JPH07286034A - Amine-hardenable composition - Google Patents

Abstract

PURPOSE: To obtain an amine curable compsn. useful for use in a floor finishing material and a coating film by compounding a monomer or oligomer having both functionalities of an epoxy and an acrylate in the same molecule with an amine curing agent.

CONSTITUTION: (A) At least one partially acrylated epoxy monomer or oligomer having a mol.wt. of 150-10,000 and containing at least one 1,2-epoxide group and at least one terminal acrylate or methacrylate group and (B) an active mono-, di- or polyamine curing agent contained in an amt. at least sufficient to react with substantially all of the 1,2-epoxide group, the acrylate group or the methacrylate group are compounded just before use to obtain a curable compsn. This curable compsn. is applied to a support to be cured to form various protective coating films, decorative coating films or floor finishing materials.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to amine curable compositions useful in a number of applications, especially floor finishes and coating applications.

[0002]

A common type of curable composition used in floor covering applications is a curable epoxide composition. However, epoxide resins have undesirable properties such as low cure rate and high viscosity, especially at low temperatures. Another type of curable composition used in floor covering applications is a curable acrylate composition. However, acrylate systems also exhibit undesirable properties, such as low alkali resistance. The method of polymerization can be a further obstacle. Free radical polymerization is inhibited by oxygen, and heat activated polymerization is problematic in some areas, such as in floor finish applications where it is difficult and even difficult to uniformly heat the entire bed due to even curing. Occurs. UV curing and electron beam curing are also unsatisfactory for floor finish applications because surface curing is generally only achieved in these systems and therefore they are not practical for bulk curing and curing of filling systems.

[0003]

The combination of properties provided by the acrylate and epoxide functionalities is often desirable, and curable compositions containing both of these functional groups are known. However, many of them have disabilities.
U.S. Pat. No. 4,051,195 discloses epoxide resins containing one or more 1,2-epoxide groups per molecule, polyacrylate or polymethacrylate esters and aromas of polyols in which the ester contains one or more terminal acrylate or methacrylate groups. At least 3 per molecule of group amine
A curable composition comprising an aromatic amine containing one amine hydrogen atom is described. Such compositions are described as having enhanced properties corresponding to compositions based on total esters. However, it is well known that amine cures of acrylates occur much faster than amine cures of epoxides, and therefore mixtures of epoxy resins and acrylate monomers cure at different rates. This difference in cure rate results in a relatively long tack free time of the cured material due to areas of uncured epoxy, especially at low temperatures, as well as areas of poor epoxy and acrylate rich areas. The result is a heterogeneous two-phase polymer.

US Pat. No. 5,198,524 discloses a storage-stable composition containing a polyacrylate, a polyepoxy resin and a ketimine in which the first step is a two-step cure in which the adhesive is moisture-cured at ambient temperature to give green strength. A curable adhesive composition is described. In the second stage, the adhesive is post-cured at elevated temperature to give a strong bond. In a preferred embodiment, the epoxy and acrylate functionalities are on the same molecule.

US Pat. No. 4,616,066 discloses vinyl or vinyl compounds which are the reaction products of (a) epoxy group-containing vinyl or acrylic polymers with (B) bisphenol compounds and (C) diglycidyl ethers of bisphenol compounds. Provided is an acrylic polymer-modified epoxy resin. Vinyl or acrylic polymer modified epoxy resins are known curing agents,
Useful in adhesive or coating compositions, for example in combination with amines, are described in columns 5, lines 20-23. Vinyl and acrylic polymer modified epoxy resins have no residual unpolymerized acrylate groups involved in the curing reaction.

[0006]

The present invention provides amine curable compositions containing materials having both epoxy and acrylate functionality in the same molecule. These compositions cure rapidly and, after amine cure, provide more uniform polymers with similarly improved properties.

"Partially acrylated epoxy monomer or oligomer" as used herein comprises at least one 1,2-epoxide group or functionality and at least one terminal acrylate group or functionality in the same molecule. The bifunctionality is defined as meaning a monomer or oligomer capable of amine curing.

It should be noted that in the art, the term "epoxy acrylate" or "acrylated epoxide" generally means a material containing acrylate groups on the molecule but no unreacted epoxide groups. The name is due to the fact that the material is produced by acrylated epoxide.

Amine curable compositions containing a partially acrylated epoxy material and an amine curing agent cure rapidly and provide improved physical properties, especially premature development physical properties, so that the polymer as a whole will It has been found to result in a more uniform, substantially single phase polymer with the desirable properties of both epoxide and acrylate functionality provided on average. Desirable properties include strength, toughness, good adhesion and good water, alkali and heat resistance provided by epoxide, and rapid cure and improved UV resistance provided by acrylate. Amine curing eliminates the problems associated with other types of curing, such as UV radiation, free radicals and electron beams when the composition is used in floor covering applications.

In particular, the invention provides (i) about 150 and 10,0.
00, preferably having a molecular weight of 300 to 5,000, more preferably 300 to 3,000, and having at least one 1,2-epoxide group and at least one terminal acrylate or methacrylate group. One partially acrylated epoxy monomer or oligomer; and (ii) at least a sufficient amount of an active mono-, di- or polyamine curing agent to react with substantially all 1,2-epoxide groups, acrylate groups and methacrylate groups. There is provided a cured composition comprising.

The components (i), (ii) and all other components are mixed just before use. In other experimental aspects, the present invention has been shown to be particularly effective and effective in combination with partially acrylated or methacrylated epoxy materials, providing all properties desired for the application, such as viscosity, working time and workability. A curable composition as described above, which additionally comprises one or more additional monomeric oligomers or polymers, which, after curing, result in a polymeric composition having the desired properties for the particular application. provide. In another embodiment, the curable composition of the present invention may comprise other additives, such as diluents; organic, inorganic or metallic aggregates; and / or fillers.

In yet another embodiment, the invention comprises a. Applying a curable composition to a substrate, the curable composition having (i) a molecular weight between 150 and 10,000, at least one 1,2-epoxide group and at least one terminal acrylate. Or at least one partially acrylated epoxy monomer or oligomer containing methacrylate groups, and (ii) an active mono-, di- or polyamine curing agent; and b. A method of forming a bed on a support comprising the step of curing the curable composition.

The present invention further provides a method of forming a protective and / or decorative coating on a substrate, and further coating a substrate, such as a floor covering, overlaid with a coating produced by such a method. provide.

The partially acrylated or methacrylated epoxy material useful in the present invention is from about 150 to about 1.
Monomers and oligomers having a calculated molecular weight of 000, preferably 300 to 5,000, and more preferably 300 to 3,000, which contain at least one 1,2-epoxide group and at least one per molecule.
Contains two terminal acrylate groups. The molecular weight is the calculated molecular weight, that is, the sum of the atomic weights of the atoms that make up the monomer or oligomer, or the molecular weight is the number average molecular weight that can be derived from end group analysis. Materials with molecular weights below about 150 (eg glycidyl acrylate and glycidyl methacrylate) tend to be highly toxic and volatile and are therefore undesirable from an environmental point of view. Moreover, such low molecular weight materials tend to result in brittle curable compounds than those made from high molecular weight materials. Materials with high molecular weight are more viscous and less workable. Generally, the molecular weight should not exceed about 10,000, preferably not more than 5,000.

The number of 1,2-epoxide groups and acrylate groups present is not critical, as long as there is at least one each present in the material. The ratio of 1,2-epoxy groups to terminal acrylate groups is not limited and the ratio selected will depend on the properties desired in the cured material.

A single partially acrylated epoxy monomer or oligomer or a combination of two or more partially acrylated epoxy monomers or oligomers may be used.

Examples of suitable partially acrylated epoxy monomers and oligomers are partially acrylated bisphenol A epoxy resins; partially acrylated bisphenol F.
Epoxy resins; partially acrylated epoxy novolac resins; partially acrylated di- or polyglycidyl ethers of various compounds, such as diglycidyl ether of 1,4-butanediol, diglycidyl ether of neopentyl glycol, neopentyl glycol alkoxylated. Diglycidyl ether, diglycidyl ether of resorcinol, diglycidyl ether of cyclohexanedimethanol, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether,
Alkoxylated trimethylolethane triglycidyl ether, alkoxylated trimethylolpropane triglycidyl ether, dibromoneopentyl glycol diglycidyl ether, aliphatic polyol polyglycidyl ether, polyglycol diepoxide and castor oil polyglycidyl ether; and at least one Polyurethanes, polyesters and polyethers containing an epoxide and at least one acrylate functionality and any other compound containing at least one epoxide and at least one acrylate functionality and meeting the molecular weight requirements set forth above.

Preferably, the partially acrylated epoxy monomers and oligomers are partially acrylated bisphenol A epoxy resin, partially acrylated bisphenol F epoxy resin, partially acrylated epoxy novolac resin, partially acrylated neopentyl glycol. Diglycidyl ether, partially acrylated diglycidyl ether of alkoxylated neopentyl glycol, partially acylated trimethylolpropane triglycidyl ether, partially acrylated alkoxylated trimethylolpropane triglycidyl ether, partially acrylated trimethylolethanetri It is selected from glycidyl ether and partially acrylated alkoxylated trimethylolethane triglycidyl ether.

Partially acrylated epoxy materials are commercially available, for example "EBECRYL3605" ™ is sold by UCB Radicure, Inc., Smyrna, GA. "EBECRYL 3605" is a partially acrylated bisphenol A epoxy resin containing 1 acrylate functionality and 1 epoxy functionality. Partially acrylated epoxy monomers and oligomers can also be readily prepared by methods well known in the art. One such method is the partial acrylation of compounds containing at least two epoxide groups. Another method, described in the above-referenced US Pat. No. 5,198,524, involves reacting an epoxy resin with a chain extender having amine functionality, and reacting the resulting intermediate with an acrylated isocyanate at least. Forming an oligomer having one epoxy and at least one acrylate functionality.

Other methods include hydroxyglycols such as glycidol, or hydroxyacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxycaprolactone acrylate (TONE M-100 ™). , Union Carbide, available from Bambury, Connecticut) and hydroxycaprolactone methacrylate (TONE M-200 ™, available from Union Carbide) are reacted with a diisocyanate compound to form a monoisocyanate acrylate or monoisocyanate. Obtaining an epoxide, and further adding the monoisocyanate acrylate or epoxide to another monoisocyanate Reacting with a acrylate or epoxide with a dihydroxy or polyhydroxy compound, or with any compound having two or more active hydrogens.

The dihydroxy compound may include a polyester or polyether segment or any internal structure that imparts properties suitable for the particular application. Any polyol or polyol combination may be used. Suitable compounds having two or more active hydrogens are amines, such as Texaco Chemical Co.
mpany), Houston, Texas "JEFFAMINE" (TM) series of di- and triamines and compounds having active methylene groups.

Many variations of the above-described method which will be apparent to those skilled in the art include one or more acrylate groups and one
Or will result in various materials with more epoxide groups.

The hardener is an active mono-, di- or polyamine. By "active" amine is meant a compound having free primary or secondary amine groups, which means that it requires other types of curing agents, such as moisture, to activate when contacted with a partially acrylated material. It is immediately and fully active compared to moisture-acting amine curing agents such as ketimines and aldimines. Monoamines are compounds containing one amine group per molecule, diamines are compounds containing two amine groups per molecule, and polyamines are compounds containing three or more amine groups per molecule. Polyamines are preferred because they enhance the crosslink density of the resulting cured compounds.

A single active amine hardener or a combination of two or more active amine hardeners may be used.

The active amine useful in the present invention can be any known in the art for curing epoxides and / or acrylates. Examples of suitable active amines are ethanolamine, nonylamine, furfurylamine, 1,3-aminopropylenenitrile, ethylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, m-xylylenediamine, diethylenetriamine, diethylenediamine. Propylenetriamine, polyoxyalkylenemonoamines, polyoxyalkylenediamines and polyoxyalkylenetriamines (for example di- and triamines from Texaco Chemical Company "JEFFA
MINE "series), 1,3-bis (aminomethyl) -cyclohexane, isophoronediamine, bis (hexamethylene) triamine, bis (aminomethyl) norbornane,
Bis (4-aminocyclohexyl) methane, cycloaliphatic diamines and polyamines, phenalkamine, triethylenetetramine (TETA), and tetraethylenepentamine, and U.S. Pat. Including all others described in No. 562,
It is not limited to these. Aminosilanes may also be used to enhance the wetting and adsorption properties of the composition in addition to acting as a curing agent.

Since the amine adduct is generally less corrosive and easier to handle than the amine itself, it is preferable that
Amine adducts known in the art, and especially those made from polyamines and epoxides, acrylates, acrylonitriles or combinations thereof are used as curing agents. Useful amine adducts are Pacific Anchor Chemical Air Products and Chemicals
Incorporated (Air Products and Chemicals, I
nc.), Allentown, PA, an adduct of triethylenetetramine and propylene oxide "ANCAMINE 1769" ™. Particularly useful amine adducts are Mitsubishi Gas Chemical
America, Inc. (Mitsubishi Gas Chem
ical America Inc.), New York, NY, “GASKAMINE 328” ™, an adduct of m-xylylenediamine and epichlorohydrin.

The reactivity of the curable composition is, as is known,
If desired, it can be adjusted by the solubility / insolubility characteristics of the amine curing agent.

The phrase "active mono-, di- or polyamine curing agent in sufficient quantity to react with substantially all 1,2-epoxide groups, acrylate and methacrylate groups" means
This means that there is at least a sufficient amount of active amine hardener present, whereby there is practically no 1,2-epoxide, acrylate or methacrylate groups available for the post cure reaction.

The amine hardener may be used in various ratios,
Generally a 1: 1 ratio of active equivalents can be used for the material to be cured. In the presence of excess amine curing agent, the physical properties of the cured material, such as tensile strength and tear resistance, tend to develop faster. However, the presence of unreacted amine reduces the chemical resistance of the cured composition. The presence of less than the equivalent amount of curing agent results in a prepolymer, ie, a polymer that does not cure completely. Prepolymers require post-cure for full development of physical properties. In floor covering applications, the amine hardener can be present in a wide range of equivalents, but the hardener is present in an amount at least sufficient to cure substantially all 1,2-epoxide groups, acrylate groups and methacrylate groups. Preferably.

Compounds useful as catalysts to accelerate amine cure may be applied, such as tertiary amines, quaternary amine salts such as tetramethylammonium chloride, and hydroxy containing compounds. Examples of suitable tertiary amines are dimethylaminomethylphenol, tris (dimethylaminomethyl)
Includes, but is not limited to, phenol and benzyldimethylamine. Suitable hydroxy-containing compounds include, but are not limited to, salicylic acid and nonylphenol. In addition, other materials believed to accelerate the curing of acrylates and / or epoxides, such as water, basic catalysts such as alkali and alkaline earth metal hydroxides; acidic catalysts such as hydrochloric acid; silicone compounds such as tetramethoxysilane; Copper compounds such as copper chloride may be used. Combinations of two or more catalysts may also be applied to accelerate amine cure. A particularly useful catalyst is a combination of water, hydrochloric acid and a tertiary amine such as imidazole.

Depending on the specific catalyst or catalysts applied, they may be added in many different ways, but they are generally added to component (B) immediately before mixing components (A) and (B). preferable.

The partially acrylated material (s) may comprise the total material to be cured, or the partially acrylated epoxy material (s) may be of any particular use for the cured composition. It may be blended with other amine curable acrylates and / or amine curable epoxy monomers, oligomers or polymers to obtain the desired properties for and / or to obtain the desired properties in the final cured composition. One of the advantages of the present invention is that different curable components in different amounts and molecular weight ranges can be used without the general problems of phase separation. Although not theoretically bound, the partially acrylated epoxy material is a compatibilizer between any epoxy compound and any acrylic compound additionally present in the composition.
bilizer).

Preferably, when the curable composition is used in floor finish applications, the partially acrylated epoxy material (s) is / are used in order to reduce the viscosity of the curable composition. It is admixed with polyfunctional acrylates, ie monomers, oligomers or polymers with one, two or more terminal acrylate or methacrylate groups. The higher the functionality, i.e. the more acrylate groups per molecule, the higher the crosslink density, the faster the cure, and the tack free time, i.e. the time from initial cure to obtaining the tack free cured composition. The time gets shorter. Generally, di- or polyfunctional acrylates having a molecular weight of about 425 or higher are preferred due to their low volatility and low odor. However, as molecular weight increases, viscosity generally increases, so an upper limit for molecular weight can be determined based on viscosity considerations. Polyfunctional acrylates can be used to control the rate of cure.

Suitable mono-, di- or polyfunctional acrylates are alkoxylated phenol monoacrylate, nonylphenol acrylate, ethylhexyl acrylate, isodecyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tripropylene glycol methyl ether monoacrylate, neopentyl glycol propoxylate. Methyl ether monoacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butane Diol dimethacrylate, diethylene glycol diacryle DOO, diethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate,
Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, 1,3
-Butylene glycol dimethacrylate, tripropylene glycol diacrylate, polybutadiene diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate,

Ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, alkoxylated aliphatic diacrylate ester, tris (2-hydroxyethyl) isocyanurate trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate. Acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, di- Trimethylolpropane tetraacrylate, dipentaerythritol pentaa Includes, but is not limited to, acrylate and ethoxylated pentaerythritol tetraacrylate. Preferably, the di- or polyfunctional acrylate is ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, epoxidized trimethylolpropane triacrylate, Selected from dipentaerythritol pentaacrylate or any combination thereof. Acrylate is generally preferred over methacrylate because it cures faster than methacrylate.

The mono-, di- or polyfunctional acrylate material may contain other groups which impart certain characteristics to the final cured material. For example, acrylated silicone or acrylated urethane can be used to obtain very soft materials; fluoroacrylates, such as Minnesota Manufacturing and Mining.
ining) (3M), 2- (N-butylperfluoro-octanesulfonamido) ethyl acrylate, available from St. Paul, Minnesota, FX-189 to give oil and water repellency and low surface energy, and May enhance the chemical resistance of the cured material; silane acrylates may be added to provide adhesion or surface wettability;
Fully acrylated epoxy or fully acrylated epoxy novolac can be used to obtain harder, chemically resistant cured materials. "Fully acrylated epoxy or fully acrylated epoxy novolac" means a material that does not contain any unreacted epoxy groups.

When a fluoroacrylate or silane acrylate is used, it is preferred to react the fluoroacrylate (or silane acrylate) with an amine curing agent to form the amine adduct before adding either to the composition. This ensures that the fluorocarbon (or silane acrylate) participates in the reaction before the difference in surface energy transfers the fluorocarbon chain (or silane acrylate chain) to the surface of the membrane.

In addition to the acrylate material, the floor finish composition preferably comprises at least one mono-monomer to enhance solvent resistance and / or modify viscosity, physical properties and / or chemical resistance. , Di- or polyfunctional epoxy monomers, oligomers or polymers. In general, di- and polyfunctional epoxides enhance crosslink density and are therefore preferred.

Examples of suitable epoxy compounds are alkyl glycidyl ethers, nonylphenyl glycidyl ethers, cresyl glycidyl ethers, phenyl glycidyl ethers, epoxy compounds derived from cashew nut oils such as Cardolith Corporation.
te Corporation), Newark, NJ, "CARDOLITE" ™, commercially available
Series, above, bisphenol A epoxy resin,
Bisphenol F epoxy resin, and epoxy novolac resin, such as Dow Chemical Company
cal functional) polyfunctional glycidyl ethers including the DE series, mono-, di- or polyfunctional ethers of various compounds such as diglycidyl ethers of 1,4-butanediol, neopentyl glycol. Diglycidyl ether, alkoxylated neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, alkoxylated trimethylolethane triglycidyl Ether, alkoxylated trimethylolpropane triglycidyl ether, dibromoneopentyl glycol diglycidyl ether, aliphatic polyol polyglycidyl ether, Included, but not limited to, glycol diepoxide as well as the polyglycidyl ether of castor oil.

Preferably, the mono-, di- or polyfunctional epoxy monomer, oligomer or polymer is a bisphenol F epoxy resin, a bisphenol A epoxy resin, an epoxy novolac resin, a diglycidyl ether of neopentyl glycol, or a diglycol of an alkoxylated neopentyl glycol. It is selected from the group consisting of glycidyl ether, trimethylolpropane triglycidyl ether, alkoxylated trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether and alkoxylated trimethylolethane triglycidyl ether.

Still other special functionalities may be added to the curable composition of the present invention to obtain improved properties. For example, epoxy resins derived from epoxidized soybean oil, acrylated epoxidized soybean oil, tall oil acrylate and cashew nut oil, all of which contain double bonds, "CARD.
OLITE "™ may be added and post-cured via another mechanism such as, for example, oxidative free radical polymerization.

The individual compounds of the curable composition are preferably selected such that upon mixing they form a liquid mixture of readily workable viscosity in which no inert diluent or solvent is required. If a low viscosity is desired, an inert diluent that avoids the problems associated with volatile organic solvents can be used. Such diluents are well known to those of ordinary skill in the art and include, for example, benzyl alcohol and (Mitsubishi Gas Chemical Co., Inc.
Includes materials such as "NIKANOL" (TM) xylene-formaldehyde resin (available from Mitsubishi Gas Chemical Company, Inc.). Do you need a solvent,
Alternatively, if desired, suitable solvents include xylene, mineral spirits or any other solvent known to one of ordinary skill in the art, such as ketones, acetates, alcohols and aromatic or aliphatic hydrocarbons.

When used for floor finish applications, the resulting floor can be used within about 24 hours, so that the resulting curable composition will have an ambient temperature (about 25 ° C. (ASTM)) within a few hours.
Partially acrylated epoxy materials, active amine curatives and any other additional components are optionally selected to cure at or near temperatures. Low temperature cure down to about 0 ° C. can be achieved with the aid of catalysts. High temperature curing is also possible by selection of starting materials. High temperature cure generally results in shorter working times and faster cure rates.

In addition to the above-mentioned components, the various compositions according to the invention also contain other additives such as pigments, fillers, flowability and leveling additives, antibacterial additives, antifoaming agents, UV stabilizers. , Fibrous reinforcing agents, conductive fillers for conductive or antistatic coatings and sand, stone, quartz, marble, metals and other inorganic and organic materials, for example aggregates containing polymers. Effective polymer aggregates include elastomers, plastics and recycled plastics.

The curable composition of the present invention comprises various supports,
For example floors, walls, ceilings, decks (including garage decks, ship decks and timber decks).
k), plastics, protective and / or decorative coatings for furniture; floor finish products, such as parquet (wood), vinyl sheet materials, asbestos tiles, masonry tiles and OEM coatings for stone surfaces; grouts; Includes sealants; linings, such as tank linings; potting materials; mortar repair compositions for filling cracks and crevices in various supports; adhesives; tie coats for repair materials; and corrosion control coatings However, it is not limited to these. Various supports are cementitious materials,
It can be composed of stone, metal, plastic and wood. The curable composition may be in emulsified form in the above applications, especially if the low viscosity or water-derived nature of the material is advantageous.
Curable compositions in emulsified form may also be added to fresh cement mortar or concrete compositions to produce polymer modified mortar and concrete prior to curing.

As previously indicated, the curable composition is useful in floor covering applications. The floor finish composition according to the present invention,
D.O.s. that are fast cure (the floors are generally usable within 24 hours), they are non-corrosive, virtually odorless, and are commonly associated with other commercially available floor finish materials. T. It can be compounded so as to eliminate the need to attach a danger indication.

In floor covering applications, the curable composition of the present invention desirably additionally comprises at least one mono-, di- or polyfunctional acrylate and at least one mono-,
Includes di- or polyfunctional epoxies. Most preferably, the composition comprises at least one di- or polyfunctional acrylate and at least one di- or polyfunctional epoxy. Generally, 5% to 80% by weight, preferably 10% to 50% by weight, of the partially acrylated epoxy material, 5% to 80% by weight, preferably 5% to 50% by weight in the curable composition. Acrylate material, and 5% to 80% by weight, preferably 10% to 50% by weight, of the epoxy material, the weight being the weight of the total curable material, that is, the fraction present in the curable composition. Acrylated Epoxy Materials Based on added epoxy and acrylate materials.

The floor covering composition may include all the aforementioned additives or any other additives known in the art. Floor finish compositions can be transparent or pigmented, and they can be self-leveling.

The floor finish support must be prepared for the application of the curable composition, which is well known to those skilled in the art, such as grit blasting, metal or shot blasting, scarifying. (Scarifying) or Thunder finish. In addition, the basecoat may be applied to the support before application of the curable composition.

The floor finish and coating composition may be applied by any method known in the art including trowel, squeegee, roller, spray or spray methods.

In another embodiment, the invention comprises a. Applying a curable composition onto a substrate, the curable composition having (i) a molecular weight between 150 and 10,000, at least one 1,2-epoxide group and at least one terminal. At least one partially acrylated epoxy monomer or oligomer containing acrylate or methacrylate groups, and (ii) at least a sufficient amount to react with substantially all 1,2-epoxide groups, acrylate groups and methacrylate groups An active mono-, di- or polyamine curing agent; and b. Curing the curable composition, which is directed to a method of forming a protective and / or decorative coating on a support.

Desirably, the curable composition comprises at least one mono-, di- or polyfunctional acrylate and at least one mono-, di- or polyfunctional epoxy in the amounts mentioned above.

The curable composition further comprises agglomerates which can be troweled and applied in a slurry, or in another embodiment, the agglomerates are applied by hand or using, for example, a blower or a rotary spreader. It can be sprinkled or evenly spread over the curable composition. If spread over the applied curable composition, the agglomerates should be applied as soon as possible before the composition has the opportunity to substantially cure.

In another embodiment, one or more additional coatings of curable composition may be applied on top of the first layer of curable composition. The curable composition of each successive layer should be applied after the preceding coating has substantially cured. The curable composition of each layer may be sanded after it is substantially cured, but prior to application of the curable composition of the additional layer.
Depending on the smoothness of the coating, any number of layers of curable composition may be applied.

The curable compositions of the present invention can be used to prepare various floor finish surfaces, such as non-slip surfaces, smooth surfaces, terrazo floors, electrically conductive floors, antistatics, by using floor making methods well known to those skilled in the art. It can be used to provide floors and clear or colored floors.

The following specific examples are provided to demonstrate the preparation of partially acrylated epoxy materials and curable compositions according to the present invention. Example 1 250 g of bisphenol F epoxy resin (D.E.R. 3)
54, commercially available from The Dow Chemical Company, Midland, Mich., With an estimated equivalent weight of 172), 52.3 g acrylic acid, 2 g triethylamine and 0.05 g hydroquinone monomethyl ether.
(MEHQ) is placed in a container equipped with a mechanical stirrer. The resulting mixture is stirred in a closed system at 60 ° C. for 20 hours. The resulting product contains a 1: 1 epoxide to acrylate functionality ratio.

The above procedure was repeated 4 times to adjust the ratio of the starting materials to produce a product having epoxide to acrylate ratios of 1: 3, 1.3: 1, 1.7: 1 and 3: 1 respectively. To get In the iterative method, tetramethylammonium chloride is used instead of triethylamine. Tetramethylammonium chloride is used in an amount of 2 to 2.5% by weight, based on the weight of acrylic acid used.
The reaction temperature ranges from 45 ° C to 60 ° C and the reaction time varies from 12 to 48 hours. Table 1 lists the epoxide to acrylate ratio, viscosity, estimated equivalent weight in grams / eq. (G / eq.) And average number of functionalities (acrylate plus epoxide) per molecule for each product obtained. , # 1 is the product as described above, and # 2- # 5 are iterative methods.

[0058]

[Table 1] Table 1 Epoxide: Acrylate Viscosity (cps) Equivalent Average Functionality Ratio (g / eq.) # 1 1: 1 20,550 @ 20.7 ° C 208 2 # 2 1: 3> 100,000 226 2 # 3 1.3 : 1 19,000 @ 21.9 ° C 204 2 # 4 1.7: 1 14,400 @ 21.3 ° C 200 2 # 5 3: 1 5,040 @ 27.8 ° C 190 2

Example 2 The general procedure of Example 1 except bisphenol A epoxy resin (DER 331, equivalent weight 187, available from Dow Chemical Company) is used in place of bisphenol F epoxy resin. Repeat the synthesis method. The starting material ratios are adjusted so that the resulting products contain epoxide to acrylate ratios of 1.2: 1, 1.7: 1 and 3: 1 respectively. Table 2 posts product data as described for Table 1.

[0060]

[Table 2] Table 2 Epoxide: Acrylate Viscosity (cps) Equivalent Average Functionality Ratio (g / eq.) 1 1.2: 1 128,000 @ 22.8 ° C 224 2 2 1.7: 1 26,260 @ 21.3 ° C 217 2 3 3: 1 67,200 @ 20.7 ℃ 208 2

Example 3 A bisphenol F epoxy resin was prepared from diglycidyl ether of butanediol (“HELOXY” 67 ™), diglycidyl ether of neopentyl glycol (“HEL”).
OXY "68 ™), diglycidyl ether of cyclohexanedimethanol (" HELOXY107 ™ "), trimethylolethane triglycidyl ether
("HELOXY" 5044 (TM)), epoxy novolac resin (DEN 431, available from Dow Chemical Company) and trimethylolpropane triglycidyl ether (TPTE) (CV-Specialty Chemicals Incorporated (CVC). Specialty
Chemical), available from Chery Hill, NJ)) and the general synthetic method of Example 1 is repeated 6 times. All "HELOXY" materials are from Shell Chemica
Company, Houston, Texas. The starting material ratios are adjusted so that each of the resulting products contains a substantially 1: 1 epoxide to acrylate ratio. Table 3 posts product data as described for Table 1.

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[Table 3] Table 3 Starting materials Epoxide: Acrylate Viscosity (cps) Equivalent average functionality ratio (g / eq.) "HELOXY" 67 1: 1 100 @ 21.1 ° C 167 2 "HELOXY" 68 1: 1 73 @ 20.7 ℃ 172 2 "HELOXY" 107 0.96: 1 757 @ 20 ℃ 1982 2 "HELOXY" 5044 0.94: 1 2140 @ 20.2 ℃ 196 3 DEN431 1: 1 838400 @ 21.1 ℃ 211.6 2.6-2 .8 TPTE 1: 1 1930 @ 23 ℃ 179 3

Example 4 This example demonstrates the preparation of a number of acrylated epoxy polyurethanes. (a) Production of monoisocyanate epoxide Isophorone diisocyanate (675 g, 3.04 mol)
In a dry nitrogen atmosphere with dibutyl tin laurate (0.31
0 g, 4.91 x 10 ^-4 mol). The mixture was stirred and gently heated to 45-50 ° C, then glycidol (225 g, 3.037 mol) was added slowly (4
-5 hours). Reactions were titrated with% NCO (colorimetric bromophenol blue back titration with excess dibutylamine hydrochloric acid-ASTM D2572 (modified)) and F
Proceed until TIR revealed completeness.

(B) Production of Monoisocyanate Acrylate This material was prepared by using TONE M-10 instead of glycidol.
Prepared in the same manner as in (a) above, but using 0 hydroxycaprolactone acrylate and conducting the reaction in a dry air atmosphere instead of a nitrogen atmosphere.

(C) Production of linear, monoepoxide, monoacrylate polyurethane 274 g (0.551 equivalents (eq.) Of "TERTHANE 1"
000 "™ polyol (polytetramethylene ether glycol, available from DuPont Company),
80.4 g (0.275 eq.) Of glycidol isophorone monoisocyanate prepared in (a), 157.3 g (0.2
275 eq.) Of M100 isophorone monoisocyanate prepared in (B) and ˜0.15 g of MEHQ are mixed in a dry atmosphere and stirred. Gently mix the resulting mixture to 6
Heat to 5-70 ° C and maintain this temperature until FTIR shows the reaction is complete. The product obtained has an equivalent weight of 922.

(D) Preparation of Branched Polyfunctional (Acrylate and Epoxide) Polyurethane 103.0 g (0.20 eq.) Of polypropylene oxide triol, 112.6 g (0.22 eq.) Of polycaprolactone diol (“TONE”). "(Trademark) polyol 021
0, commercially available from Union Carbide Corporation, Danbury, CT), 9.1g (0.20e)
q.) trimethylolpropane and 30.1 g (0.27 e)
q.) Isophorone diisocyanate is mixed under a nitrogen atmosphere. The resulting mixture is stirred and gently mixed with 65-7.
Heat to 0 ° C. The reaction is allowed to proceed to completion, i.e. the -NCO group is no longer detected by FTIR. Cool the reaction to room temperature and stop stirring. 39.3 g (0.13 eq.) of glycidol isophorone monoisocyanate prepared in (a), 154 prepared in (B).
Add 2 g (0.27 eq.) Of acrylate isophorone monoisocyanate and ˜0.15 g of MEHQ and continue stirring. Gently mix 6 of the resulting mixture in a dry atmosphere.
Heat to 5-70 ° C and allow the reaction to proceed until completion is evidenced by the absence of the -NCO band as detected by FTIR. The product obtained has a functionality of 2.6-2.7 and 1
It has an equivalent weight of 105.

"TONE" polyol 0210 was added to "RU"
COFLEX "(trademark) S-1028-110," RUC
OFLEX "S-1019-120," RUCOFLE
X "S-1015-120," RUCOFLEX "S-
Six additional linear difunctional oligomers are prepared according to Method (C) above, except substituting 105-55, "ARCOL" PPG-1025 and "ARCOL" PPG-2025 respectively. "RUCOFLEX" materials are all Ruco Polymer Corporation (Ruco Polymer
Corporation), Hicksville, NY, a saturated polyester diol available from ARCO
The "L" material is Arco Chemical Company.
ical Company), South Charleston, West
Polyether available from Virginia.

Example 5 A curable composition is prepared as follows.

Ingredient (A) Amount (g) "EBECRYL ™ 3605" 31.5 (partially acrylated bisphenol A epoxy resin) D.N.431 11.0 (obtained from Dow Chemical Company) Possible epoxy novolac resins) D.E.R. 354 11.0 (bisphenol F epoxy resin available from Dow Chemical Company) PHOTOMER ™ 4149 43.5 (available from Henkel Corporation) Component (B) Amount (g) DEHYDRAN ™ 1208 0.64 (a defoamer available from Henkel Corporation, Ambler, PA) GASKAMINE ™ 328 29.60

The composition is prepared by mixing components (A) and (B) at 21 ° C. and mixing for 1 minute. The mixture is extruded at 21 ° C to form a 20 mil film. The second composition and the film are produced by the same method except that the temperature of 10 ° C. is used instead of 21 ° C. Two comparative curable compositions at 10 ° C. and 21 ° C. respectively were compared to Comparative Example 1
Then, 26.42 g (0.139 g) of partially acrylated bisphenol A epoxy resin "EBECRLY3605"
8 eq.) Bisphenol A epoxy resin, D.E.R. 3
31, available from Dow Chemical Company, manufactured as above except replaced. In Comparative Example 2, "EBECRY3605" was removed and GAS
The amount of KAMINE-328 is reduced to 21.93g and the amount of DEHYDRAN is reduced to 0.46g.

At 21 ° C., the film containing the partially acrylated bisphenol A epoxy resin was cured to give "My
It was tack-free to lar "™ film and showed good transparency for 24 hours. On the other hand, the film containing the bisphenol A epoxy resin is cured, and "My
Non-tacky to "lar" but very cloudy at the end of 24 hours. Haze is believed to be due to the phase separation of the epoxy and acrylate materials. Comparative Example 2 without either the partially acrylated bisphenol A epoxy resin or the bisphenol A epoxy resin has a marbled or wrinkled appearance after 24 hours and feels tacky to the touch and fails the "Mylar" test.

The film containing the partially acrylated material cures at 10 ° C., is tack-free to Mylar and shows good transparency for 24 hours. On the other hand, bisphenol A
Films containing epoxy resin require at least 4 hours to cure, are non-sticky to "Mylar",
The cured film is very cloudy. Films without either partially acrylated bisphenol A epoxy resin or bisphenol A epoxy resin did not cure sufficiently after 7 days to measure physical properties.

Physical properties, ie 21 of the resulting film
Tensile strength (psi), elastic modulus (psi), hardness at ℃ and 10 ℃
(Shore D) and tensile resistance (lbs / in) are measured at 1 and 7 days. Tensile test and elastic modulus are measured by die C
TM D412 (20 in / min crosshead speed), hardness test according to ASTM D2240, and tensile resistance according to Die C to ASTM D1.
004 (20 in / min crosshead speed). The measurement results are recorded in Table 4.

[0073]

[Table 5] Table 4 Tensile strength Elastic modulus Hardness Tensile resistance (Mpa) (Mpa) (Shore D) (KN / M) 21 ℃ 10 ℃ 21 ℃ 10 ℃ 21 ℃ 10 ℃ 21 ℃ 10 ℃ (1st day (Measurement) EBECRYL3605 Example 15.5 6.0 282.9 40.7 45 30 53 13.4 Comparative Example 1 11.9 1.3 68.3 0.1 37 7 25.7 1.5 Comparative Example 2 The film is so viscous that physical properties cannot be measured. (Day 7 measurement) EBECRYL365 Example 62.8 47.9 1962.3 1203.7 69 65 80.1 86.6 Comparative Example 1 65.4 5.8 2220.0 34.4 74 22 91.8 16.1 Comparative Example 2 2.3 ** 18.6 ** 15 ** 6.2 ** ** The film is physical Does not cure sufficiently to measure physical properties.

The data obtained above show that the partially acrylated epoxy material exhibits shorter set times and better day 1 physical properties at both 21 ° C. and 10 ° C. and at 7 ° C. enhanced at 10 ° C. Shows that it gives physical properties.

Example 6 Six curable compositions according to the present invention are prepared as follows.

Table 6 Ingredient (A) Amount (g) Partially Acrylated Epoxy Material 31.5 D.E.N.431 11.0 D.E.R. 354 11.0 PHOTOMER 4149 43.5 Amount of Component (B) (g) GASKAMINE-328 Approx. 30 g * * The amount of GASKAMINE-328 used in each example varies slightly, but 1: 1 between components (A) and (B).
It is calculated that there is an activity equivalent ratio of.

The partially acrylated epoxy material used is different for each composition. EBECRYL3605
Other than that, the acrylated epoxy materials are those produced in Examples 1 and 2 above, as shown in Table 5.

Components (A) and (B) are mixed, mixed for 1 minute and cast into a 20 mil thick film. The physical properties of the film (measured as described in Example 5) on days 1 and 7 are shown in Table 5.

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[Table 7] Table 5 Partial Acrylation Tensile Strength Elastic Modulus Hardness Tensile Resistance Epoxy (Mpa) (Mpa) (Shore D) (KN / M) (Measurement on the 1st day) EBECRYL3605 26.1 740.7 53 92.1 Example 1 , # 2 20.5 560.4 50 83.4 (see Table 1) Example 1, # 1 20.5 1123.8 61 118.3 (see Table 1) Example 1, # 3 33.3 1104.5 57 115.8 (see Table 1) Example 1, # 4 32.1 1023.2 60 112.0 (see Table 1) Example 1, # 5 34.0 1218.2 60 116.1 (see Table 1) Example 2, # 1 17.8 416.4 52 68.8 (see Table 2) Example 2, # 2 27.6 629.5 61 88.0 (See Table 2) Example 2, # 3 22.6 828.9 56 85.6 (See Table 2) Example 3 8.4 46.1 30 14.8 ("HELOXY" 68) Example 3 19.3 19.3 32 12.0 ("HELOXY" 107 ) Example 3 7.1 36.3 30 15.4 ("HELOXY" 5044) Each 15.75 g EBEC 12.4 88.1 45 33.1 RYL3605 plus "HE LOXY" 5044 (7th day measurement) EBECRYL3605 70.1 4133.3 70 110.1 Example 1, # 2 68.7 3675.8 75 108.4 (see Table 1) Example 1, # 66.1 2411.5 70 65.2 (See Table 1) Example 1, # 3 77.1 4577.7 70 87.8 (See Table 1) Example 1, # 4 78.4 3653.8 75 83.1 (See Table 1) Example 1, # 5 73.2 3620.0 75 74.4 (See Table 1) Example 2, # 1 71.6 2379.1 74 67.7 (See Table 2) Example 2, # 2 73.1 2468.0 73 61.9 (See Table 2) Example 2, # 3 69.9 3010.9 69 92.8 (See Table 2) Example 3 41.1 1681.2 64 93.5 ("HELOXY" 68) Example 3 31.1 1199.6 61 100.7 ("HELOXY" 107) Example 3 39.3 1434.5 66 101.2 ("HELOXY" 5044) EBECRYL3605 Add 55.6 1863.1 73 76.3 `` HELOXY '' 5044 (15.7g each)

Example 7 Five curable compositions according to the present invention are prepared as follows.

Table 8 Component (A) Amount (g) Partially Acrylated Epoxy Oligomer 10.0 D.E.R. 354 17.0 PHOTOMER 4149 38.5 EBECRYL 3605 34.5 Component (B) Amount (g) GASKAMINE-328 ** ANCAMINE1769 **** GASKAMINE and ANCAMINE curing agents are used in an amount of 50/50 (W / W) admixture (admixture has an equivalent weight of 51.26) between components (A) and (B). Calculated so that there is a 1: 1 activity equivalent ratio.

The partially acrylated epoxy oligomers used differed for each composition and were prepared in Example 4 above, similar to those shown in Table 6 depending on the various ingredients used to prepare the oligomers. It is something.

Components (A) and (B) are mixed, blended for 1 minute and cast into a 20 mil thick film. Physical properties,
That is, the tensile strength and elongation of the film on day 1 and day 7 (measured as in Example 5) are recorded in Table 6.

[0082]

Table 9 Table 6 Partial Acrylation Tensile Strength (Mpa) Material 1 day 7 days "TONE" Polyol 0210 11.7 54.2 "RUCOFLEX" S-1028-110 13.0 59.3 "RUCOFLEX" S-1019-120 15.8 47.3 "RUCOFLEX" S-105-55 15.1 48.4 "TERAHANE" 1000 16.2 51.6

Example 8 Example 7 except that the composition of component (A) was as follows:
Two additional curable compositions are prepared in a manner similar to that of

Table 10 Component (A) Amount (g) Partially Acrylated Epoxy Oligomer 20.0 D.E.R. 354 13.0 PHOTOMER 4149 40.0 EBECRYL 3605 27.0

The measured physical properties of the films on days 1 and 7 are listed in Table 7.

Table 11 Partial Acrylation Tensile Strength (Mpa) Oligomer 1 day 7 days "RUCOFLEX" S-1028-110 61.8 70.3 "RUCOFLEX" S-1015-120 43.7 67.9

Example 9 Four curable compositions according to the invention are prepared and cast into films in the same manner as in Example 6, except that the components (A) are as follows:

Table 12 Curable “EBECRYL partially acrylated HELOXY67 (g) partially acrylated composition 3605” (g) HELOXY67 (g) DEN431 (g) (prepared in Example 3) (in Example 3) (Manufactured) # 1 35 35 − − # 2 35 − 35 − # 3 − 35 − 35 # 4 − − 35 35

The physical properties of the film were measured as described in Example 5 on days 1 and 7 and are set forth in Table 8.

[Table 13] Table 8 Composition Tensile strength Elastic modulus Hardness Tensile resistance (Mpa) (Mpa) (Shore D) (KN / M) (Measured on the 1st day) 1 59.4 2099.4 65 * 2 23.7 574.6 60 93.5 3 64.0 2139.4 72 147.0 4 82.5 2064.9 73 116.1 (7th day measurement) 1 55.0 1894.1 69 * 2 78.3 2436.3 60 111.7 3 69.8 3219.7 74 * 4 80.4 3884.6 73 * * The tensile resistance of these compositions was not measured.

Example 10 A curable composition according to the present invention is produced and cast into a film in the same manner as in Example 6, except that the components (A) and (B) are as follows.

Table 14 Ingredient (A) Amount (g) "EBECRYL3605" 15.0 D.E.N.431 16.9 D.E.R. 354 16.9 HELOXY 5048 41.2 (Trimethylolpropane triglycidyl ether, (Available from Shell Chemical Company) PHOTOMER 4127 2.0 (aliphatic difunctional acrylate, available from Henkel Corporation) PHOTOMER 4149 8.0 Component (B) Amount (g) GASKAMINE 328 31.9 Benzyl Alcohol 8.0

The physical properties of the resulting film (measured as described in Example 5) on days 1 and 7 were determined by
Describe in the table.

[Table 15] Table 9 Composition Tensile strength Elastic modulus Hardness Tensile resistance (Mpa) (Mpa) (Shore D) (KN / M) (1st day measurement) Example 10 59.3 1839.6 69 143.0 (7th day measurement) Example 10 85.9 2542.4 74 76.3

Example 11 A curable composition according to the present invention is prepared as follows.

Table 16 Ingredient (A) Amount (g) "EBECRYL3605" 16.1 D.E.N.431 18.1 D.E.R. 354 18.1 HELOXY 5048 44.1 PHOTOMER 4127 2.1 PHOTOMER 4149 8.6 Component (B) Amount (g) GASKAMINE 328 34.3 Benzyl Alcohol 8.6 Accelerator ⁺ * + See Table 10 below for specific accelerators used in each composition. * The amount of accelerator added to each composition will vary depending on the specific accelerator applied to the amount used as shown in Table 10.

The accelerator is added to the component (B) immediately before mixing the components (A) and (B). The effect of accelerators on mass cure is standard wire from Paul N. Gardner Co., Inc., Pompano Beach, FL.
It is evaluated by a 150 gram mass gelation time measured using a Stirrer model gel timer.

[0091]

[Table 17] Table 10 Accelerator Temperature (℃) Curing time (min) Increase at the speed of mass curing% None 15.5 29.8 (Control) 1.5g CuCl ₂ · 2H ₂ O + 3g H ₂ O 15.5 11.2 62.4% 3g Imidazole / HCl + 3g H ₂ O 15.5 8.2 72.5% 3g Imidazole + 3g H ₂ O 15.5 13.3 55.4% 3g 2,4,6-Tri (dimethylaminomethyl) phenol 15.5 26.5 11.1% 3g Salicylic acid 15.5 27.0 9.4% 3g Tetra Methoxysilane 15.5 27.7 7.0% None 21 21.7 (Control) 3g 10% HCl 21 9.3 57.1% 3g H ₂ O 21 12.4 42.9% 3g 10% NaOH 21 12.5 42.4% 3g Nonylphenol 21 19.4 10.6%

Example 12 A curable composition according to the present invention is prepared as follows.

Table 18 Component (A) Amount (g) EBECRYL3605 273.6 Epalloy 8250 440.1 (epoxy novolac resin available from CVC Specialty Chemicals Inc., Chery Hill, NJ) D.E.R. 354 596. .7 HELOXY5048 1073.4 PHOTOMER4127 44.2 PHOTOMER4149 177.1 component (B) amount (g) GASKAMINE328 2876.4 benzyl alcohol 584.2 component (C) amount (g) grade silica sand 33,290, 120 flint shot US Silica Co., Berkeley Springs, WV) ZEEOSPHERES ™ 2,950 (Zeelan Industries, Inc., St. Paul, available from MN)

The composition was prepared by first mixing the components (A) and (B),
Then mix with component (C). The mixture is then troweled onto a concrete support. Cube samples were also prepared for compressive strength measurements, the measurements were performed according to ASTM C109 and are described below.

[Table 19] Time Compressive strength (Mpa) 4 hours 3.2 8 hours 13.2 12 hours 20.1 16 hours 28.5 24 hours 30.5 7 days 55.5

The compositions of the previous examples, when used, for example, as floor coating compositions, are conventionally one or more defoamers, surface leveling agents, UV stabilizers, antioxidants and An additional composition containing an inhibitor (to prevent free radical polymerization of the acrylate), which adduct does not affect the physical properties of the coating, generally in a small amount of about 3% by weight, It may additionally be mixed.

Front Page Continuation (72) Inventor Benedict Es Clatro, United States 44125 Barry View, Ohio, Bryden Court 6830 (72) Inventor Thomas W. Richardson Senior United States 44202 Aurora, Ohio, Clipper Cove 10266 Turn

Claims (4)

[Claims] 1. (i) At least one partially acrylated epoxy having a molecular weight between 150 and 10,000 and comprising at least one 1,2-epoxide group and at least one terminal acrylate or methacrylate group. Monomer or oligomer, and (ii) substantially all 1,2-
A curable composition containing at least a sufficient amount of an active mono-, di- or polyamine curing agent to react with epoxide groups, acrylate groups and methacrylate groups. 2. A. Applying on the support a curable composition containing the following components: (i) having a molecular weight between 150 and 10,000, at least one 1,2-epoxide group and at least one terminal acrylate or At least one partially acrylated epoxy monomer or oligomer containing a methacrylate group, and (ii) an active mono-, di- or polyamine curing agent, and b. A method for forming a protective and / or decorative coating film on a support, which comprises curing the curable composition. 3. A support having a coating film produced by the method according to claim 2. 4. A. Applying on the support a curable composition containing the following components: (i) having a molecular weight between 150 and 10,000, at least one 1,2-epoxide group and at least one terminal acrylate or At least one partially acrylated epoxy monomer or oligomer containing a methacrylate group, and (ii) an active mono-, di- or polyamine curing agent, and b. A method of forming a floor on a support, which comprises curing the curable composition.