface. By measuring).

In addition, the cured topcoats prepared from the compositions of the present invention have post-weather scratch resistance that is retained after at least 30% of the initial 20 ° gloss is weathered for 250 hours. In a weathering cabinet available from Q Panel Company, measured using the scratch test method described above after applying simulated weathering by QUV exposure to UVA-340 bulbs. In another embodiment, at least 50% of the initial 20 ° gloss, often at least 70% of the initial 20 ° gloss, is retained after 250 hours of weathering.

The composition of the present invention can be used to form a clear top coat (ie, a clear coat) in a cured multicomponent composite coating comprising advantageously a top coat deposited from a colored coating composition and a top coat deposited from a top coat coating composition. As used herein, “transparent” means that the cured coating has a BYK blur index of less than 50 as measured using a BYK blur / gloss device. When used as above, a cured top coat can be deposited from any of the aforementioned compositions of the present invention.

The coating composition of the present invention may provide a flexible cured coating. The flexibility test can be performed according to the following "flexibility test method". The coating is applied to the flexible polymeric test panel and cured. For flexibility testing, 1 inch by 4 inch pieces are cut from the coated test panel. At a temperature of 70 ° F. (21 ° C.) ± 5 ° F., the pieces are bent using a 1/2 inch diameter steel mandrel to contact the two ends of the 4 inch length specimens with each other. The test panel is then visually inspected for coating cracks and rated on a scale of 0 to 10 for flexibility. A rating of "10" is recorded in the absence of visible paint cracks; A "9" grade having less than 5 intermittent disconnection cracks; "8" has an intermittent line crack with up to four uninterrupted line cracks; "6" has 5 to 10 uninterrupted line cracks; "4" has at least 15 uninterrupted line cracks; "0" indicates fracture of the substrate. In one embodiment, the coating composition has a flexibility rating of at least 6 at 70 ° F. upon curing. In another embodiment, the coating composition has a flexibility rating of at least 8 at 70 ° F. upon curing, while in yet another embodiment, the coating composition has a flexibility rating of 9 or more at curing at 70 ° F.

Although the present invention is illustrated by the following examples, these examples are not to be considered as limiting the invention to their details. Unless otherwise indicated, all parts and percentages throughout the specification as well as the following examples are by weight.

Film Forming Composition 1:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming composition contains hydroxyl functional group-containing polysiloxane and inorganic fine particles in the form of colloidal silica. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Film forming composition 2:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film-forming composition contains inorganic fine particles in the form of aminoplast and polyisocyanate curing agents, hydroxyl functional-containing polysiloxanes and colloidal silica. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Test panel manufacture:

MPP4100D, an adhesion promoter commercially available from Fiji Industries, Inc., is available from 0.15 to 0.25 mils in a Sequel 1440 TPO plaque (4 in x 12 in) commercially available from Standard Plaque. Spray applied by hand to a dry film thickness of 3.8 to 6.4 μ). Each Sequel 1440 plaque was washed with isopropyl alcohol before coating with the adhesion promoter. Solvent-based black undercoat CBCK8555A (used with 2K clearcoat) or CBC8555T (used with 1K clearcoat) commercially available from Fiji Industries Inc. after leaving the coated Sequel 1440 plaque for one day ) Was applied with a dry film thickness of 0.8-1.0 mil (20.3-25.4 μ). CBCK8555A and CBC8555T were applied by SPRAYMATION with two coatings using a 90 second "flash" at ambient temperature between each coating. The leftover panel was allowed to stand at ambient temperature for 90 seconds and then the above-described film forming compositions 1 and 2 were applied by SPRAYMATION with two coatings using 90 seconds "flash" at ambient temperature between the respective coatings. The clear top coat had a dry film thickness of 1.6 to 1.8 mils (40.6 to 45.7 μm). The topped panels were left at ambient temperature for 10 minutes and then thermally cured at 254 ° F. for 40 minutes. The coated test panels were tested after standing for 4 days at ambient temperature.

Test panels coated with film forming compositions 1 and 2 were subjected to the test methods described above for the 20 ° gloss, scratch test and post weathering scratch test. The weathering was performed for 250 hours in a QUV cabinet available from Q Panel Company. The cabinet is equipped with a UV340 bulb using a light cycle temperature of 70 ° C. and a condensation cycle temperature of 50 ° C. The cycle of the cabinet was fixed to alternate 4 hours of condensation and 8 hours of UV exposure. The coated test panels were also tested for flexibility at 70 ° F. For the flexibility test, 1 inch by 4 inch pieces were cut from the coated test panel. The pieces are bent using a 1/2 inch diameter steel mandrel to bring the two ends of the 4 inch length specimen into contact with each other. The visual grade scale ranged from 0 to 10. No paint cracks were seen for the "10" grade panels. A "9" grade having less than 5 intermittent disconnection cracks; "8" has an intermittent line crack with up to four uninterrupted line cracks; "6" has 5 to 10 uninterrupted line cracks; "4" has at least 15 uninterrupted line cracks; "0" indicates fracture of the substrate.

Film forming composition 3:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming compositions contain aminoplast and polyisocyanate curing agents, hydroxyl functional group containing polysiloxanes, flexible polyester polyols, and acrylic polyol film forming resins. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Film Forming Composition 4:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming compositions contain aminoplast and polyisocyanate curing agents, hydroxyl functional group containing polysiloxanes, flexible polyether polyols, and acrylic polyol film forming resins. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Film-forming composition 5:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming compositions contain aminoplast and polyisocyanate curing agents, hydroxyl functional group containing polysiloxanes, flexible polyether polyols, and acrylic polyol film forming resins. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Film Forming Composition 6:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming compositions contain aminoplast and polyisocyanate curing agents, hydroxyl functional group containing polysiloxanes, flexible polyester polyols, and acrylic polyol film forming resins. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Film Forming Composition 7:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming composition contains a polyisocyanate curing agent, a hydroxyl functional group-containing polysiloxane, a flexible polyether polyol, and an acrylic polyol film forming resin. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Film Forming Composition 8:

This example discloses a method of making a film forming composition used to prepare a transparent top coat in the multicomponent composite composition of the present invention. In another embodiment of the present invention, the composition can be used to form a transparent top coat on a colored plastic substrate or a colored plastic substrate coated with a transparent primer or an adhesion promoter. The film forming composition contains an aminoplast and a polyisocyanate curing agent, a hydroxyl functional group containing polysiloxane and an acrylic polyol film forming resin. The film forming composition was prepared from a mixture of the following components under stirring in the order shown below:

Test panel manufacture:

Sequel 1440 TPO plaques were washed as shown in Example 3 above and coated with an adhesion promoter and an undercoat. The above-mentioned film-forming compositions 3 to 8 were spray applied as a transparent coating film as shown in Example 3 above. Test panels coated with film forming compositions 3 to 8 were subjected to the test methods described above for the 20 ° gloss, scratch test and flexibility test. The test results are shown in the table below.

Claims (187)

(a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) one or more polyols having hydroxyl numbers ranging from 100 to 200; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one functional group of at least one polyol (b) A coating composition prepared from components, wherein the respective components are different, and the flexible coating prepared from the coating composition has a flexibility rating of 6 or greater according to the flexibility test method at a temperature of 70 ° F. upon curing. Having a coating composition. ^2. A compound according to claim 1, wherein each R ² may be the same or different and is hydroxyl group, carboxyl group, isocyanate group, protected polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group A coating composition representing a group comprising at least one reactive functional group selected from urea groups, urethane groups, vinyl groups, unsaturated ester groups, maleimide groups, fumarate groups, anhydride groups, hydroxy alkylamide groups and epoxy groups. The coating composition of claim 1, wherein the at least one polysiloxane (a) comprises at least two reactive functional groups. The coating composition of claim 1, 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. The coating composition of claim 4, 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. The coating composition of claim 1, wherein at least one R ² group represents a group comprising an oxyalkylene group and at least two hydroxyl groups. The coating composition of claim 1, wherein the polysiloxane has the formula II or III Formula II Formula III In the above formulas, m has a value of at least 1; 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 a mixture of any of the above groups; R ^a comprises formula IV: Formula IV -R ³ -X Where -R ³ is selected from alkylene group, oxyalkylene group, alkylene aryl group, alkenylene group, oxyalkenylene group and alkenylene aryl group; X represents a group comprising one or more reactive functional groups. 8. The coating composition of claim 7, wherein (n + m) is in the range of 2-9. 9. The coating composition of claim 8 wherein (n + m) is in the range of 2-3. 8. The coating composition of claim 7, wherein (n '+ m') is in the range of 2-9. The coating composition of claim 10, wherein (n '+ m') is in the range of 2-3. 8. A compound according to claim 7, wherein X is hydroxyl group, carboxyl group, isocyanate group, protected polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group, urea group, urethane group, vinyl group, A coating composition representing a group comprising at least one reactive functional group selected from unsaturated ester groups, maleimide groups, fumarate groups, anhydride groups, hydroxy alkylamide groups and epoxy groups. 13. The coating composition of claim 12, wherein X represents a group comprising at least one reactive functional group selected from hydroxyl groups and carbamate groups. 13. The coating composition of claim 12, wherein X represents a group comprising two or more hydroxyl groups. The method of claim 1, wherein the one or more polysiloxanes (a), when added to other components forming the composition, are present in an amount ranging from 0.01 to 90 weight percent based on the total weight of the resin solids of the components forming the composition. A coating composition present in the composition. The coating composition of claim 15, wherein the at least one polysiloxane (a) is present in an amount of at least 2% by weight. The coating composition of claim 16, wherein the at least one polysiloxane (a) is present in an amount of at least 5% by weight. 18. The coating composition of claim 17, wherein the at least one polysiloxane (a) is present in an amount of at least 10% by weight. The coating composition of claim 1, wherein the at least one polyol is selected from polyether polyols, polyester polyols, acrylic polyols, and polyurethane polyols. The coating composition of claim 19, wherein the polyol comprises one or more polyalkylene oxide polyols. 20. The coating composition of claim 19, wherein the polyol also comprises one or more reactive functional groups other than hydroxyl groups. The coating composition of claim 21, wherein at least one reactive functional group of the polyol comprises a carbamate functional group. The composition of claim 1, wherein at least one polyol is present in the composition in an amount ranging from 0.1 to 30% by weight, based on the total weight of the resin solids of the components forming the composition, when added to the other components forming the composition. Coating composition. The coating composition of claim 23, wherein the one or more polyols are present in an amount ranging from 5 to 20 weight percent, based on the total weight of the resin solids of the components that form the composition, when added to the other components that form the composition. . The coating composition of claim 1, wherein the one or more reactants are selected from one or more curing agents. The coating composition of claim 25, wherein the at least one curing agent is selected from aminoplast resins, polyisocyanates, protected polyisocyanate compounds, polyepoxides, polyacids, and polyols. The method of claim 26, Coating composition wherein at least one curing agent comprises a polyisocyanate. 27. The coating composition of claim 26, wherein the at least one curing agent comprises a mixture of polyisocyanate and aminoplast resin. The coating composition of claim 25, wherein the curing agent is present in an amount ranging from 5 to 40 weight percent, based on the total weight of the resin solids of the components that form the composition when added to the other components that form the composition. The coating composition of claim 1, wherein the components forming the coating composition comprise one or more film forming materials. 31. The coating composition of claim 30, wherein the at least one film forming material is selected from one or more additional polymers comprising at least one reactive functional group, different from the above in addition to at least one polysiloxane (a) and at least one polyol (b). 32. The coating composition of claim 30, wherein the at least one additional polymer comprises at least one reactive functional group selected from hydroxyl groups, carbamate groups, epoxy groups, isocyanate groups, and carboxyl groups. The composition of claim 1, wherein the components forming the composition comprise one or more materials having one or more reactive functional groups protected by silyl groups. 34. The composition of claim 33, wherein the silyl protecting group has the formula Formula IX Where Each of R ₁ , R ₂ and R ₃ may be the same or different and represents hydrogen, an alkyl group having 1 to 18 carbon atoms, phenyl or allyl. 34. The composition of claim 33, wherein the one or more reactive functional groups are selected from hydroxyl groups, carbamate groups, carboxyl groups and amide groups. The compound according to claim 33, wherein the compound capable of reacting with a functional group to form a silyl group is hexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine, t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride, hexamethyl Dissilylazide, hexamethyl disiloxane, trimethylsilyl triflate, hexamethyldissilyl acetamide and a mixture of any of the above compounds. The method of claim 33, wherein the at least one reactant is at least one bond selected from ester bonds, urethane bonds, urea bonds, amide bonds, siloxane bonds and ether bonds, or polyesters, acrylic polymers, polyurethanes, polyethers, polyureas, poly A composition having a backbone comprising a polymer such as an amide and a copolymer of any of the above polymers. 34. The composition of claim 33, wherein the reactant comprises at least one compound having the formula Formula X The coating composition of claim 1, wherein the components forming the coating composition also comprise one or more secondary surface active agents selected from anionic surfactants, cationic surfactants, and nonionic surfactants. The coating composition of claim 1, wherein the components forming the coating composition also comprise one or more catalysts. 41. The coating composition of claim 40, wherein the one or more catalysts are selected from one or more acid functional catalysts. 42. The coating composition of claim 41, wherein the at least one acid functional catalyst is selected from acid phosphates, substituted sulfonic acids, and unsubstituted sulfonic acids. 43. The coating composition of claim 42, wherein the at least one acid functional catalyst is selected from phenyl acid phosphate and dodecylbenzene sulfonic acid. The coating composition of claim 1, wherein the components forming the coating composition also comprise a plurality of particles different from components (a), (b) and (c). 45. The coating composition of claim 44, wherein the plurality of particles are selected from inorganic particles, composite particles, and mixtures thereof. The method of claim 44, 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 of any of the above materials Coating composition. 47. The coating composition of claim 46, wherein the particles comprise colloidal silica. The coating composition of claim 44 wherein the particles have been surface treated. The coating composition of claim 44, wherein the coating composition has an average particle size of less than 100 μ before the particles are incorporated into the composition. The coating composition of claim 44, wherein the coating composition has an average particle size in the range of 1 to 1000 nm before the particles are incorporated into the composition. 51. The coating composition of claim 50, wherein the coating composition has an average particle size in the range of 1 to 100 nm before the particles are incorporated into the composition. The coating composition of claim 51, wherein the coating composition has an average particle size in the range of 5-50 nm before the particles are incorporated into the composition. 45. The coating of claim 44, wherein the particles are present in the composition in an amount in the range of 0.01 to 75 weight percent, based on the total weight of the resin solids of the components that form the composition when added to the other components that form the composition. Composition. The coating composition of claim 53, wherein the particles are present in an amount of at least 0.1% by weight. 55. The coating composition of claim 54 wherein the particles are present in an amount of at least 0.5% by weight. The coating composition of claim 55, wherein the particles are present in an amount of at least 5% by weight. The coating composition of claim 53, wherein the particles are present in an amount of less than 50% by weight. The coating composition of claim 57, wherein the particles are present in an amount of less than 20% by weight. The coating composition of claim 57, wherein the particles are present in an amount of less than 10% by weight. The coating composition of claim 1, wherein the coating material prepared from the coating composition has a flexibility of at least 8 at a temperature of 70 ° F. upon curing. 61. The coating composition of claim 60, wherein the coating material prepared from the coating composition has a flexibility of at least 9 at a temperature of 70 [deg.] F. upon curing. The coating composition of claim 1, wherein the coating material prepared from the coating composition has an initial scratch resistance value such that at least 40% of the initial 20 ° gloss is retained after the scratch test upon curing. The coating composition of claim 1, wherein the coating material prepared from the coating composition has a glass transition temperature in the range of −20 to 100 ° C. upon curing. 64. The coating composition of claim 63, wherein the coating made from the coating composition has a glass transition temperature in the range of 40 to 90 ° C. A cured coating prepared from the coating composition of claim 1. A coated substrate comprising a flexible substrate and a composition according to claim 1 coated on at least a portion of the substrate. A coated automotive substrate comprising a substrate and a composition according to claim 1 coated on at least a portion of the substrate. A method of coating a substrate, comprising coating the composition of claim 1 over at least a portion of the substrate. A method of improving scratch resistance of a substrate, comprising coating the coating composition of claim 1 over at least a portion of the polymeric substrate. A method of improving scratch resistance of a substrate, comprising coating the coating composition of claim 1 over at least a portion of the polymer coated substrate. A method of maintaining the gloss of a substrate after a period of time comprising coating the coating composition according to claim 1 on a polymer coated surface of the polymer coated substrate. A method of revitalizing the gloss of a substrate after a period of time, comprising coating a coating composition according to claim 1 on a polymer coated surface of a polymer coated substrate. (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) one or more substances comprising one or more reactive functional groups; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one reactive functional group of at least one substance (b) A coating composition prepared from components, wherein the respective components are different, and the flexible coating prepared from the coating composition has a flexibility rating of 6 or greater according to the flexibility test method at a temperature of 70 ° F. upon curing. Having a coating composition. 74. The coating composition of claim 73, wherein the at least one material is a flexibility imparting agent present in an amount of less than 30% by weight based on the total resin solids of the components forming the composition. 74. The compound of claim 73, wherein each R ² may be the same or different and is hydroxyl group, carboxyl group, isocyanate group, protected polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group A coating composition representing a group comprising at least one reactive functional group selected from urea groups, urethane groups, vinyl groups, unsaturated ester groups, maleimide groups, fumarate groups, anhydride groups, hydroxy alkylamide groups and epoxy groups. 74. The coating composition of claim 73, wherein the at least one polysiloxane (a) comprises at least two reactive functional groups. 74. The coating composition of claim 73, 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. 78. The coating composition of claim 77, 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. 74. The coating composition of claim 73 wherein at least one R ² group represents a group comprising an oxyalkylene group and at least two hydroxyl groups. The coating composition of claim 73, wherein the polysiloxane has the formula II or III Formula II Formula III In the above formulas, m has a value of at least 1; 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 a mixture of any of the above groups; R ^a comprises formula IV: Formula IV R ³ -X Where R ³ is selected from alkylene group, oxyalkylene group, alkylene aryl group, alkenylene group, oxyalkenylene group and alkenylene aryl group; X represents a group comprising one or more reactive functional groups. 81. The coating composition of claim 80, wherein (n + m) is in the range of 2-9. 82. The coating composition of claim 81, wherein (n + m) is in the range of 2-3. 81. The coating composition of claim 80, wherein (n '+ m') is in the range of 2-9. 84. The coating composition of claim 83, wherein (n '+ m') is in the range of 2-3. 81. The compound of claim 80, wherein X is hydroxyl group, carboxyl group, isocyanate group, protected polyisocyanate group, primary amine group, secondary amine group, amide group, carbamate group, urea group, urethane group, vinyl group, A coating composition representing a group comprising at least one reactive functional group selected from unsaturated ester groups, maleimide groups, fumarate groups, anhydride groups, hydroxy alkylamide groups and epoxy groups. 86. The coating composition of claim 85, wherein X represents a group comprising at least one reactive functional group selected from hydroxyl groups and carbamate groups. 86. The coating composition of claim 85, wherein X represents a group comprising two or more hydroxyl groups. 74. The composition of claim 73, wherein the one or more polysiloxanes (a), when added to other components forming the composition, in an amount ranging from 0.01 to 90 weight percent based on the total weight of the resin solids of the components forming the composition. A coating composition present in the composition. 89. The coating composition of claim 88, wherein the at least one polysiloxane (a) is present in an amount of at least 2% by weight. 90. The coating composition of claim 89, wherein the at least one polysiloxane (a) is present in an amount of at least 5% by weight. 91. The coating composition of claim 90, wherein the at least one polysiloxane (a) is present in an amount of at least 10% by weight. 75. The coating composition of claim 73, wherein the at least one material is selected from polyether polyols, polyester polyols, acrylic polyols, and polyurethane polyols. 93. The coating composition of claim 92, wherein the at least one material comprises at least one polyalkylene oxide polyol. 93. The coating composition of claim 92, wherein the one or more materials include one or more reactive functional groups other than hydroxyl groups. 75. The coating composition of claim 73, wherein at least one reactive functional group of at least one material comprises a carbamate functional group. 75. The composition of claim 73, wherein at least one substance is present in the composition in an amount ranging from 0.1 to 30 weight percent, based on the total weight of the resin solids of the components forming the composition when added to the other components forming the composition. Coating composition. 97. The coating composition of claim 96, wherein the one or more materials are present in an amount ranging from 5 to 20 weight percent, based on the total weight of the resin solids of the components that form the composition, when added to the other components that form the composition. . 74. The coating composition of claim 73, wherein the one or more reactants are selected from one or more curing agents. 99. The coating composition of claim 98, wherein the at least one curing agent is selected from aminoplast resins, polyisocyanates, protected polyisocyanate compounds, polyepoxides, polyacids, and polyols. 107. The coating composition of claim 99, wherein the at least one curing agent comprises a polyisocyanate. 107. The coating composition of claim 99, wherein the at least one curing agent comprises a mixture of polyisocyanate and aminoplast resin. 99. The coating composition of claim 98, wherein the curing agent is present in an amount ranging from 5 to 40 weight percent, based on the total weight of the resin solids of the components that form the composition when added to the other components that form the composition. 74. The coating composition of claim 73, wherein the components forming the coating composition comprise one or more film forming materials. 109. The coating composition of claim 103, wherein the one or more film forming materials are selected from one or more additional polymers comprising one or more reactive functional groups, different from the above, in addition to one or more polysiloxanes (a) and one or more materials (b). 107. The coating composition of claim 104, wherein the one or more additional polymers comprise one or more reactive functional groups selected from hydroxyl groups, carbamate groups, epoxy groups, isocyanate groups, and carboxyl groups. 74. The composition of claim 73, wherein the components forming the composition comprise one or more materials having one or more reactive functional groups protected by silyl groups. 107. The composition of claim 106, wherein the silyl protecting group has the formula Formula IX Where Each of R ₁ , R ₂ and R ₃ may be the same or different and represents hydrogen, an alkyl group having 1 to 18 carbon atoms, phenyl or allyl. 107. The composition of claim 106, wherein at least one reactive functional group is selected from hydroxyl groups, carbamate groups, carboxyl groups and amide groups. 107. The compound of claim 106, wherein the compound capable of reacting with a functional group to form a silyl group is hexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine, t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride, hexamethyl Dissilylazide, hexamethyl disiloxane, trimethylsilyl triflate, hexamethyldissilyl acetamide and a mixture of any of the above compounds. 107. The method of claim 106, wherein the at least one reactant is at least one bond selected from ester bonds, urethane bonds, urea bonds, amide bonds, siloxane bonds and ether bonds, or polyesters, acrylic polymers, polyurethanes, polyethers, polyureas, poly A composition having a backbone comprising a polymer such as an amide and a copolymer of any of the above polymers. 107. The composition of claim 106, wherein the reactant comprises one or more compounds having the formula Formula X 74. The coating composition of claim 73, wherein the components forming the coating composition also comprise one or more auxiliary surface active agents selected from anionic surfactants, cationic surfactants, and nonionic surfactants. 74. The coating composition of claim 73, wherein the components forming the coating composition also comprise one or more catalysts. 118. The coating composition of claim 113, wherein the one or more catalysts are selected from one or more acid functional catalysts. 118. The coating composition of claim 114, wherein the at least one acid functional catalyst is selected from acid phosphates, substituted sulfonic acids, and unsubstituted sulfonic acids. 118. The coating composition of claim 115, wherein the at least one acid functional catalyst is selected from phenyl acid phosphate and dodecylbenzene sulfonic acid. 74. The coating composition of claim 73, wherein the components forming the coating composition also comprise a plurality of particles different from components (a), (b) and (c). 118. The coating composition of claim 117, wherein the plurality of particles are selected from inorganic particles, composite particles, and mixtures thereof. 119. The particle of claim 118, 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 of any of the above materials. Coating composition. 119. The coating composition of claim 119, wherein the particles comprise colloidal silica. 118. The coating composition of claim 117, wherein the particles are surface treated. 118. The coating composition of claim 117, wherein the coating composition has an average particle size of less than 100 microns before the particles are incorporated into the composition. 118. The coating composition of claim 117, wherein the coating composition has an average particle size in the range of 1 to 1000 nm before the particles are incorporated into the composition. 126. The coating composition of claim 123, wherein the coating composition has an average particle size in the range of 1 to 100 nm before the particles are incorporated into the composition. 126. The coating composition of claim 124, wherein the coating composition has an average particle size in the range of 5-50 nm before the particles are incorporated into the composition. 118. The composition of claim 117, wherein the particles are present in the composition in an amount ranging from 0.01 to 75 weight percent, based on the total weight of the resin solids of the components that form in the composition when added to the other components that form the composition. Coating composition. 126. The coating composition of claim 126, wherein the particles are present in an amount of at least 0.1% by weight. 127. The coating composition of claim 127, wherein the particles are present in an amount of at least 0.5% by weight. 129. The coating composition of claim 128, wherein the particles are present in an amount of at least 5% by weight. 126. The coating composition of claim 126, wherein the particles are present in an amount of less than 50% by weight. 131. The coating composition of claim 130, wherein the particles are present in an amount of less than 20% by weight. 131. The coating composition of claim 130, wherein the particles are present in an amount of less than 10% by weight. 74. The coating composition of claim 73, wherein the coating material prepared from the coating composition has a flexibility of at least 8 at a temperature of 70 [deg.] F. upon curing. 138. The coating composition of claim 133, wherein the coating made from the coating composition has a flexibility of at least 9 at a temperature of 70 [deg.] F. upon curing. 74. The coating composition of claim 73, wherein the coating material prepared from the coating composition has an initial scratch resistance value such that at least 40% of the initial 20 ° gloss is retained after the scratch test upon curing. The coating composition of claim 73, wherein the coating material prepared from the coating composition has a glass transition temperature in the range of −50 to 100 ° C. upon curing. 138. The coating composition of claim 136, wherein the coating made from the coating composition has a glass transition temperature in the range of 40 to 90 ° C upon curing. 74. The coating composition of claim 73 made from the components comprising one or more film forming materials. The cured composition of claim 73 cured by exposure to ionizing radiation. The cured composition of claim 73 cured by exposure to actinic radiation. The cured composition of claim 73 cured by (1) ionizing radiation or actinic radiation and (2) exposure to thermal energy. A cured coating prepared from the coating composition according to claim 73. A coated substrate comprising a flexible substrate and a composition according to claim 73 coated over at least a portion of the substrate. A coated automotive substrate comprising a substrate and a composition according to claim 73 coated over at least a portion of the substrate. A method of coating a substrate, comprising coating the composition of claim 73 over at least a portion of the substrate. A method of improving scratch resistance of a substrate, comprising coating a coating composition according to claim 73 over at least a portion of the polymeric substrate. A method of improving scratch resistance of a substrate, comprising coating a coating composition according to claim 73 over at least a portion of the polymer coated substrate. A method of maintaining the gloss of a substrate after a period of time comprising coating a coating composition according to claim 73 on a polymer coated surface of a polymer coated substrate. A method of revitalizing the gloss of a substrate after a period of time, comprising coating a coating composition according to claim 73 on a polymer coated surface of a polymer coated substrate. (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) at least one reactant comprising at least one functional group reactive with at least one reactive functional group of (a) A coating composition prepared from components comprising: wherein each of the components is different, and the coating material prepared from the coating composition has a flexibility rating of 6 or greater, depending on the flexibility test method at a temperature of 70 ° F. upon curing, The coating material prepared from the coating composition has an initial scratch resistance such that at least 40% of the initial 20 ° gloss is retained after the scratch test upon curing. (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) at least one polyol having a hydroxyl value of 100 to 200, less than 30% by weight, based on the total resin solids of the components forming the coating composition; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one functional group selected from at least one functional group of at least one polyol (b) A coating composition prepared from components, wherein the respective components are different, and the coating material prepared from the coating composition has a glass transition temperature of -20 to 100 ° C. upon curing. (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) one or more polyols selected from polyether polyols and polyester polyols and having a hydroxyl number in the range of 100 to 200; (c) one or more aminoplast resins; And (d) at least one polyisocyanate A coating composition prepared from components, wherein each of said components is different and wherein the coating material prepared from said coating composition has a flexibility of at least 6, depending upon the method of testing the flexibility of said coating material at a temperature of at least 70 ° F. upon curing. A coating composition having a flexible grade to have a grade. (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) at least one polyol selected from less than 30% by weight of polyether polyols and polyester polyols based on the total resin solids of the components forming the coating composition and having a hydroxyl number of from 100 to 200; (c) one or more aminoplast resins; And (d) at least one polyisocyanate A coating composition prepared from components, wherein the respective components are different, and the coating material prepared from the coating composition has a glass transition temperature in the range of -20 to 100 ° C. upon curing. 153. The film of claim 153, wherein the film comprises at least one functional group that is reactive with at least one component selected from aminoplast resins (c) and polyisocyanates (d) other than the above, in addition to polysiloxanes (a) and polyols (b). A coating composition also comprising a forming material. (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; And (b) carbamate functional substances different from (a) Coating composition prepared from the components comprising a. 162. The coating composition of claim 155, wherein the carbamate functional material is selected from acrylics, polyesters, polyurethanes, polyethers, and mixtures of any of the foregoing compounds. 162. The coating composition of claim 155, wherein the at least one curing agent is selected from polyisocyanates and aminoplast resins. 162. The coating composition of claim 155, wherein the coating made from the coating composition has a glass transition temperature in the range of -20 to 100 ° C upon curing. 158. The composition of claim 158, wherein the composition is heat cured. A cured coating prepared from the coating composition of claim 155. A multicomponent composite coating prepared from a top coat deposited from a colored coating composition and a top coat prepared from the top coat composition applied on the top coat, wherein the top coat composition is (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) one or more substances comprising one or more reactive functional groups; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one reactive group selected from at least one reactive functional group of at least one substance (b) Multicomponent composite coatings having a flexible rating of 6 or more according to the flexible test method at a temperature of 70 ° F. upon curing. . A multicomponent composite coating prepared from a top coat deposited from a colored coating composition and a top coat prepared from a top coat composition applied on the top coat, wherein the top coat is (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; (b) at least one polyol having a hydroxyl value of 100 to 200, less than 30% by weight, based on the total resin solids of the components forming the coating composition; And (c) at least one reactant comprising at least one reactive functional group of at least one polysiloxane (a) and at least one functional group reactive with at least one reactive functional group selected from at least one functional group of at least one polyol (b) Wherein the respective components are different and wherein the top coat has a glass transition temperature in the range of -20 to 100 ° C. upon curing. A multicomponent composite coating prepared from a top coat deposited from a colored coating composition and a top coat prepared from the top coat composition applied on the top coat, wherein the top coat composition is (a) at least one polysiloxane comprising at least one reactive functional group and at least one unit of formula (I): Formula I R ¹ _n R ² _m SiO _{(4-nm) / 2} [Wherein, Each R ¹ may be the same or different and is H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; Each R ² may be the same or different and represents a group comprising one or more reactive functional groups; m and n satisfy the requirements of 0 <n <4, 0 <m <4 and 2 ≦ (m + n) <4]; And (b) carbamate functional substances different from (a) Multicomponent composite coating material prepared from the component comprising a. 163. The coated substrate of claim 163 made from a polymeric material. A coated substrate comprising a substrate and a composition according to claim 155 coated over at least a portion of the substrate. 161. A coated substrate comprising the substrate and the composite coating according to claim 161 coated on at least a portion of the substrate. 162. A coated substrate comprising a substrate and a composite coating according to claim 162 coated over at least a portion of the substrate. 163. A coated substrate comprising the substrate and the composite coating according to claim 163 coated on at least a portion of the substrate. A coated automotive substrate comprising a substrate and a composition according to claim 155 coated over at least a portion of the substrate. A coated automotive substrate comprising a substrate and a composite coating according to claim 161 coated over at least a portion of the substrate. A coated automotive substrate comprising a substrate and a composite coating according to claim 162 coated over at least a portion of the substrate. . 163. A coated automotive substrate comprising a substrate and a composite coating according to claim 163 coated over at least a portion of the substrate. A method of coating a substrate, comprising coating a composition according to claim 155 over at least a portion of the substrate. A coating method of a substrate, comprising coating the composite coating material of claim 161 on at least a portion of the substrate. A method of coating a substrate, comprising coating the composite coating material of claim 162 over at least a portion of the substrate. 163. A method of coating a substrate, comprising coating the composite coating material of claim 163 over at least a portion of the substrate. A method of improving scratch resistance of a substrate, comprising coating a coating composition according to claim 155 over at least a portion of the polymeric substrate. A method of improving scratch resistance of a substrate comprising coating a composite coating according to claim 161 on at least a portion of the polymeric substrate. A method of improving scratch resistance of a substrate, comprising coating a composite coating according to claim 162 on at least a portion of the polymeric substrate. 163. A method of improving scratch resistance of a substrate, comprising coating the composite coating material of claim 163 over at least a portion of the polymeric substrate. A method of improving scratch resistance of a substrate, comprising coating a coating composition according to claim 155 over at least a portion of a polymer coated substrate. A method of improving scratch resistance of a substrate comprising coating a composite coating according to claim 161 over at least a portion of a polymer coated substrate. A method of improving scratch resistance of a substrate, comprising coating a composite coating according to claim 162 over at least a portion of a polymer coated substrate. 163. A method of improving scratch resistance of a substrate, comprising coating the composite coating material of claim 163 over at least a portion of the polymer coated substrate. The composition of claim 1 wherein the coating made from the composition has a crosslink density in the range of 50 to 80% of complete crosslinking upon curing. 75. The composition of claim 73, wherein the coating material prepared from the coating composition has a crosslink density in the range of 50 to 80% of complete crosslinking upon curing.