GB1581974A - Epoxy resin composition - Google Patents

Description

(54) EPOXY RESIN COMPOSITION (71) We, MITSUI PETROCHEMICAL INDUSTRIES, LTD., a Japanese Body Corporation, of 2-5, 3-chome, Kasumigaseki, Chiyoda-ku, Tokyo, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a novel epoxy resin composition, and more specifically to an epoxy resin composition especially useful in the field of paints which comprises a combination of a phenol- or naphthol-modified aromatic hydrocarbon resin and a polyepoxy compound.

Epoxy resin compositions have found extensive applications in the fields of paints, adhesives, molding materials, etc. In particular, tar epoxy resin compositions comprising a polyepoxy compound, tar, a curing agent and optional additives such as pigments, fillers, reactive diluents, flexibilizers or modifying resins are generally inexpensive and have relatively good adhesion, chemical resistance and flexibility.

-Hence, they find a wide range of applications as waterproof coatings of buildings and surface protective paints for metallic containers, various industrial apparatus and appliances, steel pipes, ships, seaside facilities and structural materials; as adhesives for floors, bricks, tiles; as road repairing materials for repairing cracks of highways; and as floor coverings for slip prevention, waterproofing, etc.

However, these tar epoxy resin compositions have one or more defects. For example, because the tar components present in a concentration of about 10 to 50 /O by weight such as coal tar, pitch and petroleum asphalt contain carcinogenic substances such as benzopyrene, they cause a problem of health hazard at the time of preparation and application of these compositions. Or they tend to bleed out from the compositions because their compatibility with polyepoxy compounds is generally not good. Since they are black in color, pale-colored coatings cannot be obtained, and their use is limited.

In an attempt to eliminate these defects, various investigations have been made for techniques of replacing the tar components of the tar epoxy resin compositions by substances which have characteristics comparable to, or better than, those of the conventional tar components, and some of the results obtained have been reported, and applied for patent.

For example, Japanese Patent Publication No. 23718/75 suggests the use of the by-product cresol distillation residue obtained in the synthesis of cresol as a substitute for the tar component of a tar epoxy resin composition composed mainly of an epoxy resin, a curing agent and the tar component.

The distillation residue (tar) formed as a by-product in the synthesis of cresol suggested in the abcve-cited Japanese Patent Publication has good compatibility with the remaining ingredients of the tar epoxy resin compositions such as epoxy resins.

However, since the distillation residue is highly reactive with the polyepoxy compounds, tar epoxy resin compositions containing the distillation residue have the defect of reduced operability because of their short curing time, and give coatings having poor water resistance. Furthermore, because the distillation residue is not constant in quality and its composition may vary from lot to lot, a product of uniform quality is difficult to obtain. Another defect is that the residue itself is colored deep, and cannot be used in applications where light colors are required.

It is an object of this invention to provide an epoxy resin composition free from the aforesaid defects.

Another object of this invention is to provide an epoxy resin composition having a light color and being useful in various applications such as paints, adhesives and molding materials.

Still another object of this invention is to provide a light-colored epoxy resin composition especially suitable as a vehicle component of paints which give coated films having better water resistance, chemical resistance (e.g., resistances to salt water, solvents or acids) and strength than do conventional tar epoxy resin compositions.

Other objects and advantages of the present invention will become apparent from the following description.

According to this invention, there is provided an epoxy resin composition comprising [A] a polymer having a hydroxyl content of 0.3 to 7 millimoles/g, said polymer being prepared by polymerizing a polymerizable material selected from (a) a cationically polymerizable hydrocarbon-containing fraction having a boiling point in the range of from 140 to 2800C obtained by the distillation of a cracking or reforming product of a petroleum, (b) a cationically polymerizable aromatic unsaturated hydrocarbon, and (c) a mixture of (a) and (b) in the presence of a cationic polymerization catalyst and modifying the resulting polymer with a phenol or naphthol, [B] a polyepoxy compound; and [C] a curing agent.

One characteristic feature of this invention is to use a phenol- or naphthol-modified aromatic hydrocarbon polymer as one ingredient of an epoxy resin composition.

The modified aromatic hydrocarbon polymer will first be described in detail.

The aromatic hydrocarbon polymer in accordance with this invention can be produced by the cationic polymerization of the following basic polymerizable materials.

(a) Cationically polymerizable hydrocarbon-containing fraction having a boiling range of 140 to 2800C obtained by the distillation of a cracking or reforming product of a petroleum: In the present specification and appended claims the term "petroleum" denotes naphtha, gas oils, kerosene, or crude oils.

The term "fraction obtained by distilling the cracking or reforming product of a petroleum" denotes a hydrocarbon-containing fraction which is formed as a by-product in the thermal or catalytic cracking, such as steam cracking, vapor phase cracking or sand cracking or reforming, such as hydroreforming, of the petroleum defined above.

As the polymerizable material (a) in accordance with this invention, a cationically polymerizable unsaturated hydrocarbon-containing fraction which has a boiling range of 140"C to 2800C, preferably 1400C to 2400C, more preferably 1600C to 2000C, is specifically used.

The petroleum cracking or reforming fraction having a boiling range of from 1400C to 2800C contains cationically polymerizable hydrocarbons and non-polymerizable hydrocarbons, most of which contain at least 8 carbon atoms. The hydrocarbons with at least 8 carbon atoms are contained generally in an amount of at least 90% by weight based on the weight of the fraction. Specifically, the composition of the petroleum fraction varies over a broad range according, for example, to the type of the petroleum cracked or reformed and the cracking or reforming conditions. According to the present invention, a fraction containing at least 20% by weight, preferably 30 to 75% by weight, more preferably 35 to 60% by weight, based on the weight of the fraction, of cationically polymerizable hydrocarbon is advantageously used.

Hydrocarbons having at least 8 carbon atoms contained in the fraction are almost all aromatic hydrocarbons, the major proportion of which consists of aromatic hydrocarbons containing 9 or 10 carbon atoms. The total amount of such aromatic hydrocarbons with 9 and 10 carbon atoms is 50 to 95% by weight, usually 60 to 95% by weight, based on the weight of the fraction. The fraction contains some amounts of aromatic hydrocarbons containing 8 carbon atoms and more than 10 carbon atoms.

Typical examples of the cationically polymerizable hydrocarbons contained in the fraction are cationically polymerizable aromatic unsaturated hydrocarbons containing 8 to 12 carbon atoms, such as styrene, a- or P-methyl-styrene, o-, m- or p-vinyltoluene, isopropenyltoluene, indene, methylindene, divinylbenzene, and vinylnaphthalene.

In an especially preferred embodiment, the fraction contains at least 20% by weight in total of such cationically polymerizable unsaturated aromatic hydrocarbons.

The term "cationically polymerizable aromatic unsaturated hydrocarbons", as used herein, denotes a hydrocarbon containing at least one aromatic ring and at least one cationically polymerizable unsaturated bond.

Other typical cationically polymerizable non-aromatic hydrocarbons include olefins and/or diolefins with 8 to 12 carbon atoms such as dicyclopentadiene or methyldicyclopentadiene which are present in minor quantities.

On the other hand, typical examples of the non-polymerizable hydrocarbons contained in the fraction include CR to C12 aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, n-propylbenzene, trimethylbenzene, indane, methylindane, naphthalene, methylnaphthalene, and dimethylnaphthalene. Other examples of the non-polymerizable hydrocarbons are Cs to C,2 paraffins and/or naphthenes which are present in small amounts.

As stated hereinabove, the composition of the petroleum cracking or reforming fraction used in this invention changes over a wide range according, for example, to the petroleum cracked or reformed, and the cracking or reforming conditions, and cannot be definitely determined. Generally, the fraction preferably has a bromine value of 50 to 90. Fractions having the following compositions are especially preferably used. It should be noted however that the present invention is not limited to the following exemplification.

Components Amounts in percent buy weight Cationically polymerizable aromatic unsaturated hydrocarbons 25 to 75, preferably 30 to 60 Olefins 0 to 15, preferably 5 to 10 Diolefins 0 to 5, preferably 1 to 3 Non-polymerizable aromatic saturated hydrocarbons 15 to 50, preferably 20 to 40 Paraffins and naphthenes 5 to 25, preferably 10 to 25 Examples of the cationically polymerizable aromatic unsaturated hydrocarbons given iii the above table are C5 to Cil cationically polymerizable aromatic unsaturated hydrocarbons such as styrene, a- or jB-methylstyrene, o-, m- or p-vinyltoluene, indene, and methylindene.

Usually cationically polymerizable aromatic unsaturated hydrocarbons having 9 to 10 carbon atoms such as a- or,P-methylstyrene, o-, m-, or p-vinyltoluene, indene and methylindene usually account for 50 to 95% by weight, usually 60 to 95% by weight, based on the cationically polymerizable aromatic unsaturated hydrocarbons.

Usually, C8 cationically polymerizable aromatic unsaturated hydrocarbons such as styrene, and Cll~ 12 cationically polymerizable aromatic unsaturated hydrocarbons are contained in an amount of 1 to 30% by weight, especially 2 to 20% by weight, and 1 to 40% by weight, especially 2 to 30% by weight, respectively.

Examples of the olefins and diolefins given in the above table are C8~12 aliphatic monoolefins and diolefins such as dicyclopentadiene or methyldicyclopentadiene. Typical examples of the non-polymerizable aromatic saturated hydrocarbons given in the table include C812 aromatic saturated hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, n-propylbenzene, trimethylbenzene, indane, methylindane, naphthalene, methylnaphthalene and dimethylnaphthalene.

The paraffins and naphthenes contained in the fraction include paraffins and naphthenes having 9 to 12 carbon atoms.

The cationically polymerizable aromatic unsaturated hydrocarbon component in be fraction typically consists essentially of the following components.

Components Amount in % by weight (*) Vinvltoluene Total 30 to 85, preferably 35 to 70 Styrene a-Methylstyrene Methylindene J p-Methylstyrene

(*) The amounts are based on the total weight of the cationically polymerizable aromatic unsaturated hydrocarbons.

The petroleum cracking or reforming fraction can be used either directly, or if desired, or as required, it may be purified prior to use by, for example, distilling it to separate the non-polymerizable hydrocarbons at least partly and to increase the content of the cationically polymerizable aromatic unsaturated hydrocarbons. In particular, a fraction having a boiling range of 140 to 240"C, most preferably 160 to 2000 C, is preferred.

(b) Cationically polymerizable aromatic unsaturated hydrocarbon: The fraction described in (a) above contains two or more cationically polymerizable aromatic unsaturated hydrocarbons in the mixed state. In the present invention, however, the aromatic unsaturated hydrocarbons can be used also in the isolated state.

Cationically polymerizable aromatic unsaturated hydrocarbons containing 8 to 12 carbon atoms, preferably 8 to 10 carbqn atoms, are especially suitable in the present invention. Typical examples of these aromatic unsaturated hydrocarbons include styrene, a- or ,3-methylstyrene, o-, m- or p-vinyltoluene, o-, m- or p-isopropenyltoluene, indene, o-, m- or p-ethylstyrene, 3-methylindene and vinyl naphthalene. Of these, styrene, la- or ,8-methylstyrene, o-, m- or p-vinyltoluene, and o-, m- or p-isopropenyltoluene are preferred. They can be used either alone or as a mixture of two or more.

(c) Mixture of ingredients (a) and (b) :- In a mixture of ingredients (a) and (b), the mixing proportions are not strictly limited, and can be varied widely according to the types of these ingredients (a) and (b), etc. Generally, the recommendable weight ratio of ingredient (a) to (b) is from 10:90 to 90:10, especially from 20:80 to 80:20.

Of the aforesaid polymerizable materials (a), (b) and (c), the cationically polymerizable aromatic unsaturated hydrocarbon (b) is especially preferred.

The polymerizable material described hereinabove is polymerized in accordance with this invention in the presence of a cationic polymerization catalyst.

The polymerization can be performed by known methods which are frequently used to produce ordinary hydrocarbon resins.

The term "cationic polymerization catalyst", as used in the present application, denotes a catalyst having the ability to form a cation in the polymerization system, and includes, for example, protonic acid, Friedel-Crafts catalysts (Lewis acids), halogens, metal oxides, metal sulfides, halogenated organometallic compounds, and cation exchange resins.

Typical examples of cationic polymerization catalysts used in this invention include Friedel-Crafts catalysts such as boron trifluoride, complexes of boron trifluoride with alcohols, phenols, ethers or organic carboxylic acids (e.g., boron trifluoride phenolate and boron trifluoride etherate), aluminum trichloride, aluminum tribromide, tin tetrachloride, tin tetrabromide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, potassium trifluoride, potassium trichloride, potassium tribromide, molybdenum pentafluoride, molybdenum pentachloride, molybdenum pentabromide, tungsten hexafluoride, tungsten hexachloride, tungsten hexabromide, tungsten pentafluoride, tungsten pentachloride, tungsten pentabromide, rhenium hexachloride, and rhenium hexabromide; and organoaluminum compounds such as diethylaluminum chloride and ethylaluminum dichloride. They may be used either singly or, if required, as a mixture of two or more.

Of these cationic polymerization catalysts, the Friedel-Crafts catalysts, especially boron trifluoride, boron trifluoride complexes, aluminum trichloride, tin tetrachloride and titanium tetrachloride, are preferred. The boron trifluoride, boron trifluoride com plexes, and aluminum trichloride are especially preferred. The amount of the catalyst is not particularly restricted. However, its suitable amount is usually 0.1 to 25% by weight, preferably 0.2 to 20% by weight, based on the weight of the polymerizable material.

The polymerization can be performed in the absence of solvent, but usually it is advantageous to perform it in the presence of a solvent. Suitable polymerization solvents are, for example, aliphatic saturated hydrocarbons such as pentane, hexane, heptane and kerosene, and aromatic saturated hydrocarbons such as benzene, toluene and xylene. When these saturated hydrocarbons are contained in the polymerizable material, they can be used as polymerization solvents.

The polymerization can be carried out usually at a temperature ranging from 0 to 2000 C, preferably 10 to 1500C. Atmospheric pressure suffices as the polymerization pressure. If desired, elevated on reduced pressures in the range of 0.1 to 50 atmos .pheres can be employed. Under these polymerization conditions, the polymerization can be completed usually within 10 minutes to 5 hours.

After the polymerization, the catalyst can be removed by such a treatment as washing with an alkali aqueous solution or with water, and the unreacted hydrocarbons or polymers with a low degree of polymerization can be removed by a suitable means such as distillation. Advantageously, the distillation is carried out generally at a tem perature of 150 to 2500C. and a pressure of 5 mmHg to 100 mmHg. As a result, hydro carbon resins are obtained as distillation bottoms.

The most characteristic feature of the present invention is to use the aforesaid aromatic hydrocarbon polymer as modified with a phenol or naphthol.

This modification can be achieved by introducing a phenol or naphthol into the polymerization reaction system of preparing the above aromatic hydrocarbon polymer at any stage of the polymerization process or into the resulting aromatic hydrocarbon polymer.

Introduction of a phenol or naphthol into the polymerization reaction system can be performed at any desired stage of the polymerization, for example, by mixing the phenol or naphthol with the polymerizable material before the initiation of the reaction; by adding the phenol or naphthol to the polymerization reaction mass during the pro ceeding of the polymerization; or by adding the phenol or naphthol to the reaction mixture after the polymerization reaction but before removing the cation polymerization catalyst, and continuing the reaction. Alternatively, the phenols or. naphthols can also be introduced into the polymer by separating the resulting polymer from the poly- merization system, adding the phenol or naphthol to the separated polymer, and reacting them in the presence of the cationic polymerization catalyst.

It is especially preferred in this invention, however,- that the phenol or naphthol be introduced into the polymerization reaction system before the initiation of the poly merization reaction.

Any conventional compounds having at least one hydroxyl group directly bonded to an aromatic ring can be used as the phenols or naphthols to modify the aromatic hydrocarbon polymer. Compounds expressed by the formula

wherein Ar represents a benzene or naphthalene ring, R1 and R2, independently from each other, represent a hydrogen atom or an alkyl group, and n is an integer of 1 or 2, can be used advantageously.

In formula (I), the alkyl group may be linear or branched, and contain up to 20 carbon atoms, preferably up to 15 carbon atoms, more preferably up to 12 carbon atoms. Examples are methyl, ethyl, n- or iso-propyl, n-sec-, iso- or tert-butyl, n-pentyl, iso-amyl, n-hexyl, n-octyl, n-nonyl, and n-decyl groups. Specific examples of the phenol or naphthol that can be used in this invention include phenol, cresol (o-, m- or p-), xylenol (2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-), isopropyl phenol, sec- or tert-butylphenol, p-tert-amyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, naphthol (r, or iP-), dihydroxybenzenes (resorcinol, catechol and hydroquinone), and pyrogallol.

Among these, phenol, cresol (o-, m- or p-), xylenol (2,6- or 3,5-), isopropyl phenol, sec- or tert-butylphenol, octyl phenol, nonyl phenol, dodecyl phenol, naphthol (a- or ,B-), and dihydroxybenzenes (resorcinol, catechol and hydroquinone) are preferred.

Phenol, cresols and dihydroxybenzenes are especially preferred.

These phenols or naphthols can be used either alone or as a mixture of two or more of them.

The amount of the phenol or naphthol is not critical, and can be varied widely according to the characteristics required of the final modified polymer, for example.

Generally, the suitable amount of the phenol or naphthol is 5 to 100 parts by weight, preferably 6.5 to 70 parts by weight, most preferably 10 to 50 parts by weight, per 100 parts by weight of all the cationically polymerizable components of the polymerizable material. When the phenol or naphthol is to be added to the resulting polymer, its amount is desirably within the above-specified ranges per 100 parts by weight of the polymer.

As stated hereinabove, the phenol or naphthol can be introduced into the polymerization reaction system at any desired stage of the polymerization of the polymerizable material. For example, it may be mixed with the starting material before the initiation of polymerization, or to the reaction mixture during the polymerization reaction, or to the reaction mixture immediately after the polymerization reaction.

The reaction after mixing of the phenol or naphthol can be performed in the presence of a cationic polymerization catalyst under the same polymerization reaction conditions as used in the polymerization, and no special attention needs to be paid.

It is also possible to add the phenol or naphthol to an aromatic hydrocarbon polymer produced by the above polymerization reaction and then separated, and react them under the same conditions as the polymerization conditions in the reaction solvent and in the presence of the cationic polymerization catalyst.

Various properties of the resulting modified polymer, such as softening point, molecular weight, molecular weight distribution, melt viscosity, solubility and compatibility, can be varied widely by properly choosing the types of the polymerizable material and/or the phenol or naphthol, the polymerization conditions, etc.

In the modified polymer so produced, the aromatic hydrocarbon polymer formed by the polymerization of the polymerizable material is chemically modified by a phenol or naphthol, and the phenol is incorporated into the chain of the aromatic hydrocarbon polymer while partly retaining its hydroxyl groups, or partly through an ether linkage ascribable to the hydroxyl groups. Accordingly, the modified polymer of this invention can have a hydroxyl content of generally 0.3 to 7 millimoles/g, preferably 0.4 to 5.5 millimoles/g, more preferably 0.5 to 4 millimoles/g, according to the amount of the phenol or naphthol introduced.

The modified polymer can have a phenol or naphthol content of generally 3 to 50% by weight, preferably 4.5 to 50% by weight, more preferably 6 to 40% by weight, according to the amount of the phenol or naphthol introduced into the polymer.

The term "hydroxyl content", as used in the present specification and the appended claims, is defined as follows: The absorbances at 3550 cm-' (the characteristic absorption wave number of a phenolic hydroxyl group) of toluene solutions containing phenol in various predetermined concentrations are measured by using an infrared spectrophotometer DS-80/G (a standard cell, thickness 0.1 m) of Nippon Bunko Kogyo K.K., and a standard calibration curve is prepared by plotting the absorbances on the axis of ordinates and the phenol concentrations on the axis of abscissas. Separately, 0.3 g of a sample is dissolved in 10 ml of toluene, and the absorbance of the solution at 3550 cm-l is read.

The phenol concentration corresponding to the absorbance read from the standard calibration curve is determined, and defined as the hydroxyl content of the sample.

The "phenol or naphthol content" is obtained by determining the oxygen content of a sample by an element analyzer (type O-corder MO--10, a product of Yanagimoto Seisakusho), and multiplying the oxygen content (% by weight) by the quotient obtained by dividing the molecular weight of the phenol or naphthol used for modification by the number of hydroxyl groups present in the phenol or naphthol.

The modified polymer ranges from a liquid state at room temperature to a solid state with a softening point (by the ball-and-ring method in ASTM E 2858T) of not more than 200"C., preferably not more than 1800C.

The modified polymer can have a number average molecular weight of generally 200 to 3000, preferably 200 to 2000, most preferably 250 to 1500. Sometimes, the modified polymer has a Gardner color number of about 17, but generally it is available in a comparatively light color with a Gardner color number of less than about 10. It can be used advantageously in applications in which coloration is undesired.

According to this invention, the modified polymer is used to prepare a tar-epoxy resinous composition in conjunction with a polyepoxy compound and a curing agent.

The polyepoxy compound that can be used in the epoxy resin composition is a compound containing at least two epoxy groups per molecule. Both low-molecularweight and high-molecular-weight polyepoxy compounds containing at least two epoxy groups per molecule can be used. They may also be aliphatic, aromatic, or araliphatic, or may contain a heterocycle. Thus, any epoxy compounds ordinarily used in the conventional tar epoxy resin compositions are feasible in this invention.

The polyepoxy. compound can be freely selected from known compounds according to the purpose of use of the final epoxy resin composition or the characteristics required of the final composition. Specific examples are given below. It should be understood however that the scope of the present invention is in no way limited by these examples.

(1) Polyglycidyl ethers of polyphenols: Diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, tetraglycidyl ether of 1,1,2,2-tetrakis(4'-hydroxyphenyl )ethane, diglycidyl ether of 2,2-bis(4-hydroxyphenyl)nonadenane, diglycidyl ether of diphenyl ether, diglycidyl ether of tetrachlorobisphenol A, diglycidyl ether of tetrabromobisphenol A, and diglycidyl ether of bisphenol-hexafluoroacetone.

(2) Polyglycidyl ethers of nuclearly hydrogenated products of polyphenol compounds:

(2,2 - (4 - [3 - Chloro - 2 - (2,3 - epoxy propoxy)propoxyj - cyclohexyl) propane)

(diglycidyl ether of hydrogenated bisphenol A)

("Epikote" (Trade Mark) 871, a product of Shell) (3) Polyglycidyl ethers of polyhydric phenols: Catechol diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, phloroglycin ditriglycidyl ether, trihydroxy biphenyl triglycidyl ether, tetraglycidoxy biphenyl, methylphloroglycin triglycidyl ether, tetraglycidyl ether of bis-resorcinol, and tetraglycidyl ether of resorcinol ketone.

(4) Polyglycidyl ethers of polyhydric alcohols:- Ethyl glycol diglycidyl ether, butanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ethers, polyoxyalkylene glycol diglycidyl ethers, and trimethylolpropane triglycidyl ether.

(5) Novolak type polyepoxy compounds: Polyglycidyl ether of phenol-formaldehyde novolak

(a=0-8, b=0-8, c=0-1) Polyglycidyl ether of o-cresol-formaldehyde novolak

(a=0-4, b=0-8) (6) Alicyclic polyepoxy compounds: Vinyl cyclohexane dioxide, limonene dioxide, dicyclopentadiene dioxide, 2,2-bis(3,4-epoxycyclohexyl )propane, bis(2,3-epoxycyclopentyl ) ether, and bisepoxy dicyclopentyl ether of ethylene glycol.

(7) Polyglycidyl esters of polycarboxylic acids or their condensates: Diglycidyl phthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalate, diglycidyl ester of dimeric acid, diglycidyl hexahydrophthalate, and diglycidyl ester of a condensate of terephthalic acid (or isophthalic acid) and ethylene glycol (polyester) having the following formula

(myl) (8) Polyglycidyl amine compounds:

(in which R is a hydrocarbon group with 1 to 25 carbon atoms, such as alkyl, aryl, aralkyl or alkaryl) [e.g. diglycidyl methyl amine, diglycidyl ethyl amine, diglycidyl propyl amine, and diglycidyl aniline], triglycidyl p-aminophenol, triglycidyl isocyanurate, and tetraglycidyl aminodiphenylmethane.

(9) Methyl epichlorohydrin-type polyepoxy compounds: Di(2-methyl)glycidyl ether of ethylene glycol, di(2-methyl)glycidyl ether of bisphenol A, di(2-methyl)glycidyl ether of bisphenol F, di(2-methyl)glycidyl phthalate, and di(2-methyl)glycidyl isophthalate, Among these polyepoxy compounds, the polyglycidyl ethers of polyphenolic compounds and novolak-type polyepoxy compounds are used conveniently in the present invention. Above all, bisphenol A diglycidyl ether, and bisphenol F diglycidyl ether are preferred.

The epoxy equivalent and molecular weight of the polyepoxy compound that can be used in this invention are not critical, and can be varied widely according to the use and properties of the final polyepoxy resin composition. Generally, it has an epoxy equivalent of at most 5,000, preferably 43 to 3,500, more preferably 80 to 3,000, and a molecular weight of 86 to 20,000, preferably 130 to 10,000, most preferably 150 to 5,000. Those which are liquid or solid at room temperature can be used. Preferably, solid polyepoxy compounds are used as a solution in a suitable solvent.

Any curing agents which are generally known as curing agents for epoxy resins can be used in the polyepoxy resin composition provided by this invention. These curing agents are polyfunctional compounds containing at least two functional groups per molecule, such as primary, secondary or tertiary amino groups, acid anhydride groups, mercapto groups, or phenolic hydroxyl group. Typical examples are given below. It should be understood that the scope of the invention is in no way limited by these examples.

(1) Linear aliphatic primary polyamines Diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene diamine, and diethylaminopropylamine.

(2) Alicyclic primary polyamines N-aminoethylpiperazine, methanediamine, 1,3-diaminocyclohexane, isophoronedi amine, bis(4 - amino - 3 - methylcyclohexyl)methane, 3,9 - bis(3 - amino propyl) - 2,4,8,10 - tetroxaspiro [5,5]undecane, and 1,3 - diaminocyclohexane.

(3) Modified aliphatic primary polyamines (i) Amine epoxy resin adducts: Diethylene triamine-bisphenol A glycidyl ether adduct (ii) Amine ethylene oxide or propylene oxide adducts: N,N'-bis (hydroxyethyl) diethylene triamine, N,N'-bis (hydroxypropyl ) diethylene triamine, N- ( hydroxypropyl ) diethylenetriamine, N- (2-hydroxy-2,4,4-trimethylphenyl) diethylene triamine, N- (2-hydroxyethyl ) diethylene triamine, and N,N,N',N'-tetrahydroxypropylene diamine.

(iii) Cyanoethylated polyamines : Cyanoethylated diethylene triamine, cyanoethylated triethylene tetramine, and cyanoethylated tetraethylene pentamine.

(iv) Ketone blocked polyamines : Reaction product between diethylene triamine and a ketone having the formula 'R2C = N-( -CH2- ) 2-NH- -CH.- )2-N - CTh (R=C1 ,, alkyl group) (4) Aromatic primary polyamines o-, or m-Phenylenediamine, diaminodiphenyl ether, 4,4'-methylenedianiline, di aminodiphenyl sulfone, dimethyl diphenyl methane, m-xylylene diamine, 4,4'-bis (o - toluidine), tetrachioro - p - xylylenediamine, 4,4' - thiodianiline, 4,4' bis ( o-toluidine), dianisidine, 2,4-toluenediamine, methylene-bis (o-chloroaniline), m-aminobenzylamine, a eutectic blend of aromatic amines (e.g., a eutectic blend of m-phenylenediamine and 4,4'-methylenedianiline), and an adduct of an aro matic amine with styrene oxide or phenylglycidyl ether.

(5) Tertiary amine-type curing agents (i) Aliphatic tertiary amines: N,N,N',N' - Tetramethyl - 1,3 - butanediamine, tetramethylguanidine, tri ethanolamine, 2-dimethylamino-2-hydroxypropane, and trialkylamines such as trimethylamine and triethylamine.

(ii) Alicyclic tertiary amines:- N,N'-dimethylpiperazine, N-methylmorpholine, and 1,4-diazabicyclo (2,2,2) octane.

(iii) Heteroaromatic ring-containing tertiary amines:- Picoline, pyridine, pyrazine, and quinoline.

(iv) Aromatic ring-containing aliphatic tertiary amines:- Benzyldimethylamine, a - methylbenzyldimethylamine, 2 - (dimethyl aminomethyl)phenol, and 2i4,6-tris(dimethylaminomethyl)phenol.

(6) Mercaptan-type curing agents

(n=1-2; R=aliphatic hydrocarbon group) Examples are Thiokol (a trademark for a product of Thiokol Company) and Epi-Cure 861 (a trademark for a product of Celanese Corporation).

(7) Acid anhydride-type curing agents Phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhy dride, hexahydrophthalic anhydride, methylbicyclo[2.2.1]heptene - 2,3 - di carboxylic anhydride, dodecenylsuccinic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, and tetrahydrophthalic anhydride.

(8) Phenolic hydroxyl-containing compounds Phenol-formaldehyde precondensates (novolak and resol types), resorcinol, phloro glucinol, 1,5-naphthalenediol, and 4,4'-dihydroxydiphenylsulfone.

(9) Other compounds (i) boron trifluorine-amine complexes, (ii) dicyandiamide, (iii) melamine resins, (iv) urea resins, (v) 2-ethyl-4-methyl imidazole, (vi) polysulfide resins, (vii) polyamide resins, (viii) amide polyamines, and (ix) polyamide amines.

The reaction products of fatty acids and polyamines (e.g., diethylene triamine, triethylene tetramine, and tetraethylene pentamine).

CH3 (CH2 )CONH(CH, ) 2NH( CH2 ) ,NH, CII,I( CH, )ONH(CH2),NH(CH,),NH(CH2 ),NH, (n=1-20) These curing agents can be used singly, or if desired, two or more of them may be used as a mixture. The curing agent to be used in a particular composition can be chosen according to the desired rate of curing and properties of the final composition, and those skilled in the art can make such a choice very easily by preliminary routine experiments.

Preferred curing agents for use in the present invention are linear aliphatic primary polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene diamine and diethylamino propane; adducts of aliphatic polyamines with epoxy resins; adducts of aliphatic polyamines with ethylene oxide or propylene oxide; modified aliphatic primary polyamines such as cyano-ethylated aliphatic primary polyamines; amide polyamines; aromatic primary polyamines; and acid anhydride-type curing agents.

In the present composition, the proportions of the modified polymer, the polyepoxy compound and the curing agent are not strictly restricted, and can be varied widely according, for example, to the properties required of the final composition.

Generally, the modified polymer can be used in an amount of 3 to 700 parts by weight, preferably 4 to 660 parts by weight, most preferably 5 to 500 parts by weight, per 100 parts by weight of the polyepoxy compound. On the other hand, it is advantageous to use the curing agent in an amount of 3 to 500 parts by weight, preferably 4 to 300 parts by weight, most preferably 5 to 250 parts by weight, per 100 parts by weight of the polyepoxy compound.

The polyepoxy resin composition provided by the present invention may further contain optional additives. Examples of the additives are phenolic resins, alkvd resins, petroleum resins, pigments (e.g., titanium oxide, antimony oxide, cadmium red, toluidine red, phthalocyanine blue), fillers (e.g., talc, silica, mica, cryolite, clay, calcium carbonate, alumina, portland cement, graphite), reactive diluents (e.g., styrene oxide, allyl glycidyl ether, butyl glycidyl ether, vinylcyclohexane monoxide, dipentene monoxide, glycidyl methacrylate), flexibilizers (e.g., polyamides, polysulfide resins, poly- urethane elastomers), and solvents.The amounts of such additives are, for example, 0 to 1000 parts by weight for the pigments and fillers; 0 to 50 parts by weight for the reactive diluents and flexibilizers; and 0 to 2000 parts by weight for the solvents, all per 100 parts by weight of the polyepoxy compound.

The polyepoxy resin compositions provided by the present invention include both room temperature-curable type compositions which cure at room temperature, and heat-curable type compositions which cure only when heated at a temperature of about 50 to about 200"C., depending upon the types of the polyepoxy compound and curing agent to be included in the compositions.

The epoxy resin composition of this invention can be prepared by any conventional methods. For example, the modified polymer is mixed first with the polyepoxy compound or the curing agent, and just prior to use in applications to be described below, the mixture is uniformly mixed with the curing agent or the polyepoxy compound. Or just prior to use in the applications to be described below, the modified polymer, the polyepoxy compound and the curing agent are simultaneously mixed to form a uniform blend. Additives such as pigments, fillers, reactive diluents and solvents can be added simultaneously with the addition of the polyepoxy compound or curing agent to the modified polymer. But advantageously, the additives are fully mixed with the polyepoxy compound beforehand, and then the mixture is mixed with the modified polymer and/or the curing agent.

The modified polymers employed in this invention have superior compatibility with epoxy resins and curing agents. Hence, epoxy resin compositions including the modified polymers according to this invention can be stored stably over long periods of time. In comparison with tar-containing epoxy resin compositions, the epoxy resin compositions of this invention have reduced bleed-out and superior mechanical strength (e.g., compression or impact strength), abrasion resistance, water resistance, and chemical resistance (e.g., alkali resistance). Therefore, these compositions can be suitably used in fields which use tar-containing epoxy resin compositions, for example as paints, road repairing materials, or slip-preventing floor materials.

Furthermore, in comparison with compositions of epoxy resins and curing agents not containing the modified polymers of this invention, the epoxy resin compositions of this invention have superior adhesion, mechanical strength (e.g., compression or impact strength), water resistance, chemical resistance (e.g., alkali or solvent resistance), and thermal stability. These epoxy resin compositions can also be used in a wide range of applications as, for example, cast articles, adhesives and laminated boards.

Since the modified polymer in accordance with this invention is available in a relatively light to colorless color, the epoxy resin composition of this invention can be obtained in a light color. Accordingly, it can be used advantageously also in applications which permit only light-colored coloration.

The following Examples specifically illustrate the epoxy resin composition of this invention.

Example 1.

(1) Preparation of phenol-modified poly(a-methylstyrene) A liter glass reactor equipped with a thermometer, a reflux condenser, a feed opening and a stirrer was charged with a mixture consisting of 170 g of a-methylstyrene, 30 g of phenol and 200 g of toluene. The mixture was stirred to form a solution.

To the resulting solution was added dropwise 2 g of a boron triflouride/phenol complex, and the polymerization was performed in a nitrogen atmosphere at 30"C. for 2 hours. To the resulting polymerization product was added 150 ml of a 0.3N aqueous solution of sodium hydroxide, and the mixture was stirred for 30 minutes. The aqueous layer was separated, and the residue was repeatedly washed with water until the aqueous layer became neutral. The aqueous layer was separated, and the residue was concentrated at 200"C. and 5 mmHg for 30 minutes to afford 195 g of a modified polymer. The properties of the polymer are shown in Table 2.

(2) Preparation of an epoxy resin composition A blend consisting of 40 parts by weight of bisphenol A diglycidyl ether (EPO MIK R-144, a trademark for a product of Mitsui Petrochemical Epoxy Co., Ltd.), 40 parts by weight of the phenol-modified poly(a-methylsryrene) prepared in section (1) above, 100 parts by weight of talc, 30 parts by weight of titanium white and 40 parts by weight of ethyl cellulose was passed through a three-roli mill three times to disperse the talc uniformly in the blend.Then, 30 parts by weight of a polyamide amine curing agent (EPOMIK Q-671, a trademark for a product of Mitsui Petro-chemical Epoxy Co., Ltd.), and the viscosity of the resulting mixture was adjusted to 2500 centipoises (measured by a B-type viscometer) with a 1:1 by weight mixture of xylene and tert-butanol. The resulting composition was coated on a mild steel plate.

(3) Test for the performance of the coated film The coated film obtained was tested for performance by the method described hereinbelow. The results are shown in Table 2.

Examples 2 to 9.

The procedure of Example 1, (1) was repeated except that 170 g of each of the polymerizable materials shown in Table 2 was used instead of 170 g of the a-methyl- styrene in Example 1, (1). Thus, phenol-modified polymers having the characteristics shown in Table 2 were prepared.

Then, the procedure of Example 1, (2) was repeated except using each of the phenol-modified polymers obtained above in the amount shown in Table 2 instead of the phenol-modified poly(a-methylstyrene), each of the polyepoxy compounds in the amounts shown in Table 2 instead of the bisphenol A diglycidyl ether, and each of the curing agents shown in Table 2 instead of the polyamide amine curing agent in Example 1, (2). Thus, epoxy resin compositions were prepared.

These compositions were tested for the performances of coated films in the same way as in Example 1, (3). The results are shown in Table 2.

Comparative Example 1.

An epoxy resin composition was prepared by repeating the procedure of Example 1, (2) except that 40 parts by weight of a coal tar (TACRON #180) was used instead of 40 parts by weight of the phenol-modified poly(a-methylstyrene) in Example 1, (2).

The composition was tested for coating performance in the same way as in Example 1, (3). The results are summarized in Table 2 below.

Examples 10 and 11.

(1) Preparation of a phenol-modified polymer A 1-liter glass reactor equipped with a thermometer, a reflux condenser, a feed opening and a stirrer was charged with a mixture consisting of 185 g of a-methyl- styrene, 15 g of ether ss-naphthol or resorcinol and 200 g of toluene, and the mixture was stirred. To the resulting solution was added dropwise 2 g of a boron trifluoride/ phenol complex, and the polymerization was performed in a nitrogen atmosphere at 50"C. for 2 hours. To the resulting polymerization product was added 150 ml of a 0.3N aqueous solution of sodium hydroxide. The mixture was stirred for 30 minutes.

and the aqueous layer was separated. The residue was repeatedly washed with water until the aqueous layer became neutral. The aqueous layer was separated, and the residue was concentrated at 2000C. and 5 mmHg for 30 minutes to afford a modified polymer having the properties shown in Table 2.

(2) Preparation of an epoxy resin composition A blend consisting of 72 parts by weight of bisphenol A diglycidyl ether (EPO MIK R-140, a trademark for a product of Mitsui Petrochemical Epoxy Co., Ltd.), 8 parts by weight of the modified poly(a-methylstyrene) prepared in section (1) above, 100 parts by weight of talc, 20 parts by weight of titanium white and 40 parts by weight of ethyl cellulose was passed through a three-roll mill three times. Then, 50 parts by weight of a polyamide amine curing agent (EPOMIK Q-671, a trademark for a product of Mitsui Petro-Chemical Epoxy Co., Ltd.) was added. The viscosity of the mixture was adjusted to 2500 centipoises (measured by a B-type viscometer) with a 1:1 by weight mixture of xylene andsec-butanol. The resulting composition was coated on a mild steel plate.

(3) Test for the performance of coated film The coated film obtained was tested for performance by the method described hereinbelow. The results are shown in Table 2.

Examples 12 to 21.

(1) Preparation of a phenol-modified polymer A 1 liter glass reactor equipped with a thermometer, a reflux condenser, a feed opening and a stirrer was charged with a mixture consisting of 170 g of a naphtha cracking hydrocarbon fraction having each of the compositions A to C shown in Table 1 below and 30 g of a phenol, and the mixture was stirred. To the resulting solution was added dropwise 2 g of a boron trifluoride/phenol complex, and the polymerization was performed in a nitrogen atmosphere at 300 C. for 2 hours. To the resulting polymerization product was added 150 ml of a 0.3N aqueous solution of sodium hydroxide, and the mixture was stirred for 30 minutes. The aqueous layer was separated, and the residue was repeatedly washed with water until the aqueous layer became neutral. The aqueous layer was separated, and the residue was concentrated at 2000 C. and 5 mmHg for 30 minutes to afford a modified polymer having the properties shown in Table 2.

TABLE 1 Content (% by weight based on the fraction) Component A B C Styrene 2.8 0.7 1.8 a-Methyl styrene 2.1 3.0 1.5 ss-Methylstyrene 2.3 3.2 1.4 Vinyltoluene 18.0 25.5 14.0 Indene 12.1 16.3 9.1 Methylindene 4.2 1.0 3.0 Trimethylbenzene 12.0 20.0 10.0 Naphthalene 5.1 0.0 4.3 Other C,-C,, aromatic saturated hydrocarbons 30.5 22.3 40.5 Paraffins and unidentified components 10.9 8.0 14.4 Total of the aromatic unsaturated hydrocarbons 41.5 49.7 30.8 Boiling range of the fraction (OC) 140-240 160-200 140-280 (2) Preparation of an epoxy resin composition A blend consisting of 40 parts by weight of bis-phenol A diglycidyl ether (EPO MIK R-144, a trademark for a product of Mitsui Petrochemical Epoxy Co., Ltd.), 40 part by weight of the polymer obtained in (1) above, 100 parts by weight of talc, 30 parts by weight of titanium white and 40 parts by weight of ethyl cellulose was passed through a three-roll mill three times to disperse the talc uniformly in the blend.

Then, a polyamide amine curing agent (EPOMIK Q-671) was added in an amount of 30 parts by weight, and the viscosity of the mixture was adjusted to 2500 centipoises (measured by a B-type viscometer) with a 1:1 by weight mixture of xylene and secbutyl alcohol. The resulting composition was coated on a mild steel plate.

(3) Test for the performance of the coated film The resulting coated film was tested for performance by the method to be described. The results are shown in Table 2.

Example 22.

(1) Preparation of a phenol-modified polymer A 1 liter glass reactor equipped with a thermometer, a reflux condenser, a feed opening and a stirrer was charged with a mixture consisting of 170 g of a naphthacracking hydrocarbon fraction having the composition (C) shown in Table 1 and 30 g of a phenol, and the mixture was stirred. To the resulting solution was added 2 g of a boron trifluoride/phenol complex, and in a nitrogen atmosphere, the polymerization was performed at 0 C. for 2 hours. 150 ml of a 0.3N aqueous solution of sodium hydroxide was added to the resulting polymerization product, and the mixture was stirred for 30 minutes. The aqueous layer was separated, and the residue was repeatedly washed until the aqueous layer became neutral.The aqueous layer was separated, and the residue was concentrated at 200PC. -and 5 mmHg for 30 minutes to afford a modified polymer having the properties shown in Table 2.

(2) Preparation of an epoxy resin composition A blend consisting of 20 parts by weight of bisohenol A diglycidyl ether (EPO MIK R-144, a trademark for a product of Mitsui Petrochemical Epoxy Co., Ltd.), 60 parts by weight of the polymer obtained in section (1) above, 100 parts by weight of talc, 30 parts by weight of titanium white and 40 parts by weight of ethyl cellulose was passed through a three-roll mill three times to disperse the talc uniformly in the blend. Then, a polyamide amine curing agent (EPOMIK Q-671) was added in an amount of 20 parts by weight, and the viscosity of the mixture was adjusted to 2500 centipoises (measured by a B-type viscometer) with a 1:1 by weight mixture of xylene and sec-butanol. The resulting composition was coated on a mild steel plate.

(3) Test for the performance of coated film The resulting coated film was tested for performance by the method described hereinbelow. The results are shown in Table 2.

TABLE 2

Example 1 2 3 Modified polymer Polymerizable material a-methyl styrene styrene isopropenyl styren Phenol or naphthol phenol phenol phenol Softening point ( C.) 35 52 41 Color (Gardner number) 4 3 3 Constant of the phenol or naphthol (% by weight) 14 12 13 Hydroxyl content (millimoles/g) 1.5 1.2 1.0 Amount used (parts by weight) 40 40 40 Polyepoxy compound (EPOMIK) (parts by weight) R-144 (40) R-144 (40) R-144 (40) Curing agent (EPOMIK) (parts by weight) Q-671 (30) Q-671 (30) Q-671 (30) Properties of the coated film Pot life (hr, 20 C.) 24 24 24 Finger touch drying time (hr, 200C.) 8.5 8.0 8.0 Curing time (hr, 200C.) 33 34 35 Crosscut test for adhesion 100 /100 100/100 100/100 Salt spray test (300 hours) No change No change No change Acid resistance test No change for No change for No change for (10% H2 SO4) one month one month one month Alkali resistance (10% NaOH) Ditto Ditto Ditto Water resistance Ditto Ditto Ditto n-Hexane resistance (300C.) Ditto Ditto Ditto Strength HB H HB Color White White I~ White TABLE 2 (Continued)

Example 4 5 6 Modified polymer Polymerizable material vinyltoluene 1) indene α;-methylstyrene Phenol or naphthol phenol phenol phenol Softening point ( C.) 55 130 35 Color (Gardner number) 7 5 4 Content of the -henol or naphthol (% by weight) 14 14 14 Hydroxyl content (millimoles/g) 1.3 1.4 1.5 Amount used (parts by weight) 40 40 40 Polyepoxy compound (EPOMIK) (parts by weight) R-144 (40) R-144 (40) R-144 (40) Curing agent (EPOMIK) (parts by weight) Q-671 (30) Q-671 (30) Q607 4) (35) Properties of the coated film Pot life (hr, 200C.) 24 23 24 Finger touch drying time (hr 200C.) 8.0 7.5 8.5 Curing time (hr, 200C.) 32 30 34 Crosscut test for adhesion 100 /100 100 '100 100 /100 Salt spray test (300 hours) No change No change No change Acid resistance test No change for No change for No change for (10% H2SO4) one month one month one month Alkali resistance (10% NaOH) Ditto Ditto Ditto Water resistance Ditto Ditto Ditto n-Hexane resistance Dittd Ditto Ditto (30CC.) Strength Ii 2H HB Color Whits White White TABLE 2 (Continued)

Example 7 8 9 Modified polymer Polymeri zable material a-methylstyrene styrene ame thy Is tyrene Phenol or naphthol phenol phenol phenol Softening point ( C.) 35 52 35 Color (Gardner number) 4 3 4 Content of the phenol or naphthol (% by weight) 14 12 14 Hydroxyl content (millimoles/g) 1.5 1.2 1.5 Amount used (parts by weight) 8 25 40 Polyepoxy compound (EPOMIK) (parts by weight) R-144 (72) R-144 (55) R-301 3) (40) Curing agent (EPOMIK) (parts by weight) Q-671 (50) Q-671 (20) Q671 (30) Properties of the coated film Pot life (hr, 20 C.) 24 24 24 Finger touch drying time (hr, 20 C.) 8.5 8.5 8.5 Curing time (hr, 200C.) 36 36 35 Crosscut test for adhesion 100/100 100/100 100/100 Salt spray test (300 hours) No change No change No change Acid resistance test No change for No change for No change (10% H2 SO4) one month one month one month Alkali resistance (10% NaOH) Ditto Ditto Ditto Water resistance Ditto Ditto Ditto n-Hexane resistance (30 C.) Ditto Ditto Ditto Strength B HB H Color White White White TABLE 2 (Continued)

Example Comp. Ex. 1 10 11 Modified polymer Polymeri zable material TARCRON #180 α-methylstyrene α-methylstyrene Phenol or naphthol - ss-naphthol resorcinol Softening point ( C.) - 63 68 Color (Gardner number) - 7 9 Constant of the phenol or naphthol (% by weight) - 7 7 Hydroxyl content (millimoles /g) 0.5 1.2 Amount used (parts by weight) 40 8 8 Polyepox compound (EPOMIK (parts by weight) R-144 (40) R-140 (72) R-140 (72) Curing agent (EPOMIK) (parts by weight) Q-671 (30) Q-67 1(50) Q-67 (50) Properties of the coated film Pot life (hr, 200C.) 24 24 24 Finger touch drying time (hr, 20 C.) 9.0 8.0 8.0 Curing time (hr, 20 C.) 40 35 30 Crosscut test for adhesion 100/100 100/100 100/100 Salt spray test Peeling by tust (300 hours) formation No change No change Acid resistance test Blister occurred No change for No change for (10% H2 SO4) in 20 days one month one month Alkali resistance Blister occurred Ditto Ditto (10% NaOH) in 22 days Water resistance No change for Ditto Ditto one month n-Hexane resistance Blister occurred Ditto Ditto (300C.) in 20 days Strength 2B B 2H Color Black brown White White TABLE 2 (Continued)

Example 12 13 14 Modified polymer Polymerizable material C9 fraction A C9 fraction B Cq fraction C Phenol or naphthol phenol phenol phenol Softening point ( C.) 57 70 65 Color (Gardner number) 15 13 16 Content of the phenol or naphthol (% by weight) 24 22 31 Hydroxyl content (millimoles "g) 2.0 1.8 2.6 Amount used (parts by weight) 40 40 40 Polyepoxy compound (EPOMIK) (parts by weight) 4-144 (40) R-144 (40) R-144 (40) Curing agent (EPOMIK) (parts by weight) Q 671 (30) Q-671 (30) Q-671 (30) Properties of the coated film Pot life (hr, 200C.) 24 24 23 Finger touch drying time (hr, 200C.) 7.5 7.5 7.5 Curing time (hr, 200C.) 32 32 29 Crosscut test for adhesion 100,'l00 100 'l00 100 100/100 Salt spray test (300 hours) No change No change No change Acid resistance test No change for No change for No change for (10% H2SO4) one month one month one month Alkali resistance (10% NaOH) Ditto Ditto Ditto Water resistance Ditto Ditto Ditto n-Hexane resistance (30 C.) Ditto Ditto Ditto Strength H 2H 2H Color Yellow Light yellow Yellow TABLE 2 (Continued)

Example 15 16 17 Modified polymer Polymerizable material (::, fraction A (', fraction A (", fraction A Phenol or naphthol cresol) isopropyl phenol sec-butyl phenol Softening point ( C.) 60 60 65 Color (Gardner number) 15 14 14 Content of the phenol or naphthol ('YO by weight) 2() 24 23 Hydroxyl content (millimoles/g) 1.7 1.4 1.2 Amount used (parts by weight) 40 40 40 Polyepoxy compound (EPOMIK) (parts by weight) R-144 (40) R-144 (40) R-144 (40) Curing agent (EPOMIK) (parts by weight) Q-67 1 (30) Q-671 (30) Q-671 (30) Properties of the coated film Pot life (hr, 200C.) 24 24 24 Finger touch drying time (hr, 200C.) 8.0 8.0 8.0 Curing time (hr, 200C.) 33 32 32 Crosscut test for adhesion 100/100 100/100 100/100 Salt spray test (30() hours) No change No change No change Acid resistance test No change for No change for No change for (10% H2SO4) one month one month one month Alkali resistance (10% NaOll) Ditto Ditto Ditto Water resistance Ditto Ditto Ditto n-llcxane resistance (30 C) Ditto Ditto Ditto Strength II II II Color Yellow light yellow Light yellow TABLE 2 (Continued)

Example 18 19 20 Modified polymer Polymerizable material C9 fraction A C9 fraction A C9 fraction A Phenol or naphthol tert-butyl phenol octyl phenol nonyl phenol Softening point (OC.) 70 63 61 Color (Gardner number) 14 15 15 Content of the phenol or naphthol (% by weight) 23 21 20 Hydroxyl content (millimoles /g) 1.2 0.8 0.8 Amount used (parts by weight) 40 40 40 Polyepoxy compound (EPOMIK) (parts by weight) R-144 (40) R-144 (40) R-144 (40) Curing agent (EPOMIK) (parts by weight) Q-671 (30) Q-671 (30) Q671 (30) Properties of the coated film Pot life (hr, 200C.) 24 24 24 Finger touch drying time (hr, 200C.) 7.5 8.0 8.0 Curing time (hr, 200C.) 31 33 32 Crosscut test for adhesion 100/100 100/100 100/100 Salt spray test (300 hours) No change No change No change Acid resistance test No change for No change for No change for (lo(r, H2 SO4) one month one month one month Alkali resistance (10% HaOH) Ditto Ditto Ditto Water resistance Ditto Ditto Ditto n-Hexane resistance (300C.) Ditto Ditto Ditto Strength 2H H H Color Light yellow Yellow Yellow TABLE 2 (Continued)

Example 21 22 Modified polymer Polymerizable material C9 fraction A C9 fraction A Phenol or naphthol dodecyl phenol phenol Softening point (OC.) 62 115 Color (Gardner number) 15 14 Content of the phenol or naphthol (% by weight) 20 23 Hydroxyl content (millimoles /g) 0.7 1.8 Amount used (parts by weight) 40 60 Polyepoxy compound (EPOMIK) (parts by weight) R-144 (40) R-144 (20) Curing agent (EPOMIK) (parts by weight) Q-671 (30) Q-671 (20) Properties of the coated film Pot life (hr, 2aOC.) 24 24 Finger touch drying time (hr, 200C.) 8.0 8.0 Curing time (hr, 200C.) 33 29 Crosscut test for adhesion 100/100 100/100 Salt spray test (300 hours) No change No change Acid resistance test No change for No change for (10% H2 SO4) one month one month Alkali resistance (10% NaOH) Ditto Ditto Water resistance Ditto Ditto n-Hexane resistance Blister occurred (300C.) Ditto in 28 days Strength H H Color Yellow Light yellow 1) m-/p- weight ratio= 6/4 2) m-/p- ratio 6/4 3) R-301, bisphenol A glycidyl ether, a product of Mitsui Petrochemical Epoxy Co., lAd.

4) Q-607, modified aliphatic polyamine, a product of Mitsui Petrochemical Epoxy Co., Ltd.

The properties shown in Table 2 were measured by the following methods.

(i) Softening point of the copolymer Measured by the ball and ring method in ASTM E 2858T.

(ii) Color (Gardncr number) Measured by the method of ASTM D154468.

(iii) The coated test plate was prepared by coating the composition on a mild steel plate by the method described in JIS K-5400. The thickness of the coated film upon drying was 150+5 microns.

(iv) The pot life of the epoxy resin composition, the finger touch drying time of the coated film, the curing time, and the acid resistance, alkali resistance and water resistance of the coated film were measured by the method of JIS K 5400.

(v) The salt spray test was performed by the method of JIS K-2371.

(vi) The strength of the coated film was measured by the method of JIS K-5651.

(vii) The color of the coated film was observed visually.

(viii) The crosscut test was performed by providing 11 parallel cuts in a substrate at an interval of 1 mm, and another set of 11 cuts at right angles to them, applying an adhesive tape to the substrate, pulling it away, and counting the number of remaining squares.

(ix) The resistance to n-hexane was performed by dipping the test sample in an n-hexane solution at 30"C., and then observing the state of the coated film visually.

WHAT WE CLAIM IS: 1. An epoxy resin composition comprising [A] a polymer having a hydroxyl content of 0.3 to 7 millimoles/g, said polymer being prepared by polymerizing a polymerizable material selected from (a) cationically polymerizable hydrocarbon-containing fractions having a boiling point in the range of from 140 to 2800C. obtained by distillation of a crack ing or reforming product of a petroleum, (b) a cationically polymerizable aromatic unsaturated hydrocarbon, and (c) a mixture of (a) and (b) in the presence of a cationic polymerization catalyst and modifying the resulting polymer with a phenol or naphthol; [B] a polyepoxy compound; and [C] a curing agent.

2. The composition of claim 1 wherein the cationically polymerizable hydrocarbon-containing fraction (a) contains at least 20% by weight of cationically polymerizable aromatic unsaturated hydrocarbons.

3. The composition of claim 1 wherein the cationically polymerizable aromatic unsaturated hydrocarbon (b) contains 8 to 10 carbon atoms.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (18)

**WARNING** start of CLMS field may overlap end of DESC **.

1) m-/p- weight ratio= 6/4

2) m-/p- ratio 6/4

3) R-301, bisphenol A glycidyl ether, a product of Mitsui Petrochemical Epoxy Co., lAd.

4) Q-607, modified aliphatic polyamine, a product of Mitsui Petrochemical Epoxy Co., Ltd.

The properties shown in Table 2 were measured by the following methods.

(i) Softening point of the copolymer Measured by the ball and ring method in ASTM E 2858T.

(ii) Color (Gardncr number) Measured by the method of ASTM D154468.

(iii) The coated test plate was prepared by coating the composition on a mild steel plate by the method described in JIS K-5400. The thickness of the coated film upon drying was 150+5 microns.

(iv) The pot life of the epoxy resin composition, the finger touch drying time of the coated film, the curing time, and the acid resistance, alkali resistance and water resistance of the coated film were measured by the method of JIS K 5400.

(v) The salt spray test was performed by the method of JIS K-2371.

(vi) The strength of the coated film was measured by the method of JIS K-5651.

(vii) The color of the coated film was observed visually.

(viii) The crosscut test was performed by providing 11 parallel cuts in a substrate at an interval of 1 mm, and another set of 11 cuts at right angles to them, applying an adhesive tape to the substrate, pulling it away, and counting the number of remaining squares.

(ix) The resistance to n-hexane was performed by dipping the test sample in an n-hexane solution at 30"C., and then observing the state of the coated film visually.

WHAT WE CLAIM IS: 1. An epoxy resin composition comprising [A] a polymer having a hydroxyl content of 0.3 to 7 millimoles/g, said polymer being prepared by polymerizing a polymerizable material selected from (a) cationically polymerizable hydrocarbon-containing fractions having a boiling point in the range of from 140 to 2800C. obtained by distillation of a crack ing or reforming product of a petroleum, (b) a cationically polymerizable aromatic unsaturated hydrocarbon, and (c) a mixture of (a) and (b) in the presence of a cationic polymerization catalyst and modifying the resulting polymer with a phenol or naphthol; [B] a polyepoxy compound; and [C] a curing agent.

2. The composition of claim 1 wherein the cationically polymerizable hydrocarbon-containing fraction (a) contains at least 20% by weight of cationically polymerizable aromatic unsaturated hydrocarbons.

3. The composition of claim 1 wherein the cationically polymerizable aromatic unsaturated hydrocarbon (b) contains 8 to 10 carbon atoms.

4. The composition of claim 1 wherein the cationically polymerizable aromatic

unsaturated hydrocarbon (b) is selected from the group consisting of styrene, a- and p-methylstyrenes, o-, m- and p-vinyltoluenes, o-, m- and p-isopropenyltoluenes, indene and mixtures of these.

5. The composition of claim 1 wherein the phenol or naphthol is a compound of the formula

wherein Ar represents a benzene or naphthalene ring, R1 and R2, independently from each other, represent a hydrogen atom or an alkyl group, and n is a integer of 1 or 2.

6. The composition of claim 1 wherein the phenol or naphthol is selected from the group consisting of phenol, cresol, xylenol, isopropyl phenol, sec- and tert-butyl phenols, octyl phenol, nonyl phenol, dodecyl phenol, naphthol and dihydroxybenzene.

7. The composition of claim 1 wherein the polymer [A] has a hydroxyl content of 0.4 to 5.5 millimoles/g.

8. The composition of claim 1 wherein the polymer [A] has a phenol or naphthol content of 3 to 50% by weight.

9. The composition of claim 1 wherein the polymer [A] has a phenol or naphthol content of 4.5 to 50% by weight.

10. The composition of claim 1 wherein the polymer [A] is a liquid at room temperature, or a solid with a softening point of not more than 200"C measured by a ball-and-ring method in ASTM E 2858T.

11. The composition of claim 1 wherein the polymer [A] has a number average molecular weight of 200 to 3,000.

12. The composition of claim 1 wherein the polyepoxy compound has an epoxy equivalent of at most 5,000.

13. The composition of claim 1 wherein the polyepoxy compound has a molecular weight of 86 to 20,000.

14. The composition of claim 1 wherein the polyepoxy compound is selected from the group consisting of polyglycidyl ethers of polyphenol compounds and novolak-type polyepoxy compounds.

15. The composition of claim 1 wherein the amount of the polymer [A] is 3 to 700 parts by weight per 100 parts by weight of the polyepoxy compound.

16. The composition of claim 1 wherein the curing agent is a polyfunctional compound having at least two functional groups selected from primary, secondary or tertiary amino groups, acid anhydride groups, mercapto groups and phenolic hydroxyl groups.

17. The composition of claim 1 wherein the amount of the curing agent is 3 to 500 parts by weight per 100 parts by weight of the polyepoxy compound.

18. A composition of claim 1 substantially as hereinbefore described in any of the Examples.