KR20050019705A - Epoxy modified organopolysiloxane resin based compositions useful for protective coatings - Google Patents

Abstract

The present invention

Polysiloxanes of the general formula

Epoxy resins having at least one 1,2-epoxy group per molecule and having an epoxy equivalent in the range from 100 to about 5,000; And

An amino curing agent component [the curing agent component has active hydrogen capable of reacting with an epoxy group in the epoxy resin to form a polymer containing hydroxyl groups, said hydroxyl group reacting with the silanol groups of the hydrolyzed polysiloxane The present invention relates to an epoxy-modified polysiloxane composition obtained by combining with an epoxy-modified polysiloxane composition, wherein an epoxy chain polymer and a polysiloxane polymer are polymerized to form a cured epoxy-modified polysiloxane polymer composition.

Formula 1

Wherein each R ¹ is independently hydroxy, are selected from the group comprising carbon number of 6 or lower alkyl, aryl and alkoxy radicals, each R ² is independently hydrogen, a carbon number less than or equal to 6 alkyl and aryl radicals N is selected so that the molecular weight range of the polysiloxane is about 400 to 10,000.

Description

EPOXY MODIFIED ORGANOPOLYSILOXANE RESIN BASED COMPOSITIONS USEFUL FOR PROTECTIVE COATINGS}

The present invention relates to epoxy modified polysiloxane resin compositions useful for protective coatings with improved flexibility.

Epoxy coatings are well known and licensed as protective and decorative coatings for steel, aluminum, galvanized steel and concrete in the finishing sectors of maintenance, ships, buildings, buildings, aircraft and products. Epoxy-based coatings have many properties that make them desirable as coating materials. Epoxy-based coatings are readily available and can be easily applied by a variety of methods including spraying, rolling and brushing. Epoxy-based coatings adhere well to steel, concrete and other substrates, have low water vapor transmission rates, act as barriers to the ingress of water, chloride and sulfate ions, provide good corrosion protection under various atmospheric exposure conditions, and Good resistance to chemicals and solvents. The basic raw materials used to make these coatings generally comprise (a) an epoxy resin, (b) a curing agent and (c) a pigment or filler component as essential components. Epoxy-based coatings are generally excellent in protection, but have the significant disadvantage of limited gloss and color retention under atmospheric exposure.

Awareness of the environment, human health and safety has increased, and special attention has been paid to the manufacture of safe paints. Environmental regulations must be stricter to reduce emissions of hazardous solvents. Fate systems with low VOC content are needed. Currently required worldwide VOC concentrations are VOC <250 g / l with respect to application viscosity.

Some paint manufacturers have recently developed high solids (HS) paint systems with low VOC content to address environmental regulations and legislation. Examples of coatings in this regard are the industrially acceptable protective and decorative isocyanate cured polyurethane coatings. Two-part isocyanate cured polyurethane coatings combine the high potential of gloss and color retention, good chemical resistance and good mechanical properties. Currently, in some countries, the use of isocyanates is no longer allowed due to safety and health legislation. It is urgent to replace these isocyanate cured polyurethane coatings with non-isocyanate coatings (NISO). However, currently commercially available NISO coatings with high to moderate VOC content exhibit a significant decrease in performance compared to polyurethane finishes.

Since the development of new polymers and curing processes is required to realize these challenges, it seems very difficult to recombine existing NISO coatings to low VOC type using common binder technology.

Low VOC content, good flexibility, NISO coating having the mechanical properties and chemical resistance of the epoxy-based or polyurethane-based paint is urgent situation.

Epoxy-polysiloxane-based compounds are known from US Pat. Nos. 5,618,860 and 5,275,645, which disclose two-part gloss epoxy-polysiloxane compositions. While these compounds have gloss and color retention properties and very good chemical resistance, they tend to be somewhat hard and brittle. It is not suitable as a finish coating on composite structural steels that require higher flexibility. In addition, the shrinkage stresses in the curing process are too high for applications on low cohesive coatings and weak substrates such as concrete.

Thus, although epoxy-polysiloxane based coatings are industrially acceptable, there is a need for epoxy-polysiloxane based materials that have improved mechanical and chemical resistance, and particularly improved resistance to mechanical abuse. Chemical and corrosion resistance, impact and wear resistance for use in the protection of steel and concrete in chemicals, power generation, railcars, sewage and wastewater treatment, and paper and pulp processing industries, for major and ancillary chemical containing structures. There is a need for this improved coating.

In particular, known epoxy-polysiloxane coatings tend to crack on composite steel structures. Cracking tendency frequently occurs in local areas, such as corner seam portions, which are predominantly thick film thicknesses.

1 shows the design of grooved panels for crack resistance testing of coated steel devices.

2 shows a photograph of a grooved panel for crack resistance testing. Panel 2a shows the thickness profile of the steel panel for crack testing on the shape and depth of the grooves. Panel 2b shows the appearance of an SA 2.5 grit blasted home panel. 2C shows a panel coated with a comparative coating after exposure, with crack defects on the grooves. Panel 2d shows a detail of the cracking in the groove with respect to the groove depth.

Accordingly, the main object of the present invention is to provide an epoxy-modified polysiloxane coating composition having a high solids content, a low VOC content, and a NISO. Another object is to provide an epoxy-modified polysiloxane composition which improves flexibility and does not exhibit cracking tendency without degrading chemical resistance or other properties such as mechanical resistance and hardness formation.

In accordance with the principles of the present invention,

Polysiloxanes of the general formula

Epoxy resins having at least one 1,2-epoxy group per molecule and having an epoxy equivalent in the range from 100 to about 5,000; And

An amino curing agent component having active hydrogens capable of reacting with epoxy groups in the epoxy resin to form polymers containing hydroxyl groups, wherein the hydroxyl groups can react with silanol groups of the hydrolyzed polysiloxane to form a polymer network ]

In combination with an epoxy modified polysiloxane composition, wherein the epoxy chain polymer and the polysiloxane polymer were polymerized to form a cured epoxy modified polysiloxane polymer composition.

Wherein each R ¹ is independently hydroxy, are selected from the group comprising carbon number of 6 or lower alkyl, aryl and alkoxy radicals, each R ² is independently hydrogen, a carbon number less than or equal to 6 alkyl and aryl radicals N is selected so that the molecular weight range of the polysiloxane is about 400 to 10,000.

Epoxy modified polysiloxane compositions are prepared using 10 to 80% by weight polysiloxane, 10 to 50% by weight epoxy resin component, stoichiometric amounts of amino curing agent of 0.5 to 1.5 with respect to epoxy groups and optionally up to about 5% by weight of catalyst do.

It was thought that the reaction of the above-mentioned components resulted in the formation of a network composition comprising a continuous epoxy-polysiloxane copolymer. The epoxy modified polysiloxane composition of the present invention has improved chemical and corrosion resistance compared to conventional epoxy resin coatings. In addition to improving flexibility.

details

As used herein, the term “independently selected” means that each disclosed radical R may be the same or different. For example, each R ¹ in the polysiloxane of Formula 1 may be different for each n value and may be present in each unit of the polysiloxane.

As used herein, the term "alkyl", alone or in combination, refers to C _1-10 , preferably C _1-8 , more preferably C _1-6 straight and branched chain saturated hydrocarbon radicals. it means. Examples of such radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, pentyl, isoamyl, hexyl, 3-methylpentyl, octyl and the like. There is this.

The term "alkoxy" or "alkyloxy", alone or in combination, refers to an alkyl ether radical, wherein the term alkyl is as described above. Examples of suitable alkyl ether radicals include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, hexaoxy and the like.

The term "alkylene", alone or in combination, refers to a divalent straight-chain branched saturated hydrocarbon radical of C _1-10 , preferably C _1-8 , more preferably C _1-6 , for example Methylene, ethylene, propylene, butylene, pentylene, hexylene and the like.

The term "alkynyl", alone or in combination, _{refers to} a C _2-10 , preferably C _2-6 , straight and branched chain hydrocarbon radical comprising one or more triple bonds. Examples of alkynyl radicals include ethynyl, propynyl, (propargyl), butynyl, pentynyl, hexynyl and the like.

The term "aminoalkylene" refers to a divalent alkylene amine radical, where "alkylene" is as described above. Examples of aminoalkylene radicals include aminomethylene (-CH ₂ NH-), aminoethylene (-CH ₂ CH ₂ NH-), aminopropylene, aminoisopropylene, aminobutylene, aminoisobutylene, aminohexylene, and the like. have.

The term "aryl", alone or in combination, refers to alkyl, alkoxy, halogen, hydroxy, amino, nitro, cyano, haloalkyl, carboxy, alkoxycarbonyl, cycloalkyl, heterocycle, amido, optionally single or Bisubstituted aminocarbonyl, methylthio, methylsulfonyl and alkyl, alkyloxy, halogen, hydroxy, optionally single or double substituted amino, nitro, cyano, haloalkyl, carboxyl, alkoxycarbonyl, Phenyl and naph which may be optionally substituted with one or more substituents independently selected from cycloalkyl, heterocycle, optionally phenyl optionally substituted with one or more substituents selected from single or disubstituted aminocarbonyl, methylthio and methylsulfonyl It includes teal; Optional substituents on any amino functional group are independently alkyl, alkyloxy, heterocycle, heterocycloalkyl, heterocyclooxy, heterocyclooxyalkyl, phenyl, phenyloxy, phenyloxyalkyl, phenylalkyl, alkyloxycarbonylamino, Selected from amino, and aminoalkyl, each of the amino groups may optionally be monosubstituted or bisubstituted with alkyl. Examples of aryl are phenyl, p-tolyl, 4-methoxyphenyl, 4- (t-butoxy) phenyl, 3-methyl-4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-nitro Phenyl, 3-aminophenyl, 3-acetamidophenyl, 4-acetamidophenyl, 2-methyl-3-acetamidophenyl, 2-methyl-3-aminophenyl, 3-methyl-4-aminophenyl, 2-amino-3-methylphenyl, 2,4-dimethyl-3-aminophenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1-naphthyl, 2-naphthyl, 3-amino-1 Naphthyl, 2-methyl-3-amino-1-naphthyl, 6-amino-2-naphthyl, 4,6-dimethoxy-2-naphthyl and the like.

The term "cycloalkyl", alone or in combination, refers to a saturated or partially saturated monocyclic, bicyclic or polycyclic alkyl radical, wherein each cyclic moiety is from about 3 to about 8, more preferably about 3 And from about 7 carbon atoms. Examples of monocyclic cycloalkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and the like. Examples of polycyclic cycloalkyl radicals include decahydronaphthyl, bicyclo [5.4.0] undecyl, adamantyl and the like.

In accordance with the principles of the present invention,

(a) a base component comprising a polysiloxane of Formula 1 and an epoxy resin having at least one 1,2-epoxy group per molecule and having an epoxy equivalent range of 100 to about 5,000;

(b) an amino curing agent component as disclosed above;

(c) optionally, a catalyst;

(d) optionally, a pigment and / or filler component; And

(e) Optionally, in combination with other additives, an epoxy modified polysiloxane composition is prepared.

In the case of the polysiloxanes used to make up the base component, the preferred polysiloxanes consist of the polysiloxanes of the formula

Formula 1

Wherein each R ¹ is independently hydroxy, are selected from the group comprising carbon number of 6 or lower alkyl, aryl and alkoxy radicals, each R ² is independently hydrogen, a carbon number less than or equal to 6 alkyl and aryl radicals It is selected from the group containing. "n" is selected such that the molecular weight range of the polysiloxane is about 400-10,000. R ¹ and R ² include groups having less than 6 carbon atoms to promote rapid hydrolysis of polysiloxanes, which reaction is induced by the volatility of the alcohol-like product of hydrolysis.

Suitable polysiloxane components include, but are not limited to, alkoxy- and silanol-functional polysiloxanes. Non-limiting examples of suitable alkoxy-functional polysiloxanes include DC-3074 and DC-3037 from Dow Corning; Silres SY-550, and SY-231 from worker silicon; Rhodorsil Resin 10369 A, Rhodorsil 48V750, 48V3500 from Rhodia Silicone; General Electric's SF1147. Non-limiting examples of suitable silanol-functional polysiloxanes include Silres SY 300, Silres SY 440, Silres MK and REN 168 from Walker Silicone, DC-840, DC233 and DC-431 HS silicone resins from Dow Corning and DC-Z- 6018 intermediates, Rhodorsil Resin 6407 and 6482 X from Rhodia Silicones.

In another embodiment, the epoxy modified polysiloxane composition may further comprise an organo-functional polysiloxane. Non-limiting examples of suitable organo-functional polysiloxanes include the organo-functional polysiloxanes disclosed in JP 2000-319582, which is incorporated by reference. Non-limiting examples of other suitable organo-functional polysiloxanes include organo-functional polysiloxanes of Formula 1 '.

Wherein each R ^{1 '} is independently selected from the group comprising alkyl and aryl radicals, each R ² is independently selected from the group comprising hydrogen, alkyl and aryl radicals, n is an organic-functional polysiloxane The molecular weight range is selected to be about 400 to 10,000, R ³ is a divalent radical, or -OR ^3- (X) _z is hydroxy or alkoxy, z is 1, 2 or 3 and X is reacted with an amine radical It is a reactive functional group, and 0-90% of -OR ^3- (X) _z is hydroxy or alkoxy.

The organo-functional polysiloxane of formula 1 'preferably has the following stoichiometry:

Wherein each R ¹⁰ is independently selected from hydrogen, alkyl, or -R ^3- (X) _z , R ¹ , R ² , R ³ , X and z are as described above and a and b are each 0.0 to 2.0, more specifically 0.1 to 2.0 real, c is 0.1 to 1.0 real, b / a is in the range 0.2 to 2.0, a + b + c is less than 4, and 0 to 0 in -OR ¹⁰ 90% is hydroxy or alkoxy. For example, suitable reactive functional groups X include unsaturated esters, imidyl, phthalimidyl, cyclocarbonates, acetylacetanoates, acetylalkylamides, epoxies, cyclic anhydrides, carbamates, isocyanates, vinyls Can be selected from the group.

As used herein, “real number” means a number that is positive and includes integers and fractions of integers or any rational or irrational number. For example, the fact that a is a real number of 0.0 to 2.0 indicates that a can have any value in the range of 0.0 to 2.0.

The divalent radical R ³ is preferably alkylene, alkenylene, arylene, aralkylene, aralkenylene, aryloxy, aminoalkylene, -C (= 0)-, -C (= S)-,- S (= O) _2- , alkylene-C (= O)-, alkylene-C (= S)-, alkylene-S (= O) _2- , -NR ⁴ -C (= O)-, -NR ⁴ -alkylene-C (= 0)-, or -NR ⁴ -S (= 0) ₂ , wherein the C (= 0) group or S (= 0) ₂ group is selected from NR ⁴ Bonded to the moiety, alkyl, aryl, cycloalkyl, halogen, hydroxy, alkoxy, thioalkyl, amino, amino derivatives, amido, amidoxy, nitro, cyano, keto, acyl derivatives, acyloxy derivatives, carboxy, Optionally substituted by ester, ether, esteroxy, sulfonic acid, sulfonyl derivative, sulfinyl derivative, heterocycle, alkenyl or alkynyl, R ⁴ is hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, cycloalkyl Alkyl, aryl, heterocycle or heterocycloalkyl.

In another embodiment of the present invention, the polysiloxane of formula 1 may be exchanged with an organo-functional polysiloxane as described above.

Preferred epoxy modified polysiloxane compositions comprise 10 to 80% by weight of polysiloxane. When the polysiloxane component is used in an amount outside this range, a composition having poor flexibility, weather resistance, and chemical resistance may be formed. Particularly preferred epoxy modified polysiloxane compositions comprise about 30% by weight of polysiloxane.

Base components include blends of epoxy resins and polysiloxanes. Epoxy resins useful for forming epoxy modified polysiloxane compositions according to the present invention may be prepared by attaching an epoxy group at the end of a paraffinic hydrocarbon chain (e.g., diepoxy derived from butanediol) or polyether chain (e.g., α-ω-di Epoxy polypropylene glycol). Non-limiting examples of more exotic diepoxy resins suitable for the reaction include vinylcyclo hexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane monocarboxylate, 3- (3,4 -Epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspiro- [5.5] undecane, bis (2,3-epoxycyclopentyl) ether, bis (3,4-epoxy-6-methylcyclo Hexyl) adipate and resorcinol diglycidyl ether. Other suitable epoxy resins may include two or more epoxy functional groups per molecule, such as epoxidized soybean oil, polyglycidyl ethers of phenolic resins of the novolac type, p-aminophenoltriglycidyl ether or 1,1 , 2,2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether and the like. Another class of epoxy resins useful for forming epoxy modified polysiloxane compositions is epoxy polyethers obtained by reacting polyphenyls with epihalohydrin (e.g. epichlorohydrin or epibromohydrin) in the presence of an alkali. Include. Suitable polyphenols include resorcinol, catechol, hydroquinone, bis (4-hydroxyphenyl) -2,2-propane, ie bisphenol A; Bis (4-hydroxyphenyl) -1,1-isobutane, 4,4-dihydroxybenzophenone; Bis (4-hydroxyphenyl-1,1-ethane; bis (2-hydroxyphenyl) -methane; bis (4-hydroxyphenyl) -methane, ie bisphenol F, 1,5-hydroxynaphthalene and the like A very common polyepoxy is polyglycidyl ether of polyphenols such as bisphenol A. Another class of epoxy resins suitable for forming epoxy modified polysiloxane compositions is hydrogenated epoxy resins based on bisphenol A as a main component. For example, Eponex 1510 from Resolution Performance Products Another example of a suitable epoxy resin is polyglycidyl ethers of polyhydric alcohols These compounds are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol Derived from 1,4-butylene glycol, 1,5-pentanediol, 1,2,6-hexane-triol, glycerol, trimethylolpropane and bis (4-hydroxycyclohexyl) -2,2-propane Epoxy modified A detailed list of suitable epoxy compounds useful for forming polysiloxane compositions can be found in AM Paquin, "Epoxidverbindungen und Harze" (Epoxide Compounds and Resins), Springer Verlag, Berlin 1958, Chapter IV and H. Lee and K. Neville, "Handbook of Epoxy Resins "MC Graw Hill Book Company, New York 1982 Reissue, as well as CA May," Epoxy Resins-Chemistry and Technology ", Marcel Dekker, Inc. New York and Basle, 1988.

More specifically, the epoxy resin suitable for the epoxy modified polysiloxane composition is a non-aromatic epoxy resin containing at least one 1,2-epoxy group per molecule. Preferred non-aromatic epoxy resins comprise two 1,2-epoxy groups per molecule. The epoxy resin is preferably liquid rather than solid, has an epoxy equivalent in the range of about 100 to 5,000, and has a functionality of at least two. In another embodiment, the epoxy resin suitable for the epoxy-polysiloxane composition is a non-aromatic hydrogenated epoxy resin.

Non-limiting examples of suitable epoxy resins include non-aromatic diglycidyl ethers of cyclohexane dimethanol, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (DGEBA) type epoxy resins such as resolution Heloxy 107, Eponex 1510 and 1513 from Performance Products; Erisys GE-22, Epalloy 5000 and 5001 from CVC Specialty Chemicals; Polypox R11 from UPPC GmbH; Epo Tohto ST-1000 and ST-3000 by Toto Kasei; Epodil 757 from Air Products; Vantico's Araldite DY-C, DY-0397 and DY-T.

Other suitable non-aromatic epoxy resins include DER 732 and 736 from Dow Chemical; Heloxy 67, 68, 48, 84, 505 and 71 from Resolution Performance Products; Erisys GE-20, GE-21, GE-23, GE-30, GE-31 and GE-60 from CVC Specialty Chemicals; Polypox R3, R14, R18, R19, R20 and R21 from UPPC GmbH; Aliphatic epoxy resins such as Araldite DY-T and DY-0397 from Vantico; Union Carbide's ERL4221; Aroflint 607 and bisphenol F diglycidyl ether type epoxy resins from Recold Chemicals, such as Epikote 862 and hydrogenated bisphenol F diglycidyl ether type epoxy resins from Resolution Performance Products, such as Rutapox VE4261 / from Rutger Bakelite R and the like.

Preferred epoxy modified polysiloxane compositions comprise 10 to 50% by weight of epoxy resin. If the composition comprises less than about 10 weight percent epoxy resin, the chemical resistance of the coating is reduced. If the composition comprises more than about 50 weight percent epoxy resin, the weather resistance of the coating may be impaired. Particularly preferred compositions comprise about 20% by weight epoxy resin.

In an embodiment, the epoxy modified polysiloxane composition may comprise a polysiloxane / epoxy resin in a ratio of 15/85 to 90/10 weight percent, preferably 40/60 to 70/30 weight percent. In another embodiment, the composition may comprise polysiloxane / epoxy resin in a ratio of 58/42% by weight.

Examples of suitable amino-curing agents for the composition include aliphatic, cycloaliphatic amines, aromatics, aromatic aliphatic amines, imidazoline group-containing polyaminoamides, and addition products thereof, including monobasic or polybasic acids as main components. It is not limited to this. These compounds belong to the general technical level and are particularly disclosed in Lee & Neville, "Handbook of Epoxy Resins", MC Graw Hill Book Company, 1987, chapter 6-1 to 10-19. More specifically, useful amino-curing agents that can be added to the composition include polyamines that are distinguished in that they each have at least two primary amino groups bonded to aliphatic carbon atoms. The amino-curing agent may comprise secondary or tertiary amino groups. Suitable polyamines include polyaminoamides (from aliphatic diamines and aliphatic or aromatic dicarboxylic acids) and polyiminoalkylene-diamines and polyoxyethylene-polyamines, polyoxyethylene / polyoxypropylene-polyamines mixed with polyoxypropylene-polyamines, Or amine addition products, such as amine-epoxy resin addition products. The amine may contain 2 to 40 carbon atoms. For example, the amine can be selected from polyoxyalkylene-polyamines and polyiminoalkylene-polyamines having 2 to 4 carbon atoms in the alkylene group, and have a number average degree of polymerization of 2 to 100. Other examples of amines may be straight chain, branched or cyclic C _2-40 aliphatic primary diaminoalkanes. In addition, the amine may be an aliphatic amine having two or more primary amino groups, each of which is bonded to an aliphatic carbon atom.

Preferred amino curing agents are polyamines. More specifically, the polyamine may be a polyoxyalkylene amine curing agent. More preferably, examples of the polyoxyalkylene polyamine curing agent are represented by the following formula (2).

Wherein Q is a residue of an active hydrogen-containing polyvalent compound; Each R ⁵ is independently hydrogen or alkyl; x is at least 1; y is at least 2, but the average value for x is less than 10 when low molecular weight polyoxyalkylene polyamines are used.

Variables in the above formulas have the following meanings: Q is the residue of the active hydrogen-containing polyvalent compound used as initiator. The valence of Q is represented by y, where y is 2 or more, preferably 2 to 8, most preferably 2 to 3. Each R ⁵ is independently hydrogen or alkyl, such as methyl or ethyl. The R ⁵ group is preferably hydrogen and / or methyl (including mixtures). The average number of oxyalkylene repeat units per amine group is given by x and is at least 1, preferably 1 to 100, most preferably 1.5 to 7. Preferably Q is residue alkyl, alkenyl, alkynyl, most preferably C _1-18 alkyl.

Typical oxyalkylene repeat units include oxyethylene, oxypropylene, oxybutylene, and the like, including mixtures thereof. If two or more oxyalkylenes are used, they may be present in any form, such as randomly or in block form.

Examples of suitable polyoxyalkylene polyamines are polyoxyalkylenetriamines and polyoxyalkylenediamines. Examples of suitable polyoxyalkylenepolyamines are polyoxypropylenetriamine and polyoxypropylenediamine. Non-limiting examples of polyoxyalkylene polyamines include JEFFAMINE® polyoxyalkylene amines from HUNTSMAN, such as diamines D-230, D-400, D-2000 and D-4000, triamine T-403, T- 3000 and T-5000. According to a preferred embodiment, the polyoxyalkylene polyamine is JEFFAMINE® T-403 (Huntsman) or JEFFAMINE® D230.

Some suitable polyoxyalkylene polyamines and methods for their preparation are disclosed in US Pat. Nos. 5,391,826 and 4,766,245, which are incorporated by reference.

In preparing the epoxy modified polysiloxane composition of the present invention, the ratio of the curing agent component to the resin component may vary regardless of whether the curing agent is selected from a general kind of amine or a compound of formula (2), or any combination thereof. Can be. Generally, the epoxy resin component is cured with a curing agent sufficient to provide at least about 0.5 to 1.5 amine equivalents per epoxy equivalent.

In another embodiment, the epoxy modified polysiloxane composition according to the present invention may comprise an epoxy-functional silane. The epoxy-functional silane is useful as an accelerator. Non-limiting examples of such suitable epoxy functional silanes are glycidoxymethyltrimethoxysilane, 3-glycidoxypropyltrihydroxysilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltributoxysilane, 1, 3-bis (glycidoxypropyl) tetramethyldisiloxane, 1,3-bis (glycidoxypropyl) tetramethoxydisiloxane, 1,3-bis (glycidoxypropyl) -1,3-dimethyl-1, 3-dimethoxydisiloxane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 6,7-epoxyheptyltrimethoxysilane, 9,10-epoxydecyltrimethoxysilane , 1,3-bis (2,3-epoxypropyl) tetramethoxydisiloxane, 1,3-bis (6,7-epoxyheptyl) tetramethoxydisiloxane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane and the like.

The epoxy-modified polysiloxane composition of the present invention may further include other components such as rheology modifiers, plasticizers, thixotropic agents, adhesion promoters, antifoaming agents, and solvents and the like to achieve desired properties desired by the user.

The epoxy modified polysiloxane compositions of the present invention are formulated for application using conventional air, airless, air-assisted airless and electrostatic spraying devices, brushes or rollers. This composition is intended to be used as a protective coating for coating steel, galvanized steel, aluminum, concrete and other substrates with a dry film thickness of about 50 to about 500 μm.

Suitable pigments can be selected from organic and inorganic pigments and include titanium dioxide, carbon black, lampblack, zinc oxide, natural and synthetic red, yellow, brown and black iron oxide, toluidine and benzidine yellow, phthalocyanine blue and green, carba Sol violets and thickening pigments such as ground and crystalline silica, barium sulfate, magnesium silicate, calcium silicate, mica, mica-containing iron oxide, calcium carbonate, zinc powder, aluminum and aluminum silicate, gypsum, feldspar and the like. The amount of pigment used to form the composition depends on the use of the particular composition and may not be added if a clear composition is desired. Preferred epoxy-polysiloxane compositions may comprise up to about 50% by weight of particulate and pigments and / or fillers. Depending on the specific end use, the preferred coating composition may comprise about 25% by weight particulate size filler and / or pigment. More specifically, the pigment or filler material selected from the group comprising organic and inorganic pigments has a particulate size, wherein at least 90% by weight of the pigment has a particle size of less than 40 microns.

Typically the pigment and / or filler component is added to the epoxy resin portion of the resin component and dispersed using a high speed dissolution / mixer to a powder fineness of at least 50 μm, or alternatively ball milling or sand milling to the same powder fineness do. Selecting a pigment or filler of particulate size and dispersing or milling it into a powder of about 50 μm, atomizes the mixed resin and cured components with conventional air, air-assisted airless, airless and electrostatic spraying devices, and smoothes them after application. And a uniform surface appearance is provided.

The presence of water in the curing process is an important requirement of the present invention and the water must be present in an amount sufficient to cause hydrolysis of the polysiloxane and subsequent condensation of the formed silanol. The source of water is mainly atmospheric moisture and moisture adsorbed onto the pigment or filler material. In addition, the amino curing agent may include or attract an additional amount of water. Additional water may be added to promote curing depending on ambient conditions, such as the use of coating compositions in a dry environment. Preferred epoxy modified polysiloxane compositions contain up to stoichiometric amounts of water to promote hydrolysis.

If necessary, water may be added to the epoxy resin or the amino curing agent. Other water sources may include traces of water present in epoxy resins, amino curing agents, diluent solvents, or other components. Regardless of its source, the total amount of water used should be the stoichiometric amount required to promote the hydrolysis reaction. Water above the stoichiometric amount is undesirable because excess water acts to reduce the surface gloss of the last cured composition product.

Up to about 5% by weight of catalyst may be added to the resin component, or as a completely separate component, to promote drying and curing of the epoxy modified polysiloxane composition of the present invention. Useful catalysts are metal desiccants known in the paint industry such as zinc, manganese, zirconium, titanium, cobalt, iron, lead and tin containing desiccants. Suitable catalysts include organotin catalysts of formula (3).

Wherein R ⁶ and R ⁷ are each independently selected from the group comprising alkyl, aryl and alkoxy radicals having up to 11 carbon atoms, and R ⁸ and R ⁹ are each independently from the same group as R ⁶ and R ⁷ Or from the group comprising inorganic atoms such as halogen, sulfur or oxygen. Dibutyl tin dilaurate, dibutyl tin diacetate, organotitanate, sodium acetate and aliphatic secondary or tertiary polyamines such as propylamine, ethylamino ethanol, triethanolamine, triethylamine and methyl diethanol amine alone Or in combination with each other to promote hydrolytic polycondensation of polysiloxanes. Preferred catalyst is dibutyl tin dilaurate.

Other suitable catalysts include acids such as organic acids, inorganic acids, organic sulfonic acids, esters of sulfuric acid and super acids. Organic acids include acetic acid and formic acid. Inorganic acids include sulfuric acid, hydrochloric acid, perchloric acid, nitric acid, phosphoric acid, and the like. Organic sulfonic acids include aromatic and aliphatic sulfonic acids. Typical sulfonic acids on the market include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, dodecyldiphenyloxide sulfonic acid, 5-methyl-1-naphthylenesulfonic acid and p-toluene Sulfonic acids, sulfonated polystyrenes, and sulfonates derived from polytetrafluoroethylene. Superacids suitable as catalysts are disclosed in GA Olah, GKS Prakash, and J. Sommer, Superacids, John Wiley & Sons: New York, 1985. Useful superacids include perchloric acid, fluorosulfuric acid, trifluoromethanesulfonic acid and perfluoroalkylsulfonic acid. Lewis superacids such as SbF ₅ , TaF ₅ , NbF ₅ , PF ₅ , and BF ₃ . Superacids also include hydrogen fluoride with fluorinated Lewis acids such as SbF ₅ , TaF ₅ , NbF ₅ , PF ₅ , and BF ₃ . Superacids also contain oxygenated Bronsted acids such as sulfuric acid, fluorosulfuric acid, trifluoromethanesulfonic acid, and broad fluoroalkylsulfonic acid, such as SbF ₅ , TaF ₅ , NbF ₅ , PF ₅ , and BF _3. Contains with Lewis acid.

Other examples of suitable catalysts include nitrates of polyvalent metal ions such as calcium nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate or strontium nitrate.

The epoxy modified polysiloxane composition of this invention is low in viscosity generally, and can be spray-coated without adding a solvent. However, organic solvents may be added to improve atomization and application using electrostatic spray devices, or to improve flow, leveling and appearance when applied using brushes, rollers or standard air and airless spray devices. Can be. Exemplary solvents useful for this purpose include aromatic hydrocarbons, esters, ethers, alcohols, ketones, glycol ethers and the like. The amount of solvent added to the composition of the present invention is preferably less than 250 g per liter, more preferably less than about 120 g per liter.

The epoxy modified polysiloxane compositions of the present invention may also include rheology modifiers, plasticizers, antifoams, thixotropic agents, pigment wetting agents, adhesion promoters, antisettling agents, diluents, UV light stabilizers, air release agents and dispersing aids, and the like. have. Preferred epoxy modified polysiloxane compositions can include up to about 10% by weight of such modifiers and agents.

The epoxy modified polysiloxane composition of the present invention can be supplied as a two-package system in a waterproof container. One package contains an epoxy resin, polysiloxane, optional pigment and / or filler components, and optionally a catalyst, additives, and solvent, as desired. The second package contains the addition reaction product of polyamines and / or polyamines and optionally catalysts, solvents and additives.

The epoxy modified polysiloxane composition of the present invention may be applied and completely cured at room temperature conditions in the range of about −10 to 50 ° C. The absence of water at temperatures below 0 ° C. has a profound effect on the rate of cure and the final properties of the coating. However, additional heating may cure the composition of the present invention.

In addition, the present invention relates to a method for producing an epoxy-modified polysiloxane composition according to the present invention, the polysiloxane of Formula 1; Epoxy resins having at least one 1,2-epoxy group per molecule and having an epoxy equivalent of from 100 to about 5,000; Sufficient amount of amino curing agent component with active hydrogen, preferably two or more active hydrogens, optionally a catalyst such as an organotin catalyst; Mixing with a sufficient amount of water to promote hydrolysis and polycondensation reactions to form a fully cured and crosslinked epoxy modified polysiloxane polymer composition at room temperature. Preferably, the amino curing agent is provided in the range of 0.5-1.5 amine equivalents per one epoxy equivalent. According to an embodiment, said polysiloxane is selected from the group comprising alkoxy- and silanol-functional polysiloxanes having a molecular weight range of about 400 to 10,000.

If desired, other components such as organo-functional polysiloxanes, epoxy functional silanes, other adhesion promoters, rheology modifiers, plasticizers, thixotropic agents, antifoaming agents, solvents, and the like may be combined with the components of the composition.

The invention also includes a substrate having at least one cured network layer of the epoxy modified polysiloxane polymer composition according to the invention.

In addition, the present invention relates to a method for producing a fully cured thermosetting epoxy modified polysiloxane composition according to the present invention,

Epoxy resins mentioned above; Combining the polysiloxanes of Formula 1 to form a base component, and

An amino curing agent having an active hydrogen, preferably two or more active hydrogens, which can react with an epoxy group in the epoxy resin to form a polymer comprising hydroxyl groups, wherein the hydroxyl group is a silane of hydrolyzed polysiloxane Reacting with the forming to form a polymer network, wherein the epoxy chain polymer and the polysiloxane polymer polymerize to form a fully cured epoxy-modified polysiloxane polymer composition, and optionally an organotin catalyst for promoting the curing of the base component at room temperature. Adding a catalyst to cure the base component at room temperature.

In another embodiment, the polysiloxane is selected from the group comprising alkoxy- and silanol-functional polysiloxanes having a molecular weight of 400 to 10,000.

Without wishing to be bound by any particular theory, the epoxy modified polysiloxane composition of the present invention comprises: (1) reacting an epoxy resin with an amine and / or a polyoxyalkylenepolyamine curing agent to form an epoxy polymer chain; (2) hydrolytic polycondensation of the polysiloxane component to form alcohol analogs and polysiloxane polymers; (3) It is considered to be cured by copolymerizing an epoxy polymer chain with a polysiloxane polymer. This copolymerization reaction is thought to occur through the condensation reaction of the silanol group of the hydrolyzed polysiloxane (polymer) with the silanol and hydroxyl groups of the epoxy polymer chain. As a result, a fully cured epoxy modified polysiloxane polymer coating is formed. In the cured form, the epoxy modified polysiloxane coating is present as a homogeneously dispersed arrangement of the continuous polysiloxane polymer matrix entangled with the epoxy polymer chain fragments, forming a polymer network chemical structure that is quite advantageous over conventional polysiloxane systems.

The compositions of the present invention can be used with suitable dispenser tinting systems and can easily supply a variety of colors.

Coloring of these compositions can generally be carried out using ordinary light fast paint pigments, and it is believed that the addition of glass fragments under certain conditions can further reduce water permeability and extend service life.

These compositions can be used in a variety of industrial applications because they can cure fairly quickly, even under humid atmospheres, and have desirable properties (eg, long pot life). Typical industrial uses for the composition include, for example, the manufacture of shaped articles (casting resins) for tool making, or substrates of various kinds, such as substrates of organic or inorganic nature (eg, textiles of natural or synthetic origin, plastics). Coatings on glass, ceramic and building materials, such as concrete, fiberboard and artificial stone, in particular metals (such as plated steel, cast iron, aluminum and non-ferrous metals, as the case may be, if desired) and And / or use for the preparation of intermediate coatings.

In addition, the compositions of the present invention are constituents of adhesives, putties, laminated resins and synthetic resin cements, in particular industrial articles, household appliances and furniture, shipbuilding, land storage tanks and pipelines and construction industries such as refrigerators, dishwashers electrical appliances, windows And door coating materials and coatings.

For example, these coatings can be applied using brushes, sprays, rollers, dipping, and the like. A particularly preferred field of use of the coatings of the invention is paint formulations.

The compositions of the present invention comprise primarily (but not absolute) reticulated compositions for low VOC, NISO finish applications. The amine cured epoxy polymer dose and the modified moisture cured polysiloxane are combined to form a network during the room temperature curing process after application. It is also possible to modify these compositions with other binder polymers. These compositions have a gloss and color retention similar to that of conventional polysiloxanes, while providing coatings that exhibit unexpected additional strength and flexibility that tolerate high film forming applications on composite structures without cracking tendencies.

These and other features of the present invention will become more apparent with reference to the following examples and figures.

Example 1

Preparation of Epoxy-Modified Polysiloxane Compositions According to the Invention

To prepare the epoxy modified polysiloxane compositions according to the present invention, polysiloxanes of formula 1 having a molecular weight of about 1,400 g / mol were mixed with different epoxy resins in various proportions:

-Bisphenol A epoxy resin

-Bisphenol F epoxy resin

Hydrogenated Bisphenol A Epoxy Resin

Hydrogenated Bisphenol F Epoxy Resin

These combinations were cured in amine (eg Jeffamine) in pure form or in pre-reacted form (addition product form to reduce volatility).

The epoxy modified polysiloxane composition of this invention was manufactured by the following method (preparation of the coating 6).

240 g hydrogenated bisphenol A epoxy resin (epoxy equivalent = 210-238 g / eq), 135 g polysiloxane (e.g. DC-3074), 5 g thixotropic agent, 5 g defoamer, and 415 g titanium dioxide Prepare the base ingredient. These ingredients are mixed in 1 L cans and dispersed in a dissolver so that the powder fineness is less than 40 μm. The temperature of the mixture is raised to 65 ° C. and held constant at this temperature for about 10 minutes to activate the thixotropic agent.

The mixture is then cooled to 40 ° C. and then 225 g of polysiloxane (eg DC-3074) are added. At this time, the mixture is homogenized with a high speed dissolver, and finally 15 g of light stabilizer, 20 g of catalyst, 25 g of xylene and 50 g of epoxy-functional silane (e.g., γ-glycidoxypropyltrimethoxysilane) are mixed. . The final mixture has a theoretical epoxy equivalent (EEW) of 873 g / equivalent. Table 1 shows the components used in the coating according to the invention.

Example 2

General Properties of Coatings According to the Invention

Each epoxy modified polysiloxane composition was air-sprayed onto a suitable test panel. The coatings were tested after they had fully cured at room temperature for 2 weeks. After the curing period has elapsed, the coating is tested for relevant properties. The epoxy modified polysiloxane coatings (1-11) according to the invention were tested and compared with the comparative examples. The coating of the comparative example is a commercial coating comprising polysiloxane, hydrogenated bisphenol A epoxy resin and aminosilane as curing agent and sold under the trade name Ameron PSX 700 from Ameron.

To simulate the cracking behavior of coatings, possibly with excessive thickness, on composite structures, crack resistance tests were developed. In order to test the crack resistance, a "home panel" was produced. The steel panels were 2.5 SA grit blasted and made three grooves with depths of 0.8 mm, 1.4 mm and 2.0 mm, respectively. The design of the home panel is shown in FIG. 1. The coating is applied to the home panel. First, the paint is filled into the grooves using a disposable plastic pipette, and the paint overflowing from the grooves is removed using a putty-knife. Then a paint layer having a thickness that is about 1.5 times the recommended film thickness is applied by air-spray.

After two weeks of curing at room temperature, the panels are placed in a temperature cabinet and exposed to the next cycle.

18 hours at 60 ℃

From 60 ° C to -5 ° C within 1 hour

4 hours at -5 ℃

From -5 ℃ to 60 ℃ within 1 hour

The panel was exposed for 84 cycles, during which periods of crack formation were examined every 7 cycles. Report results after 84 cycles.

0 = pass, no crack

1 = 1 groove represents a crack.

2 = two grooves show cracks.

3 = 3 grooves show cracks.

General properties obtained with the coatings 1-9 are disclosed below. The results are illustrated in Table 2.

coating One 2 3 4 5 6 7 8 9 Comparative coating VOC [g / ℓ] 150 120 100 100 100 90 100 80 80 120 Pot life approximately 20 degrees Celsius [time] 4 8 4 8 6 6 6 6 6 4 Dry at 20 ° C, 50% RH-Dry for handling [time]-Surface defect-Initial gloss [%, 60 °] 8 None 90 16 None 90 8 None 90 16 None 90 10 None 90 10 None 90 10 None 91 10 None 92 10 None 92 8 None 90 Drying [time] -surface defects for drying-handling at 20 ° C and 90% RH 8 none 16 none 8 none 16 none 8 none 8 none 8 none 8 none 8 none 6 None Flexibility-Crack Test After 84 Cycles 0 0 0 0 0 0 0 0 0 2

As illustrated in FIG. 2 (Panels 2c and 2d), the coating according to the invention is very flexible while the comparative example shows cracks.

Looking at the VOC content, all coatings according to the invention have values below the 250 g / L limit.

Because of the high solids content, the coatings according to the invention can be applied by airless spraying to a minimum wet film thickness in the range of 80 to 150 μm.

The pot life of the coating of the invention is at least 4 hours at room temperature. These coatings show a good balance for use in the tropical climate of the Atlantic.

The drying time for handling after the coating according to the invention has been applied at room temperature is similar to the comparative coating. In addition, the coating of the present invention is free of surface defects, is high gloss, and exhibits good crack resistance even when locally having a thick thickness.

The coatings according to the invention have good resistance to chemicals / reagents.

The coatings of the present invention are very good in gloss and color retention and exhibit additional features such as flexibility, crack resistance and good compatibility with existing tinting systems.

The epoxy modified polysiloxane coatings of the present invention have the advantages of NSIO compositions with surprisingly improved mechanical cohesive strength while providing a high degree of flexibility that limits the risk of cracking and enables the application of this kind of coating on composite steel structures. Indicates.

In addition, the coatings of the present invention have unexpectedly long pot life and good curing properties, exhibiting sufficient flexibility, low stress and can be easily applied. In addition, these coatings have good crack resistance. Due to the high solids content, low solvent emissions are observed in these coatings.

Claims (21)

Polysiloxanes of the general formula (1); Epoxy resins having at least one 1,2-epoxy group per molecule and having an epoxy equivalent in the range from 100 to about 5,000; And A polyoxyalkylenepolyamine curing agent of formula (2), wherein said curing agent has active hydrogen capable of reacting with an epoxy group in an epoxy resin to form a polymer containing hydroxyl groups, said hydroxyl groups being Can react with silanol groups to form a polymer network], wherein the epoxy-modified polysiloxane composition is polymerized to form an epoxy-modified polysiloxane polymer composition by polymerization of an epoxy chain polymer and a polysiloxane polymer. : Formula 1 [Wherein, each R ¹ is independently hydroxy, carbon atoms and is selected from the group comprising 6 or lower alkyl, aryl and alkoxy radicals, each R ² is independently hydrogen, a carbon atom number of alkyl and aryl or lower 6 Selected from the group containing radicals, n is selected such that the molecular weight range of the polysiloxane is about 400 to 10,000; Formula 2 [Wherein Q is a residue of an active hydrogen-containing polyvalent compound; Each R ⁵ is independently hydrogen or alkyl; x is at least 1; y is at least 2, but the average value for x is less than 10 for low molecular weight polyoxyalkylene polyamines] The composition of claim 1, wherein the polysiloxane of Formula 1 is an alkoxy-functional polysiloxane or silanol-functional polysiloxane. The composition of claim 1 or 2, wherein said composition comprises an organo-functional polysiloxane. The composition of claim 1, wherein the composition comprises an epoxy-functional silane. The composition according to claim 1, wherein the polyoxyalkylenepolyamine is polyoxyalkylenetriamine or polyoxyalkylenediamine. The composition of claim 1, wherein the polyoxyalkylenepolyamine is polyoxypropylenetriamine or polyoxypropylenediamine. The polyoxyalkylenepolyamine of claim 1, wherein the polyoxyalkylenepolyamine is selected from the group comprising polyoxypropylene triamine JEFFAMINE® T-403 and polyoxypropylene diamine JEFFAMINE® D230. The composition selected. The composition of any one of claims 1 to 7, wherein the epoxy resin is a non-aromatic epoxy resin. The composition of claim 8, wherein the epoxy resin is a hydrogenated non-aromatic epoxy resin. The alicyclic epoxy resin according to claim 8 or 9, wherein the non-aromatic epoxy resin is selected from the group of alicyclic epoxy resins comprising diglycidyl ether of cyclohexane dimethanol and diglycidyl ether of hydrogenated bisphenol A epoxy resin. Composition. The composition of claim 1, wherein the composition further comprises one or more metal catalysts to promote curing at room temperature, the catalyst comprising zinc, manganese, zirconium, titanium, cobalt, iron, lead And a tin-containing desiccant. 12. The rheology modifier, plasticizer, antifoaming agent, thixotropic agent, pigment wetting agent, adhesion promoter, antisettling agent, diluent, UV light stabilizer, air release agent, dispersion according to any one of claims 1 to 11. A composition comprising one or more additional ingredients selected from the group comprising preparations and mixtures thereof. The method of claim 1, further comprising a pigment or filler having a particulate size selected from the group comprising organic and inorganic pigments, wherein at least 90% by weight of the pigment has a particle size of less than 40 μm. Composition. The stoichiometric amount of the polyoxyalkylenepolyamine curing agent according to any one of claims 1 to 13, wherein the stoichiometric amount is about 10 to 80% by weight of polysiloxane, 10 to 50% by weight of epoxy resin component, and 0.5 to 1.5 with respect to the epoxy group. And optionally up to about 5 weight percent of a catalyst. The composition of claim 1, wherein the polysiloxane / epoxy resin has a ratio in the range of 15 / 85-90 / 10 wt%. The composition according to claim 15, wherein the polysiloxane / epoxy resin has a ratio of 40/60 to 70/30% by weight, preferably 58/42% by weight. As a method for producing the epoxy-modified polysiloxane polymer composition of any one of claims 1 to 16, Polysiloxanes of the general formula (1); Epoxy resins having at least one 1,2-epoxy group per molecule and having an epoxy equivalent in the range from 100 to about 5,000; A sufficient amount of the polyoxyalkylenepolyamine curing agent of formula (II) having active hydrogens; Optionally a catalyst; And Combining with a sufficient amount of water to promote hydrolysis and polycondensation reactions to form a fully cured and crosslinked epoxy modified polysiloxane polymer composition at room temperature. Formula 1 [Wherein, each R ¹ is independently hydroxy, carbon atoms and is selected from the group comprising 6 or lower alkyl, aryl and alkoxy radicals, each R ² is independently hydrogen, a carbon atom number of alkyl and aryl or lower 6 Selected from the group containing radicals, n is selected such that the molecular weight range of the polysiloxane is about 400 to 10,000; Formula 2 [Wherein Q is a residue of an active hydrogen-containing polyvalent compound; Each R ⁵ is independently hydrogen or alkyl; x is at least 1; y is at least 2, but the average value for x is less than 10 for low molecular weight polyoxyalkylene polyamines] 18. The method of claim 17, wherein the polysiloxane is selected from the group comprising alkoxy-functional polysiloxanes and silanol-functional polysiloxanes having a molecular weight range of about 400 to 10,000. A substrate provided with at least one layer of the cured epoxy modified polysiloxane composition of claim 1. 17. A process for preparing the fully cured thermosetting epoxy modified polysiloxane composition of any one of claims 1-16. Epoxy resins having at least one 1,2-epoxy group per molecule and having an epoxy equivalent in the range of from 100 to about 5,000; Combining the polysiloxanes of formula (1) to form a base component; Here A polyoxyalkylenepolyamine curing agent of formula (2), wherein said curing agent has active hydrogen capable of reacting with an epoxy group in an epoxy resin to form a polymer containing hydroxyl groups, said hydroxyl groups being React with silanol groups to form a polymer network, wherein the epoxy chain polymer and the polysiloxane polymer polymerize to form a cured epoxy modified polysiloxane polymer composition; and Optionally, adding a catalyst that promotes curing of the base component at room temperature to cure the base component at room temperature: Formula 1 [Wherein, each R ¹ is independently hydroxy, carbon atoms and is selected from the group comprising 6 or lower alkyl, aryl and alkoxy radicals, each R ² is independently hydrogen, a carbon atom number of alkyl and aryl or lower 6 Selected from the group containing radicals, n is selected such that the molecular weight range of the polysiloxane is about 400 to 10,000; Formula 2 [Wherein Q is a residue of an active hydrogen-containing polyvalent compound; Each R ⁵ is independently hydrogen or alkyl; x is at least 1; y is at least 2, but the average value for x is less than 10 for low molecular weight polyoxyalkylene polyamines] 21. The method of claim 20, wherein said polysiloxane is selected from the group comprising alkoxy-functional polysiloxanes and silanol-functional polysiloxanes having a molecular weight range of 400 to 10,000.