FR2742762A1 - CURABLE COMPOSITION COMPRISING A NOVOLAQUE VINYL ESTER RESIN, METHOD OF FORMING A COATING ON A SUBSTRATE, COMPRISING THE APPLICATION OF SUCH A COMPOSITION, AND SUBSTRATE COVERED BY THIS COATING - Google Patents

Abstract

The present invention relates to a novolak vinyl ester resin composition, thermosetting, useful for the formation of coatings, linings, and floor coverings to protect steel, iron, concrete and other substrates. , the corrosive action of acids, acalis and aggressive solvents.

Description

BACKGROUND OF THE INVENTION

  1. Field of the Invention The present invention relates to thermosetting compositions which cure at room temperature to provide coatings having exceptional chemical resistance to acids, alkalis and aggressive solvents such as methylene chloride. More particularly, the invention relates to a composition of thermosetting novolak vinyl ester resin, useful in the formulation of protective coatings, trimmings and floor coverings to protect steel, iron, concrete and

other corrosion substrates.

2. Description of the prior art

  Thermosetting novolak polymer resins are often used in the formulation of anticorrosion coatings because they are significantly more resistant to chemical attack than many other types of thermosetting polymers. The most common types of novolak resins used include novolak epoxy resins and

of novolak vinyl ester.

  Novolac based epoxy resins are produced by reacting a novolak resin with an epichlorohydrin. Although these thermosetting resins, when it is an amine cured at room temperature, give cured materials having excellent resistance to alkalis, salts, weak non-oxidizing acids, and certain weak solvents, they generally have poor resistance to organic acids, concentrated non-organic acids (except 98% sulfuric acid), oxidants and aggressive solvents such as methylene chloride. Improvements in their chemical resistance can generally be obtained by using high temperatures during the curing process. However, this is impractical in many situations, since it is difficult to heat large areas evenly, not to mention the additional time and expense associated with the heating process. In addition, slow curing rates, short working times and high viscosities are additional shortcomings associated with the use of epoxy novolak resins in

  formulation of anti-corrosion coatings.

  The commercially available novolak vinyl ester resins are methacrylated novolac resins produced by the reaction of methacrylic acid with an epoxy novolak resin. These resins are hardened by a mechanism involving free radicals,

  usually initiated by peroxides, to produce a hardened material.

  Novolac vinyl ester resins have been used for many years as corrosion resistant coatings, since they generally have good resistance to many chemicals, including acids, alkalis, hypochlorites and many solvents. However, they generally have poor resistance to organic solvents, in particular chlorinated organic solvents such as methylene chloride, and to concentrated sulfuric acid. In addition, novolak vinyl ester resins are viscous materials, which makes them difficult to handle. Commercially available novolak vinyl ester resins are generally

  dissolved in a styrene monomer to reduce viscosities.

  However. this gives highly odorous and 2 flammable compositions. which are of little interest both from a health and environmental point of view. In addition, novolak vinyl ester resins have a short pot life, generally not more than 6 months, and

usually less than 3 months.

  US Pat. Nos. 4,363,889 and 4,443,503 describe anti-corrosion coating compositions comprising an unsaturated polyester resin. glass flakes of a specific size, a ketone peroxide and a hydroperoxide and / or peroxyester. All known unsaturated polyesters are described as being useful in the coating compositions. including polyester resins obtained by reaction of a

  epoxy resin with a ct unsaturated monocarboxylic acid, -

  monoethylenic (see column 4, lines 19 to 52). polyester resins can be diluted with polymerizable monomers which include both mono monomers. di- and multifunctional, comprising ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate 3 (see the paragraph connecting columns 4 and 5), although styrene is the only monomer specifically used in the examples. The patents do not offer any suggestion as to the specific combination of a resin

  of novolak vinyl ester with an α, 3- unsaturated monomer

  ethylenic, di- or multifunctional, or that such a combination could give cured coatings with improved anti-corrosion properties, compared to other resin compositions

unsaturated polyester / monomer.

  US Patent No. 4,083,890 generically describes curable compositions comprising an unsaturated polyester resin and a copolymerizable monomer. However, there is no teaching as to a specific combination of a novolak vinyl ester resin with a ct, p-ethylenic, di- or multifunctional unsaturated monomer, nor any hint or suggestion that such a combination would provide superior properties, compared to other resin combinations

unsaturated polyester / monomer.

SUMMARY OF THE INVENTION

  According to the present invention, a composition based on novolak vinyl ester resin has been found which hardens at room temperature to provide a material having improved resistance to the corrosive effects of organic solvents such as acetone, methanol, chlorinated solvents, for example methylene chloride, as well as acids such as concentrated sulfuric acid and 50% nitric acid, relative to the materials resulting from the curing of epoxy and corrosion-based compositions commercially available novolak vinyl ester. In addition, the compositions of the present invention generally have a longer pot life (an accelerated pot life study at 120 F (49 C) indicating a longer pot life of 9 months), compared to the

  conventional novolak vinyl ester compositions.

  Furthermore, the resin / monomer components of the present invention have low viscosities, without the need for styrene, and they avoid the health and environmental defects of conventional novolak vinyl ester resins (and therefore do not not require labeling

  risk of flammability or corrosion).

  Specifically, the present invention provides a curable composition comprising (i) one or more novolak vinyl ester resin (s), the one or more novolak vinyl ester resin (s) containing at least two α, t-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two ca, 5-ethylenic unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixtures of

these compounds.

  In another embodiment, the invention provides a

  composition formed by combination of the above materials.

  In yet another embodiment, the invention provides a method of forming a coating on a substrate comprising the following steps: A) applying a curable composition to a substrate, said curable composition comprising (i) one or more novolak resin (s), the novolak resin (s) containing at least two ot-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two ot, 3-ethylenically unsaturated sites per molecule; and (iii) an organic hydroperoxide, a peroxide or a mixture of these compounds; and

  B) allow the hardening of said curable composition.

  The invention further provides substrates, for example floor covering substrates and trim substrates, coated with a

  coating produced by the above mentioned process.

  DETAILED DESCRIPTION OF THE INVENTION

  The novolak vinyl ester resins useful in the present invention preferably have a calculated molecular weight of 300 to 5,000 g / mole, more preferably 1,000 to 3,000 g / mole, and contain on average at least two ct, 513-ethylenically unsaturated groups terminal per molecule. If the molecular weight is less than 300 g / mol, the resulting cured materials tend to be brittle, and good results are difficult to obtain because brittle coatings have a propensity to

  cracks and generally have poor impact resistance.

  Since an increase in molecular weight generally increases the viscosity of the resin, thus making them less suitable for working, it is preferable to use materials with molecular weights of 000 g / mol or less. The preferred novolak vinyl ester resin has a calculated molecular weight range of 2,200 to 3,000 g / mole, a functionality of more than 2.5 and a viscosity of more than 90,000 cps

  when measured at 25 C (77 F) by a Brookfield viscometer.

  Novolak vinyl ester resins useful in this invention

  are prepared by reaction of an a, 3- unsaturated monocarboxylic acid

  ethylene with an epoxy novolak resin. The epoxy novolak resin can be synthesized by reaction of phenol or of a substituted phenol, for example an alkylphenol such as a cresol, with formaldehyde, in the presence of an acid or alkaline catalyst, and subsequent reaction of the novolak or cresol compound. resulting with epichlorohydrin or

  methylepichlorohydrin. Cc-unsaturated monocarboxylic acids, -

  Useful ethylenics include acrylic acid, methacrylic acid, crotonic acid, monoesters of unsaturated polycarboxylic acids and monoesters of maleic acid. Unsaturated acids and monoesters can

  be used alone or as a mixture of two or more.

  The novolak vinyl ester resin is present in the compositions of the present invention in an amount between 20% and 90% c, preferably between 30% and 60% by weight, based on the weight of

the total composition.

  The reactive monomers useful in this invention are acrylates

  and methacrylates containing at least two ct, 3- unsaturated sites

  ethylenic per molecule, having a low viscosity, generally less than 500 cps measured by a Brookfield viscometer at 25 C (77 F), and preferably less than 200 cps, and having a flash point greater than 60 C (140 F) , measured by the closed cup method of Pensky-Martins. The preferred reactive monomers have a calculated molecular weight of 150 to 1,500 g / mole, more preferably 200 to 300 g / mole. If the molecular weight is less than about 150 g / mole, the monomers tend to be highly toxic and volatile, and therefore are undesirable from an environmental point of view. If the molecular weight exceeds 1500 g / mole, the materials tend to be too viscous, yielding monomers which are less able to be worked and which have reduced dissolving power for the novolak vinyl ester resin. Of

  suitable monomers include, but are not limited to 1,4- diacrylate

  butanediol, 1,4-dimethacrylate, butanediol, 1,6- diacrylate

  hexanediol, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate and diethylene glycol dimethacrylate. These monomers can be used alone or as a mixture of two or more of them. Methacrylates are generally preferred to acrylates because the coatings

  resulting tend to exhibit improved corrosion resistance to

live alkalies.

  The reactive monomers may contain other groups which confer certain characteristics on the final cured material. For example, urethanes or a, [- ethylenically unsaturated silicones can be used to increase the flexibility of the cured material; α, 3-ethylenically unsaturated fluorine-containing monomers can be used to impart increased repellency to oils and water, lower surface coatings, and improved resistance to certain chemicals; and α-B-ethylenically unsaturated monomers containing silanes can be used to improve the adhesion and / or properties of

surface wetting.

  The reactive monomers are present in the compositions in an amount between 10% and 90%, preferably between 20% and 60% in

  weight, based on the weight of the total composition.

  The organic peroxide or hydroperoxide curing agents useful in the present invention can be any organic peroxide or hydroperoxide known in the art. Organic peroxides and hydroperoxides decompose, producing free radicals that initiate the polymerization reaction. Specific examples of useful peroxides and hydroperoxides are those which contain from 3 to 18

  carbon atoms, such as benzoyl peroxide, tert-perbenzoate

  butyl, methyl ethyl ketone peroxide, dilauryl peroxide,

  di (t-butylcyclohexyl) peroxide, bis (I -

  hydroxycyclohexyl), t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone hydroperoxide,

  diisopropylbenzene, and mixtures of these compounds.

  The peroxide, hydroperoxide, or mixture of these compounds, if used, is present in the composition in an amount of between about 0.2% and 10.0%, preferably between 1% and 4% by weight over the basis of the weight of the total composition. The preferred curing agent is

cumene hydroperoxide.

  Decomposition of the curing agent can be accomplished by heat or by the use of promoters and / or accelerators, which accelerate decomposition at a given temperature. When curing the compositions of the present invention at temperatures below 50 C (122 F), it is generally preferred to use promoters and / or accelerators. The most commonly used promoters are aromatic amines, although any promoter can be used. Examples of suitable aromatic amine promoters are those of formula:

I _ I NR2R3

  o RI is -H, -CH3 or -CHO, and R2 and R3 are independently chosen from -CH3, -CH2CH3 or -CH2CH2OH. Preferred amine promoters

  are aniline, N, N-dimethylaniline, N, N-diethylaniline, N, N-

  di (hydroxyethyl) aniline, N, N-dimethyl-p-toluidine, N, N-

  di (hydroxyethyl) toluidine and p-dimethylaminobenzaldehyde.

  If present, the promoters are generally used in amounts of between 0.01% and 2% by weight, based on the weight of the

total composition.

  Accelerators are generally polyvalent metallic compounds including salts and complexes which accelerate the action of a

  organic hydroperoxide and promote oxidative surface hardening.

  These salts or metal complexes are generally known in the art as "drying" or "drying" agents. The most useful polyvalent metal salts are metal salts of naphthenic acids, resinic acid, abietic acid or aliphatic acids, comprising from 7 to 30 carbon atoms, such as 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and monotannic acid. The polyvalent metal compound of the salts is generally chosen from calcium, copper, zinc, magnesium, manganese, lead, cobalt, iron, vanadium and zirconium. A metal salt

  single polyvalent or mixtures of these salts can be used.

  The preferred accelerator is cobalt octoate.

  If present, accelerators are typically used in amounts of between 0.01% and 2% by weight based on the weight of the

total composition.

  In addition to the components mentioned above, the compositions of the present invention may include other ingredients known to those skilled in the art. These components include, but are not limited to. pigments such as titanium dioxide, retarders such as 2,4-pentanedione, corrosion inhibitors such as zinc phosphate, fluids and leveling agents; rheology modifiers such as fumed silica; wetting agents; dispersants; anti-foaming agents: stabilizers against ultraviolet; reinforcements with fibers such as kevlar or glass, inhibitors such as hydroquinone, anti-foaming agents, antimicrobial adjuvants, antioxidants, conductive fillers such as graphite or carbon, and mineral fillers such as sand, ceramics, mica,

  glass flakes and metallic particles.

  The novolak vinyl ester resin compositions of the present invention, after curing at room temperature, give materials having excellent chemical resistance to acids, alkalis and aggressive solvents such as methylene chloride. In addition, the compositions have viscosities suitable for easy formulation in corrosion resistant materials such as adhesives, fiber reinforced plastic structures, laminates, molding compositions, encapsulants, coatings protectors, trim and floor coverings, to protect steel, iron, concrete and other substrates from corrosion, without the health and environmental concerns associated with compositions containing styrene monomers. The compositions of the present invention are particularly useful in the formation of protective linings for primary and secondary containment on glass substrates.

steel and concrete.

  As will be readily understood from the examples and test results included herein, the resin compositions of the present invention are greatly improved in terms of corrosion resistance compared to conventional high chemical resistance novolak resins. It is assumed that these effects are obtained by the synergistic action between the ac, 3-ethylenically unsaturated novolak vinyl ester resin and the monomer to

  unsaturation a. 3-ethylenic multifunctional.

  The examples below are compositions according to the present

  invention, of course, in no way limiting its scope.

EXAMPLE 1

  A resin composition comprising the components of Table 1 is prepared by mixing IRR1022 (novolak vinyl ester resin) with SR206 (a difunctional methacrylate monomer) and COPAC (6% cobalt), using conventional mixing methods. Cumene hydroperoxide curing agent is added just before

2 5 the application.

TABLE 1

  Resin component: Amount of a-ethylenically unsaturated novolak resin (IRR 64.74 g 1022, produced by UCB Chemical Co .. Radcure Division) Ethylene glycol dimethacrylate (SR206, produced by 34.86 g Sartomer) COPAC (naphthenate cobalt at 6%, produced by Huls 0.40 g America) Curing agent: 2.0 g cumene hydroperoxide (80%. produced by Aztec) __ A comparison composition comprising the components indicated in table 2 is prepared by mixing DERAKANE (novolak vinyl ester resin), dimethylaniline, 12% cobalt, and MTBHQ (methyl-tert-butylhydroquinone), using conventional mixing methods. Cumene hydroperoxide (2.0 g) is added just before application.

TABLE 2

  Resin component: Quantity Novolak vinyl ester resin containing 36% 99.61 g styrene (DERAKANE 470.36, produced by Dow Chemrnical) Dimethylaniline (DMA) 0.07 g Methyl-tert-butylhydroquinone (MTBHQ) 0.08 g Cobalt at 12% 0.24 g Curing agent: 2.0 g cumene hydroperoxide (80%, produced by Aztec) Moldings 38 mm in diameter by 3 mm thick are made from each of the two compositions above. The molds are allowed to cure at room temperature for seven days, then immersed in various chemicals at several temperatures to compare chemical resistance. The percentage change in weight after 3. 7, 14 and 28 days at 21 C (70 F), 38 C (100 F) and 60 C (140 F), for casts immersed in various chemical substances, is reported in

table 3.

TABLE 3

  Example 1 Comparative example I 21 C (70 F) 7 days 14 days 28 days 7 days 14 days 28 days Acetone 0.686 0.654 1.122 8.039 11.035 20.769 Methanol 1.467 1.721 2.428 5.380 7.890 13.367 Methylene chloride 2.936 3.614 4.800 42.529 43.552 43.822 Toluene --0.33 0.12 0.21 N-methylpyrrolidinone 0.137 0.241 0.409 1.522 1.682 2.041 30% nitric acid 0.527 0.735 1.145 1.404 1.554 1.715 50% nitric acid 0.887 0.938 1.001 1.740 0.848 1.170 30% sodium hydroxide -0.110 0.038 0.255 -0.037 0.045 0.101 Sodium hydroxide % -0.533 -0.642 -0.648 -0.336 -0.496 -0.562 30% sulfuric acid 0.463 0.493 0.924 0.798 0.851 1.021 50% sulfuric acid 0.020 -0.014 0.020 0.040 0.115 0.029 98% sulfuric acid - 9.027 -11.899 -14.419 -38.974 - 57,872 destroyed 38 C (100 F) 7 days 14 days 28 days 7 days 14 days 28 days N-methylpyrrolidinone 0.462 0.58 0.726 2.271 5.356 4.014 30% nitric acid 0.897 1.284 1.585 0.962 1.195 1.306 Nitric acid 50% 0.931 1.153 1.290 1.576 1.926 3.034 30% sulfuric acid 0.687 1.184 1.481 0.538 0.837 1.113 50% sulfuric acid -0.016 0.259 0.447 0.017 0.232 0.243 98c sulfuric acid% -18.881 -21.453 - 21.653 destroyed C (140 F ) 3 days 7 days 14 days 3 days 7 days 14 days N-methylpyrrolidinone 0.659 0.872 1.183 4.475 4.122 - 7.729 30% nitric acid 1.338 1.617 1.680 0.901 1.061 1.010 50% nitric acid 0.958 1.080 1.401 4.002 9, 541 25.322 0.33 0.302 0.33 0.837 0.924 50% sulfuric acid c -0.134 -0.043 0.230 -0.161 -0.093 -0.040 98% sulfuric acid -29.219 destroyed destroyed As can easily be understood from this example, in particular from after the data in Table 3, the resin composition of the present invention is greatly improved in terms of resistance to

  corrosion compared to conventional vinyl ester novolak resin vis-à-vis

  vis organic solvents such as acetone and methanol, chlorinated solvents such as methylene chloride, concentrated sulfuric acid, and

  50% nitric acid at elevated temperatures.

EXAMPLE 2

  A coating composition according to the present invention comprising the components of Table 4 is prepared as follows:

TABLE 4

  Resin component: Quantity (grams) Ao3-ethylenically unsaturated novolak resin (IRR 48.85 1032) 1,4-Butanediol dimethacrylate (SR214B, produced by 26.31 Sartomer) Titanium dioxide 3.00 Defoaming agent (BYK A515, produced by BYK Chemrnie) 0.24 Anti-foaming agent (Coroc A-22- 1 - M, produced by Dow 0.36 Comrning) Smoked silica 1.80 Polar agent (BYK R605, produced by BYK Chemrnie) 0.45 Pigment dispersion (Black Tinting CC844-9960, 0.20 produced by American Colors) Propoxylated alcohol (Arcal AP 1375, produced by Arco 3, 00 Chemical Co.) Glass flakes (1/64 "(0.04 cm) 15.00 Cobalt at 12% in mineral spirits 0.40 2.4-pentadione 0.07 Hydroquinone 0.02 Silane coupling agent (Z-6030, produced by Dow 0.30 Corning) Curing agent: Hydroperoxide cumene (80%, produced by Aztec 2.00 Industries) The IRR 1032 resin is stored in a warm room, at approximately 90 F (32 C), for 24 hours, to reduce its viscosity, and cha stored in a clean, dry mixing container. Fifteen percent of the total amount of SR214B required is then added, and the mixture is mixed until it is homogeneous. Titanium dioxide is added slowly and dispersed until a Hegman grind of 7 is obtained. The following materials are then added with stirring: Byk A515, Coroc A-2201-M, Black Tinting CC844- 9960, Arcal AP 1375, hydroquinone, Z-6030 and fumed silica. The mixture is mixed until it is homogeneous. Then, BYK R605 is added and an increase in the viscosity and thixotropy of the resin is observed. The 1/64 "glass flakes are then added, and the mixture of the remaining SR214B monomer, 12% cobalt in mineral spirits, and 2,4-pentanedione is premixed. The resulting mixture is mixed until homogeneous. The viscosity of the resin component is 3200 to 3800 cps at 77 F (25 C), measured on a Brookfield viscometer. An accelerated pot life test at 120 F (49 C) suggests that the resin component has a pot life of more than 9 months, the flexural strength of the composition, measured on a Gardner Co. flexometer, is 24 mil (500 to 600 microns). the catalyzed composition is poured into a mold and allowed to cure for seven (7) days The tensile strength of the cured composition is 3600 psi (24.8 Mpa), determined according to ASTM D-638 and the strength at flexion is 5200 psi (35.8 MPa),

determined according to ASTM D-790.

EXAMPLE 3

  A resin composition comprising the components of Table 5 is prepared as in Example I. A comparative example is prepared, comprising the components of Table 6, as well as a control, prepared using

  of the components indicated in table 7.

TABLE 5

  Resin component: Q Quantity (erammes) Novolac resin unsaturated a, p-ethylene 65.00

(IRR 1022)

  1,4-Butanediol dimethacrylate (SR214B, produced 35.00 by Sartomer) Cobalt at 12% in mineral spirits 0.40 Aeent of hardening: Cumene hydroperoxide 2.00 TABLE 6 (Comparative example) Resin component: Quantity (grams) Novolac resin unsaturated a, 4-ethylenic 65.00

(IRR 1022)

  Styrene 35.00 Cobalt at 12% in mineral spirits 0.40 Curing agent: Cumene hydroperoxide 2.00 TABLE 7 (control) Component of the resin: Quantity l (rammes) Novolak c.-ethylenically unsaturated resin 100.00

(IRR 1022)

  Cobalt at 12% in mineral spirits 0.40 Curing agent: cumene hydroperoxide 2.00 Five moldings (38 mm in diameter by 3 mm thick) are made from each resin formulation, they are left to harden to 21 C (70 F) for three days and immersed in methylene chloride. Weight change data as an average percentage is summarized in the

table 8, below.

TABLE 8

  3 days 7 days 14 days Example 3 3.50% 3.88% 4.67% Example 30.98% 45, 67% destroyed comparative 3 Witness 3.49% 4.78% 6.70% The results of the Example 3, in particular the data in Table 8, clearly demonstrate that the resin composition of the present invention

  containing the bifunctional monomer, i.e. 1, 4- dimethacrylate

  butanediol, is superior to the comparison composition which contains the monofunctional monomer, that is to say styrene, as regards the resistance to methylene chloride. Although the performance of the control (no reactive monomer) is similar to that of the present invention as regards the resistance to methylene chloride, the viscosity of the resin component of the control was greater than 90,000 cps at 21 C (70 F ), measured by a Brookfield viscometer, making it difficult to apply using conventional tools such as a roller, brush or spraying equipment, while the viscosity of the resin component of the composition according to the present invention was less than 1000 cps at 21 C (70 F),

  2 0 measured by a Brookfield viscometer.

EXAMPLE 4

  A resin composition according to the present invention is prepared and molded as in Example 3. Two comparative moldings are made from commercially available resin compositions. "Comparative Molding A" is a composition based on novolak vinyl ester resin and "Comparative Molding B" is a composition based on epoxy novolac. The resulting moldings are immersed in various chemicals, at different temperatures to compare chemical resistance. Weight variation after 7, 14 and 28 days at 21 C (70 F), 38 C (100 F) and 60 C (140 F), for castings immersed in

  various chemicals are reported in Table 9.

  As can easily be seen from Example 4, in particular from the data in Table 9, moldings prepared from the compositions of the present invention are far superior to moldings prepared from the resin of commercially available vinyl ester novolak in terms of corrosion resistance to organic solvents, i.e. acetone, methanol and methylene chloride, and to moldings prepared from the composition commercially available epoxy novolac resin in terms of resistance to corrosion by methylene chloride and 50% nitric acid. While the corrosion resistance of moldings prepared from the composition according to the present invention is generally comparable to that of coatings prepared from both novolak vinyl ester resin and epoxy novolak resins in in terms of resistance to acids and bases, it is far superior in terms of resistance to corrosion by concentrated sulfuric acid, compared with

  novolak vinyl ester molds.

TABLE 9

  Example Molding Molding 4 comparat. To appear. BF (21 C) 7 days 14 days 28 days 7 days 14 days 28 days 7 days 14 days 28 days Acetone 0, 686 0.654 I, 122 8.039 11.035 20.769 without data Methanol 1.467 1.721 2.428 5.380 7.890 13.367 without data Methylene chloride 2.936 3.614 4.800 42.529 43.552 43.822 destroyed in I day -0.033 0.125 (0.336 0.141 0.217 0.447 0.007 0.102 0.227 50% Nitric Acid 0.887 0.938 1.001 1.74 0.848 1.170 destroyed Sodium hydroxide at -,)% -0.533 -0.642 -0.648 -0.336 -0.496 -0.562 -0.142 -0.174 - 0.199 Sulfuric Acid at 50)% 0.02 () -0.014 0.020 0.040 0.115 0.029 0.852 1.313 1.828 Sulfuric Acid Concentrate 9.027 -11.90 -14.42 -38.97 -57.87 destroyed 1.494 0.746 0.576 F (38 C) 7 days 14 days 28 days 7 days 14 days 28 days 7 days 14 days 28 days 50% Nitric Acid 0.931 I, 153 1.290 1.576 1.926 3.034 destroyed in I day 50% Sodium Hydroxide -0.293 - 0.210 without data 0.288 -0.348 without data 0.136 0.070 0.076 Sulfuric Acid at 50% -0.016 0.259 0.447 0.017 0.232 0.243 1, 759 1,464 3,166 Sulfuric Acid Concentrate -18.88 -21.45 -21.65 destroyed 0.351 -0.430 -0.906 F (60 C) 3 days 7 days 14 days 3 days 7 days 14 days 3 days 7 days 14 days Nitric acid at 50% 0.958 1.080 1.401 4.002 9.541 25.322 destroyed in 8 hours 50% Sodium Hydroxide 2,325 4,580 7,000 -0.209 -0.143 0.014 -0.215 -0.293 -0.334 50% Sulfuric Acid -0.134 -0.043 0, 230 -0.161 -0.093 -0.040 2.047 2.697 3.309 Sulfuric Acid Concentrate -29 .22 destroyed destroyed -30.71 destroyed

Claims (10)

  1. A curable composition comprising (i) one or more novolak vinyl ester resin (s), the one or more novolak vinyl ester resin (s) containing at least two unsaturated sites a , f-ethylenic per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two ao, ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixtures of these compounds.   2. A curable composition according to claim 1, wherein the novolak vinyl ester resin has a calculated molecular weight of 300 to 5,000 g / mole, preferably 1,000 to 3,000 g / mole, more preferably still from 2,200 to 3,000 g / mole.   3. A curable composition according to claim 1 or claim 2, wherein the novolak vinyl ester resin has a functionality greater than 2.5.   4. A curable composition according to any one of   claims 1 to 3, wherein the reactive monomer is an acrylate or a   methacrylate containing at least two α, 1-ethylenically unsaturated sites per molecule.   5. A curable composition according to any one of   claims 1 to 4, wherein the reactive monomer has a weight   molecular weight calculated from 150 to 1500 g / mole, better still from 200 to 300 g / mole. 6. A curable composition formed by the combination of: (i) one or more novolak vinyl ester resin (s), the novolak vinyl ester resin (s) containing at least two at, -ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two α, 3-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixtures of these compounds. 7. A method of forming a coating on a substrate comprising the following steps: A) application of a curable composition on a substrate, said curable composition comprising (i) one or more resin (s) of novolak vinyl ester (s), the novolak vinyl ester resin (s) containing one or more α, 4-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two α, 3-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or a mixture of these compounds; and   B) allow the hardening of said curable composition.   8. A method according to claim 7, wherein the substrate is a floor covering substrate.   9. A method according to claim 7, wherein the substrate   2 5 includes steel, iron or concrete.   10. A substrate covered with the coating produced by the The method of claim 7.