CA2193423A1

CA2193423A1 - Novolac vinyl ester compositions

Info

Publication number: CA2193423A1
Application number: CA002193423A
Authority: CA
Inventors: Frank V. Apicella; Nancy A. Dulzer
Original assignee: Individual
Current assignee: SGL Acotec GmbH
Priority date: 1995-12-21
Filing date: 1996-12-19
Publication date: 1997-06-22
Also published as: JPH09216923A; GB9626302D0; FR2742762B1; CH691126A5; IT1290158B1; DE19652812B4; DE19652812A1; MX9606714A; FR2742762A1; ITRM960887A1; GB2308375A; ITRM960887A0; GB2308375B

Abstract

A thermosetting novolac vinyl ester resin composition useful for forming coatings, linings and floorings for protecting steel, iron, concrete and other substrates from the corrosive action of acids, alkalis, and aggressive solvents.

Description

Case No. 154-0301 2 1 9 3 4 2 3 NOVOLAC VINYL ESTER COMPOSITIONS
~ BACKGROUND OF THE INVENTION

1. Field of the Invention The present invention relates to thermosetting compositions which cure at room telllpel~lulc to providç coatings having exceptional chemical resistance to acids, alkalis, and aggressive solven~s such as methylene chloride. More particularly, the invention is S directed to a thermosetting novolac vinyl ester resin composition useful in the formulation of protective coatings, linings and floorings for protecting steel, iron, concrete or other substrates from corrosion.

2. Description of the Related Art Thermosetting novolac polymer resins are often used in the formulation of anti-corrosive coatings since they are significantly more resistant to chemical attack than many other types of thermosetting polymers. The most common types of novolac resins employed include novolac epoxy and novolac vinyl ester resins.
Novolac-based epoxy resins are produced by reacting a novolac resin with an 15 epichlorohydrin. While these thermosetting resins, when amine cured at room temperature, result in cured materials having excellent resistance to alkalis; salts; weak, non-oxidizing acids; and some weak solvents, they generally exhibit poor resistance to organic acids, concentrated inorganic acids (with the exception of 98% sulfuric acid), oxidizers and aggressive solvents such as methylene chloride. Improvements in their 20 chemical resistance can generally be achieved by using elevated telllpelatures during the curing process. However, this is impractical in many situations since it is difficult to heat large areas uniformly, not to mention the added time and expense associated with the heating process. Moreover, slow cure rates, short work times and high viscosities are additional shor. omings associated with using epoxy novolac resins in the 25 formulation of anti-corrosive coatings.
The commercially-available novolac vinyl ester resins are methacrylated novolac resins produced by the reaction of a m~th~crylic acid with an epoxy novolac resin.
These resins are cured by a free radical mechanism, usually initi~ted by peroxides, to produce a hardened material. Novolac vinyl ester resins have been used for many years Case No. 154-0301 2 1 9 3 4 2 3 -as corrosion resistant coatings as they generally exhibit good resistance to many chemicals including acids, alkalis, hypochlorites and many solvents. However, they generally exhibit poor resistance to organic solvents, particularly chlorinated organic solvents such as methvlene chloride, and to concentrated sulfuric acid. Moreover, the 5 novolac vinyl ester re- ins are viscous materials which makes them difficult to handle.
The commercially-ava lable novolac vinyl ester resins are generally dissolved in a styrene monomer to rf duce viscosities. However, this results in highly odorous and fl~mm~hle compositiohs which are unattractive from both health and an environmental standpoints. In addition, the novolac vinyl ester resins have a short shelf life, generally 10 no longer than 6 months and usually less than 3 months.
U.S. Patents Nos. 4,363,889 and 4,443,503 disclose anti-corrosive coating co".posilions comprising an unsaturated polyester resin, glass flakes of a specific size, a ketone peroxide and a hydroperoxide and/or peroxy ester. All known unsaturatedpolyesters are described as being useful in the coating compositions including polyester 15 resins obtained by reacting an epoxy resin with an a,~-monoethylenically unsaturated monocarboxylic acid (-ee column 4, lines 19-52). The polyester resins may be diluted with polymerizable monomers which include both mono-, di- and multifunctional monomers including ethylene glycol dimethacrylate and trimethylol propane trimethacrylate (see paragraph bridging columns 4 and 5) although styrene is the only 20 monomer specifically used in the examples. The patents offer no suggestion as to the specific combination of a novolac vinyl ester resin with a di- or multifunctional a"B-ethylenically unsaturated monomer or that such a combination would result in cured coatings having enh~n~ed anti-corrosive properties relative to other unsaturated polyester resin/monomer col~-posilions.
U.S. 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 the specific combination of a novolac vinyl ester resin with a di- or multifunctional a,~-etlylenically unsaturated monomer nor any hint or suggestion that such a combination would provide superior properties relative to other unsaturated 30 polyester resin/monorner combinations.

Case No. 154-0301 2 ~ 93423 SUMMARY OF THE INVENTION
According to the present invention, there has been found a novolac vinyl ester resin-based colllposilion which cures at room tellll)eldture to provide a material having improved resistance to the corrosive effects of organic solvents such as acetone, 5 methanol, chlorinated olvents, e.g. methylene chloride, as well as acids such as concentrated sulfuric _cid and 50% nitric acid, relative to materials resulting from the cure of commercially--.vailable epoxy and novolac vinyl ester-based anti-corrosive compositions. In addition, the compositions of the present invention generally have a longer shelf-life (accelerated shelf-life study at 120F (49C) indicating a shelf-life in 10 excess of 9 months) relative to traditional novolac vinyl ester compositions.Furthermore, the resin/monomer components of the present invention exhibit low viscosities without the need for styrene and they avoid the health and environmental shortcomings of traditional novolac vinyl ester resins (and therefore do not require fl~mm~ble or corrosivo hazard labels).
Specifically, tle present invention provides a curable composition comprising (i) one or mor~ novolac vinyl ester resins, the novolac vinyl ester resin(s) containing at least two a, ~-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers cont~il-i1-g at least two a,~-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixtures thereof.
In another embodiment, the invention provides a composition formed by combining the above tnaterials.
In a still furth, r embodiment, the invention provides for a method of forming acoating on a substrate comprising the steps of A) applying a curable composition on a substrate, said curable composition comprislng (i) one or more novolac resin(s), the novolac resin(s) cont~ining at least two a, ,I~-ethylenically unsatu-ated sites per molecule, (ii) one or more reactive monomers, the reactive monomers cont~ining at least 30 two a,~-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixture thereof; and B) allowing said curable composition to harden.

Case No. 1 54-0301 2 1 9 3 4 2 3 The invention additionally provides for substrates, e.g. flooring substrates and lining substrates, overlaid with a coating produced by the aforementioned method.

DETAILED DESCRIPTION OF THE INVENTION
The novolac v nyl ester resins useful in the present invention preferably have aS calculated molecular weight of 300 to S,000 g/mole, more preferably l,000 to 3,000 g/mole, and contain, on average, at least two terminal a,~-ethylenically unsaturated groups per molecule. If the molecular weight is less than 300 g/mole, the resulting cured materials tend to be brittle and good results are difficult to achieve because the brittle coatings are prope to cracking and generally exhibit poor impact strength. Since lO an increase in molecular weight generally increases the viscosity of the resin, thus making the materials less workable, it is preferable to use materials with molecular weights of S,000 g/mole or less. The pl~fell~d novolac vinyl ester resin has a calculated molecular weight range of 2200-3000 g/mole, a functionality of greater than 2.5 and a viscosity gr~ater than 90,000 cps when measured @ 25C (77F) by a l S Brookfield viscometer.
The novolac vinyl ester resins useful in this invention are prepared by reactingan a"B-ethylenically unsaturated monocarboxylic acid with an epoxy novolac resin.
The epoxy novolac resin can be synthesized by reacting phenol or a substituted phenol, e.g. an alkyl phenol such as a cresol, with formaldehyde in the presence of an acidic or 20 alkaline catalyst and further reacting the resulting novolac or cresol compound with epichlorohydrin or methyl epichlorohydrin. Useful a,~-ethylenically unsaturated monocarboxylic acids include acrylic acid, methaerylic acid, crotonic acid, monoesters of unsaturated polycarboxylic acids, and monoesters of maleic acid. The unsaturated acids and monoesters may be used singly or as a mixture of two or more of them.
The novolac vinyl ester resin is present in the compositions of the present invention in an amount ranging from 20% to 90%, preferably 30% to 60%, by weightbased on the weight of the entire colllposition.
The reactive rr onomers useful in this invention are acrylates and methacrylatescontaining at least two a"B~thylenically unsaturated sites per molecule, having low viscosity, generally le-s than 500 cps as measured by a Brookfield viscometer at 25C
(77F) and preferably less than 200 cps, and having a flashpoint greater than 60C

Case No. 1 54-0301 2 1 9 3 4 2 3 (140F) as measured qy the Pensky-Martins closed cup method. Preferred reactive monomers have a calculated molecular weight of 150 to 1500 g/mole, more preferably 200 to 300 gtmole. 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 5 environmental standpoint. If the molecular weight is in excess of 1500 g/mole, the materials tend to be too viscous, resulting in monomers which are less workable and which have reduced d ssolving power for the novolac vinyl ester resin. Suitable monomers include, but are not limited to, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylol 10 propane triacrylate, ethoxylated trimethylol propane triacrylate, ethylene glycol fiim~th~rrylate, 1,3-butylene glycol diacrylate, and diethylene glycol dimethacrylate .
These monomers can be used singly or as a mixture of two or more of them. The methacrylates are generally preferred over the acrylates as the resulting coatings tend to exhibit improved corrosion resistance to alkalis.
The reactive monomers may contain other groups which impart certain characteristics to the final cured material. For example, a"B-ethylenically unsaturated urethanes or silicones may be used to increase the flexibility of the cured material; a"B-ethylenically unsaturated monomers Co~ g fluorine may be used to impart improvedoil and water repellency, lower surface energy, and enhanced resistance to certain 20 chemicals; and a,~-ethylenically unsaturated monomers containing silanes may be used to improve adhesion and/or surface wetting pr~pel~ies.
The reactive monomers are present in the compositions in an amount ranging from 10% to 90%, preferably 20% to 60% by weight, based on the weight of the entire composition.
The organic peroxide or hydroperoxide curing agents useful in the present invention may be any organic peroxide or hydroperoxide known in the art. The organic peroxides and hydrop~roxides decompose, producing free radicals which initiate the polymerization reaction. Specific examples of useful peroxides and hydroperoxides are those which contain f-om 3 to 18 carbon atoms, such as benzoyl peroxide, tert-butyl 30 pell,ellzoate, methyl ehyl ketone peroxide, dilaurylperoxide, di(t-butylcyclohexyl) peroxide, bis(l-hydroxycyclohexyl)peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methy ethyl ketone hydroperoxide, diisopropylbenzene hydroperoxide Case No. 154-0301 2 1 9 3 4 2 3 `

and mixtures thereof.
The peroxide, hydroperoxide or combination thereof, if used, is present in the co.llposilion in an amount ranging from about 0.2% to 10.0%, preferably 1% to 4%, by weight based on the weight of the entire composition. The preferred curing agent is S cumene hydroperoxide.
Decomposition of the curing agent can be accomplished by heat or by the use of promoters and/or accelerators which accelerate the decomposition at a given le.~.pe.~ture. When curing the compositions of the present invention at temperatures below 50C (122F), it is generally ~-~fe,lcd to use promoters and/or accelerators.
The promoters most commonly employed are aromatic ~mines, although any promoter can be used. Examples of suitable aromatic amine promoters are those having the formula:

Rl [~NR2R3 wherein Rl is -H, -CH3 or -CHO and R2 and R3 are independently selected from -CH3 -CH2CH3 or -CH2CH20H. F`lefelled 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 ?romoters are generally used in amounts of from 0.01% to 2% by weight based on the weight of the entire composition.
The acceleratots are generally polyvalent metal compounds including salts and complexes which accelerate the action of an organic hydroperoxide and promote oxidative surface cure. These metal salts or complexes are generally known in the art as "siccatives" or "driers". The most useful polyvalent metal salts are metal salts of naphthenic acids, resinic acid, abietic acid or aliphatic acids having from 7 to 30 carbon 25 atoms such as 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and monotannic acid. The polyvalent metal co..lponent of the salts is generally selecte~l from calcium, copper, zinc, magnesium, m~ng~nese, lead, cobalt, iron, vanadium, and z rconium. A single polyvalent metal salt or mixtures thereof may be used. The plc;fe.lcd accelerator is cobalt octoate.
If present, the accelerators are generally used in amounts of from 0.01% to 2%

Case No. 154-0301 2 1 9 3 4 2 3 by weight based on the weight of the entire composition.
In addition to ~he abovementioned components, the compositions of the present invention may include other ingredients known to those skilled in the art. Theseinclude, but are not limited to, pigments such as titanium dioxide; retarders such as 2,4-5 pentanedione; corrosion inhibitors such as zinc phosphate; flow and leveling additives;rheology modifiers such as fumed silica; wetting agents; dispersants; defoamers;
ultraviolet stabilizers; fibre reinforcements such as kevlar or glass; inhibitors such as hydroquinone; defoamers; antimicrobial additives; antioxidants; conductive fillers such as graphite or carbon, and inorganic fillers such as sand, ceramics, mica, glass flakes 10 and metallic particles.
The novolac vinyl ester resin compositions of the present invention, after room temperature curing, re ult in materials having excellent chemical resistance to acids, alkalis, and aggressiv~ solvents such as methylene chloride. In addition, the compositions have suitable viscosities for easy formulation into corrosion-resistant 15 materials such as adhesives, fibre-reinforced plastic structures, l~min~tes, moulding compositions, encapsulates, protective coatings, linings, and floorings for protecting steel, iron, concrete and other substrates from corrosion, without the health and environmental concerns associated with compositions cont~ining styrene monomers.The compositions of the present invention are particularly useful in forming protective 20 linings for primary and secondary containment over steel and concrete substrates.
As will readily be understood from the examples and test results included herein, the resin compositions of the present invention are highly improved in corrosionresistance over conventional highly chemical resistant novolac resins. It is believed that these effects are attained by synergistic action between the a,~-ethylenically unsaturated 25 novolac vinyl ester resin and the multifunctional a,~-ethylenically unsaturated monomer.
The following are examples of compositions according to the present invention, but of course, should not be construed as in any way limiting its scope.

EXAMPLF I
A resin composition comprising the components in Table 1 is prepared by 30 mixing IRR1022 (novolac vinyl ester resin) with SR206 (a difunctional m~th~-~rylate monomer) and COPA'' (6% cobalt) using conventional blending methods. The cumene Case No. 154-0301 2 1 9 3 4 2 3 hydroperoxide curing agent is added just prior to application.

TABI,E 1 Resin Component: Amount Sa"B-Ethylenically unsaturated novolac resin (IRR1022, manufactured by UCB Chemical Co., Radcure Division)64.74 grams Ethylene glycol dimethacrylate (SR206 manufactured by Sartomer) 34.86 grams COPAC
10(6% cobalt naphthenate manufactured by Huls America)0.40 grams Cur;n~ A~ent:
Cumene hydroperoxide (80%, manufactured by Aztec) 2.0 grams A comparative composition comprising the components listed in Table 2 is 15 prepared by mixing the DERAKANE (novolac vinyl ester resin), dimethylaniline, 12%
cobalt, and MTBHQ (methyl tert-butylhydroquinone) using conventional blending methods. The cumene hydroperoxide (2.0 g) is added just prior to application.

~esin Component: Amount 20Novolac vinyl e ter resin containing 36% styrene (DERAKANE 470.36 manufactured by Dow Chemical) 99.61 grams Dimethylaniline (DMA) 0.07 grams Methyl tert-butylhydroquinone(MTBHQ), 20% 0.08 grams 12% cobalt 0.24 grams 25Curin~ A~ent:
Cunene hydroperoxide (80%, manufactured by Aztec) 2.0 grams 38mm ~i~met~Lr by 3mm thick castings are made from each of the above two compositions. The c~ctingc are allowed to cure at room temperature for seven days, 30 then immersed in various chemicals at several temperatures to compare chemical Case No. 154-0301 2 1 9 3 4 2 3 resistance. The percent weight change after 3, 7, 14 and 28 days at 21C (70F), 38C
(100F) and 60C (140F) for the c~ting~ immersed in the various chemicals are reported in Table 3.

Example 1 Comparative Example 1 21C (70F) 7 Day 14 Day 28 Day 7 Day 14 Day 28 Day Acetone 0.686 0.654 1.122 8.039 11.035 20.769 M: ,anol 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 -0.033 0.125 0.336 0.141 0.217 0.447 N-Methyl Pyrrolidinon~ 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 50% Sodium Hydroxide-0.533 -0.642 -0.648 -0.336 -0.496 -0.562 lS 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 Destroy ed 38C (100F) 7 Day 14 Day 28 Day 7 Day 14 Day 28 Day N-Methyl Pyrrolidinone 0.462 0.588 0.726 2.271 5.356 4.014 30% Nitric Acid 0.897 1.284 1.585 0.962 1.195 1.306 50% Nitric Acid 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 98% Sulfuric Acid -18.881 -21.453 -21.653 Destroyed 60C (140F) 3 Day 7 Day 14 Day 3 Day 7 Day 14 Day N-Methyl Pyrrolidinone 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 30% Sulfuric Acid 1.093 1.263 1.402 0.834 0.837 0.924 50% Sulfuric Acid -0.134 -0.043 0.230 -0.161 -0.093 -0.040 98% Sulfuric Acid -29.219 Destroyed Destroyed Case No. 154-0301 2 1 9 3 4 2 3 .

-As can be readily understood from this example, particularly the data in Table 3, the resin composition of the present invention is highly improved in corrosion resistance over the traditional vinyl ester novolac resin with regards to organic solvents such as acetone and methanol, chlorinated solvents such as methylene chloride, concentrated 5 sulfuric acid, and 50% nitric acid at elevated telllpcl~lul~s.

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

Resin Component Amount (grams) a"B-Ethylenically unsaturated novolac resin (IRR1032) 48.85 1,4-Butanediol ~imP-h~crylate (SR214B manufactu ~ed by Sartomer) 26.31 Titanium Dioxide 3.00 Defoamer (BYK A515, manufactured by BYK Chemie) 0.24 Defoamer, (Coroc A-22-1-M, manufactured by Dow Corning) 0.36 Fumed Silica 1.80 Polar Agent (BYK R605, manufactured by BYK Chemie) 0.45 Pigment Dispersion (Black Tinting CC844-9960, manufactured 0.20 by American Colors) Propoxylated alcohol (Arcal AP 1375, manufactured by Arco 3.00 Chemical Co.) Glass flakes (1/64 irch (0.04cm)) 15.00 12% Cobalt in mine-al spirits 0.40 2,4-pentanedione 0.07 Hydroquinone 0.02 Silane Coupling Ag~nt (Z-6030, manufactured by Dow Corning ) 0.30 Case No. 154-0301 2 1 9 3 4 2 ~

TABLE 4 (contd.) Curing Agent Cumene hydroperox de (80%, manufactured by Aztec Industries) 2.00 The IRR 1032 resin is stored in a hot room at approximately 90F (32C) for 24 hours 5 to reduce its viscosity and charged into a clean, dry mixing vessel. Fifteen percent of the total amount o SR214B required is then added and the mixture blended until homogenous. The lil .niulll dioxide is added slowly and dispersed until a Hegman grind of 7 was achieved. The following m~teri~ls are then added with stirring: Byk A515, Coroc A-2201-M, Bl ck Tinting CC844-9960, Arcal AP 1375, Hydroquinone, Z-6030, 10 and the fumed silica. The mixture is blended until homogenous. Next, the BYK R605 is added and an increase in resin viscosity and thixotropy is observed. The 1/64 inch glass flakes are t~en added, followed by a pre-blended mixture of the rem~ining SR214B monomer, 12% cobalt in mineral spirits, and the 2,4-pentanedione. The rt;sulting mixture is blended until homogenous.
15 The viscosity of the r~sin coll.ponent is 3200-3800 cps @ 77F (25C) as measured on a Brookfield Viscomete~. An accelerated shelf-life test @ 120F (49PC) suggests the resin component has a shelf life greater than 9 months. The sag resistance of the composition, as measured on a anti-sag meter from Gardner Co., is 20-24 mils (500-600 microns). The catalyzed composition is poured into a mould and allowed to cure for 20 seven (7) days. The tensile strength of the cured composition is 3600 psi (24.8 MPa), determined according to ASTM D-638 and the Flexural Strength is 5200 psi (35.8 MPa), determined according to ASTM D-790.

A resin composition comprising the colllpol1ellL~, in Table S is prepared as in 25 example 1. A comparative example is prepared comprising the components in Table 6, as well as a control prepared using the components listed in Table 7.

Case No. 154-03012 1 9 3 4 2 3 . .

Resin Component: Amount (prams) a,~-Ethylenically unsaturated novolac resin (IRR1022) 65.00 1,4-butanediol dirnethacrylate (SR 214B manufactured by 35.00 5 Sartomer) 12% cobalt in mineral spirits 0.40 Curin~ Apent:
Cumene hydroperoxide 2.00 TABLE 6 (Comparative Example) 10Resin Component: Amount (prams) a,~-Ethylenically unsaturated novolac resin (IRR1022) 65.00 Styrene 35.00 12% cobalt in mineral spirits 0.40 Curin~p Apent:
15Cumene hydroperoxide 2.00 TABLE 7 (Control) Resin Component: Amount (prams) a,~-Ethylenically unsaturated novolac resin (IRR1022) 100.00 12% cobalt in mineral spirits 0.40 20Curinp Apent:
Cumene hydroperoxide 2.00 Five castings (38 mm diameter by 3 mm thick) are made from each resin formulation, allowed to cure at 21C (70F) for three days, and then immersed in methylene chloride. The average percent weight change data is summarized in Table 8, below.

Case No. 154-0301 2 1 9 3 4 ~ 3 3 Day 7 Day 14 Day Example 3 3.50% 3.88% 4.67%
Comparative Example 3 30.98% 45.67% Destroyed Control 3.49% 4.78% 6.70%

The results of ~xample 3, particularly the data in Table 8, clearly demonstrate that the resin composition of the present invention cont~ining the difunctional monomer, i.e. 1,4-butanediol dimethacrylate, is superior to the comparative composition which contains the monofunctional monomer, i.e. styrene, with regards to methylene chloride resistance. Although the performance of the control (no reactive monomer) is similar to 10 that of the present invention regarding methylene chloride resistance, the viscosity of the resin component of th~ control was greater than 90,000 cps at 21C (70F), as measured by a Brook~leld Viscameter, making it diMcult to apply using conventional tools such as a roller, brush or spray equipment, whereas the viscosity of the resin component of the composition according to the present invention was less than 1,000 cps at 21C
15 (70F), as measured by a Brookfield Viscometer.

A resin composition according to the present invention is prepared and cast as in Example 3. Two comparative castings are made from commercially-available resin compositions. "Comp_rative A" is a novolac vinyl ester resin-based composition and 20 "Comparative B" was an epoxy novolac-based composition. The resulting castings are immersed in various chemicals at several te",pc,atures to COlllpalc chemical resistance.
The weight change af:er 7, 14 and 28 days at 21C (70F), 38C (1'`0F) and 60C(140F) for the castin-rs immersed in various chemicals are reported in Table 9.
As can be reacily seen from example 4, particularly the data in Table 9, castings 25 prepared from the conpositions of the present invention are far superior to c~cting~
prepared from the commercially-available novolac vinyl ester resin in terms of corrosion Case No. 154-0301 2 1 9 3 4 2 3 resistance to organic solvents, i.e. acetone, methanol and methylene chlorid,e and to the castings prepared from the commercially-available epoxy novolac-based composition in terms of corrosion res stance to methylene chloride and 50% nitric acid. While the corrosion resistance of the castings prepared from the composition according to the 5 present invention is g~nerally colllp~able to the co~tingc prepared from both the novolac vinyl ester re~in and the epoxy novolac-based resins in terms of resistance to acids and bases, it is far superior in terms of corrosion resistance to concentrated sulfuric acid when compared with the novolac vinyl ester-based castings.

Case No. 1 54-0301 2 1 9 3 4 ~ 3 :

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Claims

1. A curable composition comprising (i) one or more novolac vinyl ester resins, the novolac vinyl ester resin(s) containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixtures thereof.

2. A curable composition according to claim 1 wherein the novolac vinyl ester resin has a calculated molecular weight of 300 to 5,000 g/mole.

3. A curable composition according to claim 1 wherein the novolac vinyl ester resin has a calculated molecular weight of 1,000 to 3,000 g/mole.

4. A curable composition according to claim 1 wherein the novolac vinyl ester resin has a calculated molecular weight range of 2,200 to 3,000 g/mole.

5. A curable composition according to claim 1 wherein the novolac vinyl ester resin has a functionality greater than 2.5.

6. A curable composition according to claim 1 wherein the reactive monomer is anacrylate or methacrylate containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule.

7. A curable composition according to claim 6 wherein the reactive monomer has acalculated molecular weight of 150 to 1500 g/mole.

8. A curable composition according to claim 7 wherein the reactive monomer has acalculated molecular weight of 200 to 300 g/mole.

9. A curable composition according to claim 1 which additionally includes glass flakes.

10. A curable composition according to claim 1 which additionally includes an accelerator.

11. A curable composition according to claim 10 wherein the accelerator is a polyvalent cobalt salt.

12. A curable composition formed by combining (i) one or more novolac vinyl ester resins, the novolac vinyl ester resin(s) containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixtures thereof.

13. A method for forming a coating on a substrate comprising the steps of A) applying a curable composition on a substrate, said curable composition comprising (i) one or more novolac vinyl ester resin(s), the novolac vinyl ester resin(s) containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule, (ii) one or more reactive monomers, the reactive monomers containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule, and (iii) an organic hydroperoxide, a peroxide or mixture thereof; and B) allowing said curable composition to harden.

14. A method according to claim 13 wherein the novolac vinyl ester resin has a calculated molecular weight range of 300 to 5,000 g/mole.

15. A method according to claim 13 wherein the novolac vinyl ester resin has a calculated molecular weight of 1,000 to 3,000 g/mole.

16. A method according to claim 13 wherein the novolac vinyl ester resin has a calculated molecular weight of 2,200 to 3,000 g/mole.

17. A method according to claim 13 wherein the novolac vinyl ester resin has a functionality greater than 2.5.

18. A method according to claim 13 wherein the reactive monomer is an acrylate or methacrylate containing at least two .alpha.,.beta.-ethylenically unsaturated sites per molecule.

19. A method according to claim 13 wherein the reactive monomer has a calculatedmolecular weight of 150 to 1500 g/mole.

20. A method according to claim 19 wherein the reactive monomer has a calculatedmolecular weight of 200 to 300 g/mole.

21. A method according to claim 13 wherein the substrate is a flooring substrate.

22. A method according to claim 13 wherein the substrate comprises steel, iron or concrete.

23. A substrate overlaid with the coating produced by the method of claim 13.