CA1134990A - Epoxy resin composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
An epoxy resin composition comprising (A) a polymer having a hydroxyl content of 0.3 to 7 millimoles/g, said polymer being prepared by polyme-rizing a polymerizable material selected from the group consisting of (a) cationically polymerizable hydrocarbon-containing fractions having a boiling point in the range of from 140 to 280°C 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 poly-merization catalyst andmodifying the resulting polymer with a phenol or naphthol;
(B) a polyepoxy compound; and (C) a curing agent.
The epoxy resin composition thus obtained is especially useful in the field of paints.

Description

.
~3~9~) ~ his invention relates to a novel epoxy re~in composition, and more speci~ically to an epoxy resin com-position especially useful in the ~ield of paints which comprises a combination of a phenol~ or naphthol-modified arOmatic hydrocarbon resin and a polyepoxy compound~
~ poxy resin compositions have found ext~nsi~e applications in the ~ields of paints, adhesives, moldin~
materials, etcO In particular, tar epoxy resin composition~
comprisin~ a polyepox~ compou~d, tar, a curing agent and optional additi~es such as pigments, fillers, reactive diluents, ~lexibilizers or modi~ying resins are generally inexpensive and have relatively good adhesion, chemical resistance and flexibility4 Eence, they find a wide range of applications as waterproo~ coatings of buildings and surface protective paints for metallic containers, variOus industrial apparatus and appliances3 steel pipes, ships, seaside facilit.ies and structural materials; as adhesives for floors, bricks, tiles9 as road repairing materials for repairing cracks of highways; and as floor co~erings for slip prevention, waterproofing, etcO
However, these tar epo~y resin composi-tions have one or more defectsO ~or example, because the tar components present in a concentration of about 10 to 50% by weight such as coal tar, pitch and petroleum asphalt contain carcinogenic substances such as benzopyrene, they cause ~ problem of health hazard at the time of preparation and application of these compositions. Or they tend to bl~ed out from the compositions because their compatibility with polyepoxy compounds is generally not goodO Since they

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are black in color, pale-colored coa-tings CannOt be ob-tained~ and their use is limitedO
In an attempt to eliminate these defects, variOus investigations have been made for techniques of replacing the tar components of the -tar epoxy resin com-positions by substances which have characteristics com-parable to, or better than, those o~ the conventional tar components, and some of -the results obtained have been reported, and applied for patentO
~or exa~.ple, Japanese Patent Publication NoO
23718/75 suggests the use of the by-product cresol distil-l~tion residue obtained in the synthesis of cresol as a : ~
substitute for the tar component of a tar epoxy resin com- :
position composed mainly of an epoxy resin, a curing agent and the tar componentO
~he distillation residue (tar) formed as a by--product in the synthesis of cresol suggested in the above-cited Japanese Patent Publication have good compatibility with the remaining ingredients of the tar epoxy resin ~0 compositions such as epoxy resinsO 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 oper-ability because of their short curing -time, and give coat-ings having poor water resistanceO ~lrthermore, 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 ~,

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~:~34~

be used in applications where li~ht colors are requiredO
It is an object of this invention to provide an epoxy resin co~position Pree from the aforesaid de-fects~
Another obâect 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 materialsO
Still another object of this invention is to pro--vide a light colored epo~J resin composition especiall~
suitable as a vehicle component of paints which give coated films having better water resistance, chemical resistance (eOg~, resistances to salt water, solvents or acids) and strength than do conventional tar epoxy resin compositionsO
Other objects and advantages of the present in-vention will become apparent from the following descriptionO
According to this invention, there is provided an epoxy resin composition comprising (A~ a polymer having a hydroxyl content of 003 to 7 millimoles/g, said polymer bein~ prepared by poly-merizing a polymerizable material selected fron the group consisting o~ :~
(a) a cationically polymerizable hydrocarbon-containing fraction having a boiling point in the range of from 140 to 280C obtained by the distillation of a cracking or reform-ing product of a petroleum, (b) a cationically polymerizable aromatic un-saturated hydrocarbon, and - , . , .: : i .. .

(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 agentO
One characteristic feature of this invention is to use a phenol~ or naphthol-modified aromatic hydrocarbon polymer as one ingredient of an epoxy resin compositionO
~he modified aromatic hydrocarbon polymer will first be described in detailO
~he aromatic hydrocarbon polymer in accordance with this invention can be produced by the cationic poly-merization of the following basic polymerizable materialsO
(a) Cationically polymeri~able hydrocarbon-containing fraction having a boiling range of 140 to 280C obtained by the distillation of a cracking or reforming product of a petroleum:~
In the present specifica-tion and appended claimsO
the term "petroleum" denotes naphthag gas oils9 kerosene, i or crude oil s O
~he term "fraction obtai1led by distilling the cracking or re~orming product of a pe-troleum" denotes a hydrocarbon-con-taining fraction which is formed as a by-product in the thermal or catalytic cracking~ such as steam cracki.ng9 vapor phase cracking or sand cracking or reforming, such as hydroreforming, of the petroleum --defined aboveO

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As the polymerizable material (a) in accordance with this invention, a cati.onically polymerizable un--saturated hydrocarbon containing fraction whic1l has a boiling range of 140C to 280C 1 preferably 140C to 240C , more preferably 160Co to 200C ~ is specifically usedO
~he pe-troleum cracking or reforming fraction having a boiling range of from 140C to 280C contains cationically polymerizable hydrocarbons and non-polymeriz able hydrocarbons7 mos-t of which contain a-t least ~ carbon atomsO ~he 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 fractionO 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 refor~ing con~
ditionsO According to the present invention~ a fraction containing at least 20% by weight, preferably 30 to 75%
by weight, more preferabl~ 35 to 60% by weight~ based on the weight of the fraction, of ca-tionically polymerizable hydrocarbon is advantageously used Hydrocarbons having at least 8 carbon atOms con~
tained in the fraction are almost all aromatic hydrocarbons, the major proportion of which consists of arOmatic hydro carbons containing 9 or lO carbon atoms~ ~he total amount ; of such aromatic hydrocarbons with 9 and lO carbon atoms is 50 to 95% by weight, usuall~ 60 to 95/0 by weight, based on the weight of the fractionO The fraction contains some amounts of aromatic hydrocarbons containing 8 carbon atOms . ~:
~ 6 --`~ .

.; .~ ; . : . ~ 1' , , .

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and more than 10 c~rbon atomsO
~ypical examples of the cationically polymeriz- -able hydrocarbons contained in -the .~raction ~re cationically polymerizable arOmatic unsaturated hydrocarbons containing 8 to 12 carbon atoms, such as styrene7 ~- or ~--methyl s-tyrene9 o-, m- or p vinyltoluene9 isopropenyltoluene, indene, methylindene, divinylbenzene, and vinylnaphthaleneO
In an especi~lly preferred embodiment9 the fraction contains at least 20% by weight iD. total of such cationically polymerizable unsaturated aromatic hydrocarbonsO
~he term "cationically polymerizable arOmatic unsaturated hydrocarbons"9 as used herein, denotes a hydro-carbon containing at least one arOma-tic ring and at least one cationically polymerizable unsaturated bond.O
Other typical cationically polymerizable non~
arOmatic hydrocarbons include olefins and/or diolefins wi-th 8 to 12 carbon atOms such as dicyclopen-tadiene or methyl--dicyclopentadiene which are present in minor quantitiesO
;~ On the other hand9 typical examples of the non-: : 20 polymerizable hydrocarbons contained in the fraction in-: clude C8 to C12 arOmatic hydrocarbons such as ~ylene9 ethyl- ~.
: benzene, cumene9 ethyltoluene, n-propylbenzene9 trimethyl- ~ ~
benzene9 indane9 me-thylindane9 n~phthnlene, methylnaphthalene, ~:
and dimethylnaphthaleneO Other examples of the non-poly- ~
~: 25 merizable hydrocarbons are C~ to C12 paraffins and/or ;: .
naphthenes which are present in small ~mountsO
As stated hereinabove9 the composition of the petroleum cracking or reforming fraction used in this in~
vention changes over a wide range according9 for example9 ~ 7 ~ ;;`

~l~3~

to the petroleum cracked or reformed, and the cracking or reforming conditions, and CannOt be definitely deter-minedO Generally~ -the fraction pre~erably has a bromine value of 50 to 90O Fractions having the following com-posi~ions are especially preferably usedO It should beno-ted however that the present invention is no-t limited to the following exemplificationO
~5m~a~a~Amounts in_percen~
C~ti nical~y poly25 to 75, preferably ~0 to 60 unsaturated hydro carbons 01efins0 to 15, preferably 5 to 10 Diolefins0 to 5, prefera.bly 1 to 3 Non--polymerizable aromatic saturated15 to 50, preferably 20 to 40 hydrocarbons Pcaraffins and5 to 25, preferably 10 to 25 Examples of the cationically polymerizable arOmatic unsaturated hydrocarbons given in the above table are C8 to C12 cationically polymerizable aromatic unsaturated hydro-carbons such as styrene~ a- or ~-methylstyrene, o , m- or p-~inyltoluene, indene, and methylindeneO
USUR11Y cationically polymerizable arOmatic un-saturated hydrocarbons having 9 to 10 carbon atOms such as a- or ~-methylstyrene, o , m-, or p-vinyltoluene, indene and methylindene usually account fo.r 50 to 9~/0 by weight, -usually 60 -to 95% by weight, based on the cationically polymerizable aromatic unsaturated hydrocarbons~ Usuallyq C8 catio~ically polymerizable arOmatic unsaturated hydro-carbons such as styrene, and Cll 12 cationically polymerizable ~3~

~roma-tic unsaturated hydrocarbGns are contained in an amount of 1 to ~0% by weightl especi~lly 2 to 20% by weight 9 and 1 to 40% by weight9 especially 2 to 30% by weight, respectivelyO
~xamples of the ole~ins and diolefins given in the above table are C8 12 aliphat:ic monoolefins and di-olefins such RS dicyclopent~diene or me-thyldicyclopenta-dieneO Typical examples of the non--polymerizable arO~atic saturated hydrocarb~ns given in the table include C8 12 aromatic saturatecl hydrocarbons such as xylene7 ethylbenzene7 cumene7 ethyl-toluene7 n propylbenzene? trime-thylbenzene, indane, methylindane, naphthalene9 me-thylnaphthalene and dimethylnaphthaleneO
The paraffins and naphthenes con-tained in the fraction include paraffins and naphthenes having 9 to 12 carbon atomsO
The cationicc~lly polymerizable arOmatic unsaturated hydrocarbon componen-t in the fraction typically consists essentially of the following componentsO :
Co~po_ents ~ L~
Vinyltoluene ~Total 30 to 859 preferably 35 to 70 Indene ~ ~ ~
S-tyrene ~ ~.
~.. MethylStyrenel Total 5 to 509 preferablY 15 to 40 Me-thylindene J
~--Methylstyrene (*) The amounts are based on the total welght of the ca-tionically polymerizable aromatic unsaturated hydro~
carbonsO

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~ he pe-troleum crflcking or refo:rming fraction can be used either directly9 or if desir~d9 or ~s req1ired, it may be purified prior to use by9 for example, distil-ling it to separate the non-polymerizable hydrocarborls at least partly and to increase the content of the cation-ically polymerizable aromatic uns~turated hydrocarbonsO
In particulc~r, a fraction having a boiling range of 140 to 240C g most preferably 160 to 200C 7 iS preferredO
(b) Cationically polymerizable aromc~tic un-saturated hydrocarbon:~
The fr~ction described in (a) above contains twoor more cationically polymerizable aromatic unsaturated hydrocarbons in the mixed stateO In the present invention, however9 -the arOmatic unsPturated hydrocarbons can be used also in the isolated stateO
: Cati.o.nically polymerizable aromatic unsaturated ; hydrocarbons con-tai.ning 8 to 12 carbon atmsg preferably 8 to 10 carbon atomsg are especially suitable in the pre~
~ sent invention~ ~ypical examples of these aromatic unsaturated : ~0 hydrocarbons include styrene, a~ or ~--methylstyrene, o-~
m- or p-vinyltolueneg o~-, m-- or p-isopropenyltoluene, indeneg ~: :
~: ~ O-- 7 m~ or p-ethyls-tyreneg 3-methylindene and vinyl naphtha~
: leneO 0f theseg styrene9 a-- or ~-methylstyrene~ G-, m-or p-vinyltoluene, and o~, m- or p--isopropenyltoluene are .:
preferredO ~hey can be used either alone or as a mixture of two or moreO
(c) Mixture of ingredients (a) and (b):-In c~ mixt-ure of ingredients (a) and (b), the mixing proportions are not strictly limitedg and can be '`' ~ 1 0 -~ , . ' -~3~

varied widely according to the types of these ingredients (a) ~nd (b)9 etcO Generally9 thc recommendPble weight ratio of ingredient (a) to (b) is from 10:90 to 90:109 especially from 20 80 to 80:200 Of the aforesaid polymerizable m~aterials (a)9 (b) and (C)9 the cationi.ca.lly polymerizable arOmatic un satura-ted hydrocarbon (b) is especially preferredO
The polymerizable materlal described hereinabove is polymerized in accordance with this invention in the 10presence of a catiOnic polymerization catalystn ~he polymerization can be performed by known methods which e.re frequently used to produce ordinary hydro~ :
carbon resins~ ;
~he term "CatiOniC polymerization catalyst", as 15used in the present application9 denotes a catalyst having ::- ;
the ability to form a cation in -the polymerization system9 and includ~s9 for ~xampleg protonic acidg ~riedel~Crafts :: :~
catalysts (Lewis acids), he.logens9 metal oxides, metal sulfides, halogenated ~rganometallic compounds9 and CatiOn 20exchange resinsO
Typical exe~mples of cationic polymerization catalysts used in this invention include ~riedel~Grafts cata]ysts such as boron trifluoride9 complexes of ~oron ~ ~
trifluoride with alcohols9 phenols9 ethers or organic carbo~ ~;
25xylic acids (eOgOg boron trifluoride phenolate and boron ~ :
trifl~uoride etherate)g aluminum trichloridea aluminum tri- :
bromideg tin te-trachlorideg tin tetrabromideg -titanium `.
tetrafluorideg -titanium tetrachloride9 titanium tetrabromide, potassium trifluoridea pOtassium trichlorideg potassium ;', : ~
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tribromide9 molybdenum pentafluoride~ molybdenum penta--chloride, molybdenum pentabromide9 tungsten hexafluoride9 tungsten hexachloride7 tungsten hexabromide, tungsten pentafluori.de9 tungsten pentachloride9 tungsten penta bromide7 rhenium hexachloride9 and rhenium hexabromide; and organocîluminum compounds such as diethylaluminum chloride and ethylaluminum dichlorideO They m~y be used either singly OX7 i.f required9 as a mixture of two or moreO
Of these catiOnic polymerization calalysts7 the Friedel Crafts catalysts9 especially borbn trifluoride7 boron trifluoride complexes9 alumimlm trichloride, tin tetrachl.oride and titanium tetrachloride7 are preferredO
The boron trifluoride7 boron trifluoride complexes7 and aluminum trichloride are especially preferredO The amount 1.5 of the ca~-talyst i5 not particularly restrictedO ~owever7 its suitable amount is usually Ool to 25% by weigh-t9 pre-ferably 0O2 to 20% by weight9 based on the weigh-t of the polymerizable materialO
The polymerization can be performed in the absence : 20 of solvent7 but usually i-t is adva.n-tageous to perform it in the presence of a solventO Suitable polymerization solvents are, for example9 alipha-tic saturated hydrocarbonc such as pentane, hexane, heptane and kerosene7 and aromatic SatU--rated hydrocarbons such as benzene7 toluene and xyleneO
~Ihen these saturated hydrocarbons are con-t.ained in -the polymerizable material9 they can be used a.S polymerization ~
solventsO : ;
The polymerizatioxl can be carried out usually at a temperature ranging from 0 to 200C 9 preferably 10 to ~- 12 -150Co Atmospheric pressure suffices as the polymerization pressure~ If desired, elevated on reduced pressures in the range of 0~1 -to 50 atmospheres can be employedO
Under these polymerization conditions, the polymerization can be completed usually within 10 minutes to 5 hours~
After the polymeriza-tion9 the catalyst can be removed by such ?. -treatmen-t as washing with an alkali aqueous solution or with w~ter9 and the unreacted hydro~
carbons or polyrners with a low degree of polymerization can be removed by a suitable means such as distillationO
Adv?.~ntageously9 the distill~tion is carried out generallg at a -temperature of 150 to 250Co and a pressure of 5 mr~g to 100 mr~g. As a result9 hydrocarbon resins are obtained ;
as distilla-tion bottomsO
The most characteristic feature of the present invention is to use -the aforesaid aromatic hydrocarbon polymer as modified with a phenol or naphtholo ~his 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 ~-arom~tic hydrocarbon polymerO ;~
In-troduction of ~ phenol or naphthol into the polymerization reaction system can be performed at any ~5 desired stage of the polymerization9 for example9 by mix- : :
ing tho phenol or naphthol with the polymerizable material before the initiation of the reaction9 by adding the phenol or naphthol to the polymerizatioll reaction mass during the proceeding of -the polymerization9 or by adding the pheno:l or naph-tho], to the reaction mixture after the polymerization reaction bu-t before removing the CatiOn polymeriza-tiOn catalyst~ and continuing the reaction=
Alterna-tively, the phenols or naphthols can al,so be in-troduced into the polymer by separa-ting the resulting polymer from the polymerization system~ adding the phenol or naphthol to the separa-ted polymer9 and reacting them in the presence of the cationic polymerization catalystu It is especially preferred in this invention9 however9 that the pheno]. or naphthol be introduced into the polymerization reaction system before the initiation of the polyme:Li%ation reactionO
Any conventional compou~ds having at least one hydroxyl group directly bonded to an aromatic ring can be used as the phenols or naphthols to modify the arOma-tic hydrocarbon polymerO Compounds expressed by the formula Rl--~Ar--~OH)n (I) wherein Ar represents a benzene or naphthalene ring~ ~ and R2, independently from each o-therg represent a hydrogen ato~
or an alkyl group9 and n is an integer of 1 or 29 can be used advantageouslyO
In formula (I)9 the alkyl group may be linear or branched9 a~d contain up -to 20 carbon atoms, preferably up to 15 carbon atoms, more preferably up t~ 12 carbon atomsO ~xamples are methyl9 ethyl9 n- or iso-~propyl 9 n-sec 9 iso-- or tert-butyl9 n-pentyl9 iso amyl~ n-hexyl9 n-octyl9 n-nonyl9 and n~decyl groupsO Specific examples of the phenol or naphthol that can be used in this inven-tion ~3~

include- phenol, creso] (o-, m or p )9 xylenol (2,3 7 274-, 2,5 , 2,6-7 3,4-- or :~,5-), i.sopropyl phenol1 sec- o~ tert-butylphenol, p-tert-a~yl phcnol, octyl phenol, nonyl phenol 9 dodecyl phenol, naphthol (~ or ~-), dihydroxybenzenes (resorcinol, catechol and hydroquinone), and pyrog~llolO
Among these, ohenolg cresol (o-, m- or p--), xylenol (296-or 3,5-~), isopropyl phenol, sec- or tert-butylph~J3nol, octyl phenol, nonyl phenol, dodecyl phenol, naphthol (a-or ~ ), ancl dihydroxybenzenes (resorcinol, catechol and hydroquinone) are preferredO Phenol, cresolcv and dihydro~-xybenzenes are especially preferredO
~hese phenols or naphthols can be used either alone or as a mixture of two or more of themO
~he am0unt of the phenol or naphthol is no-t cri-tical7 and can be varied widely according to the characte~
~: ~ ristics required of the final modified polymer9 for exampleO ~:
Generally, the suitable amount of the phenol or naphthol is 5 to 100 parts by weight, preferably 605 -to 70 parts by : ~ :
~::: weightg most preferably 10 to 50 parts by weight, p~ir 100 ; .
par-ts by weight of all the ca.tionically polymerizable ~
component.s of the polymerizable materi~lO When the phenol ;
or .naphthol is to be added to the resulting polymer, its amount is desir~bly within the above-specified ranges per 100 parts by weight of the polymerO
~25 As stated hereinabove9 the phenol or naphthol .
can be introduced into -the polymeriza-tion reaction system at any desired stage of the polymerization of the poly~
merizable materialO ~or example9 it may be mixed with the ~: starting material before the initiation o~ polymerization, ::~
~ ~ `' ' ~';' :~ - 15 - -:.
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or to the reRc-tion mixture during the polymerization re-action, or to the reaction mixture immedic~.-tely after -the polym~3rlzation reactionO
~ e re.~ction after mixing of the phenol or naph-thol can be performed in the presence of a cationic polymeri zation catalyst under the same polymerization reactiorl con~
ditions as used in the po:L.ymerization~ and ~o special atten-tion needs to be paidO
It is also possible to add the phenol or naphthol.
to an aromatic hydrocarbon polymer produced by -the above polymerization reaction and then separatecl9 and react thcm under the same conditions as the polymerization conditions in -the reaction so].vent and in the presence cf the CatiOniC
polymerization catalystO
Various properties of the resulti.ng modified polymer~ such as softening point9 molecular weight, molecular : weight distribu-tion, melt viscosity~ solubility and com-patibillty, can be varied widely by properly choosing the : types of the polymerizable ma-terial and/or the phenol or ~ .
~O naphtholg the polymerization conditions, etcO
In the modified polymer so produced9 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 :~
f the aromatic hydrocarbon polymer while partly retain-ing its hydroxyl groups~ or partly through an ether linkage ascribable to the hydroxyl groups~ Accordingly~ the modi~
fied polymer of -this invention can have a hydroxyl con-tent of generally OO~ to 7 millimoles/g~ preferably 004 to 505 millimoles/gg more preferably 0O5 to Lr millimo]es/g9 according to the am0unt of the phenol or naphthol intro-ducedO
The modified polymer can have a phenol or naphthol content of generaLly 3 to 50% by weightg prefer-ably 4O5 to 50% by weightg more preferably 6 to 40% by weight, according to the amount o~ the phenol or naphthol introduced into the polymerO
The term "hydroxyl content 1l 9 as used in -the pre~
sen-t specification and -the appended claims, is defined as follows:
The absorbances at 3550 cm 1 (the characteristic absorpti.on wave number of a phenolic hydroxyl group) of toluene solutions containing phenol in vari.ous predetermined concentrations are measured by using an infrared spectro- .
photometer DS-~0/G (a standard cellg thickness 0~1 m) of Nippon Bunko Kogyo K~KDg and a standard calibration curve is prepared by plotting the absorbances on the axis of ordinates and the phenol concentrations on the axis of :~20 abscissasO Separately9 0O3 g of a sample is dissolved in -10 ml of toluene, and tlle absorbance of the solution at ; 3550 cm 1 is readO The phenol concentration corresponding to the absorbance read from the standard calibra-tion curve is determinedg and defined as the hydroxyl con-tent of the ~:
sampleO
The "phenol or naphthol conten-t" is obtained by determining the oxygen con-tent of a sample by an element ` `:
analyzer (-type 0--corder M0-109 a product of Yanagimoto : Seisakusho)g and multiplying the oxygen content (% by weigh-t) -~ 17 ~- ~

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by -the quotient obtalned by diviciing -the molecular weight of -the phenol or naphthol used for modification by the number of hydrog~l groups present in the phenol or naph-thol~
~he modi~ied polymer ranges from a liquid st~te at room temperature to a solid sta~te wi-th a softening point (by the ball-and ring method in AS'~M ~ 2858'1') of not more than 200Co, preferably not more than 1~0Co ~ he modified polymer c(qn have a number average molecular weight of generally abou-t 200 -to abou-t 3000, 10preferably about 200 -to abou-t 2000, most preferably about 250 to about 15000 ~ometimes, the modified polymer has a Gardner color number of about 17, but generally it is avail-able in a comparative:Ly ]igh-t color with a Gardner color number of less than about l0O It can be used adv~ntageouslY
in applications in which coloration is undesiredO
According -to this invention, the modified polymer is used to prepare a tar-ep0xy resinous composition ln con--junction with a polyepoxy compound and a curing agentO
The polyepoxy compound that can be used in the epoxy resin composi-tion is a compound containing at least two epoxy groups per moleculeO Both low-molecular-weight and high-molecular-wei Bt polyepoxy compounds containing a~t least two epoxy groups per molecule can be used~ ~hey ; ma~ also be alipha-tic, aromatic7 or araliphatic~ or may contain a heterocycleO ~hus, any epoxy compounds ordinarily used in the conventional tar epoxy resin compositions are feasible in this inventionO
; ~he polyepoxy compound can be freely selected from known compounds according to the purpose of use of the final -~ .
~- 18 -~ ' ' epoxy resin cornposition or the characteristics required of the final compositionn Specifi( examples are glven belowO It should be unclerstood howeve:r that the scope of the present invention is in no way limited by these examplesO
(1) Po].yglycidyl ethers of polyphenols:~
Diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F 7 tetraglycidyl ether of 1. ~ 1 9 2,2 tetrakis(4'-hydroxy-phenyl)ethane9 diglycidyl ether of 2,2~bis(~-hydroxypheny])nona- ~ :
denane9 diglycidyl e-ther of diphenyl ether9 diglycidyl e-ther of tetrachlorobisphenol A9 dig]yci.dyl ether o~ te-trabromobisphenol A9 and diglycidyl ether o~ bisphenol-hexafluoroacetoneO
(2) Polyglycidyl e~thers of ~uclearly hydrogenated products of polyph~nol compounds:

CH~Cl CH CH2Cl r~ I
CH2~CH-CH2-0-CH--CH2 02- ~ C~ CH2--CH--0~CH2~c\ icH2 CH

(292--(4-~3 Chloro-2-(293-epoxy propoxy)propoxyl) cyclohexyl)propane) CH

2 ^ ~ I ~ .o-cH2~-cH

(diglycidyl ether of hydrogenated bisphenol A) , , CH~
r~ I r~
CH2~CE~-CH2~ H ~ ~ ~ 2 1 2t2~rl 2 1 2 ~

~ ,.

0-~3C-O-CH2-C\I-~ H2 CH~
(n2 1) (~pikote 871, a product of She].l) (~) Polyglycidyl ethers of polyhydric phenols:-C~techol diglycidyl ether~
resorcinol diglycidyl ether~
hydroquinone diglycidyl e-ther 9 phloroglycin ditriglycidyl ether, trihydroxy biphenyl triglycidyl ether, tetraglycidoxy biphenyl, : methylphloroglycin triglycidyl ether, -~:~ tetraglycidyl ether of bis-resorcinol~ and ~:~ tetr~.glycidyl ether of resorcir.~.ol ketone

(4) Polyglycidyl e~thers of polyhydric alcohols:--~thyl glycol diglycidyl ether butanediol diglycidyl ether~
glycerln digl.ycidyl ether, :~
; gl.ycerin triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythri.trol tetraglycidyl ether sorbitol polyglycidyl ethers~
~ polyoxyalkylene glycol diglycldyl ethers~ and : ~;'';
~ ':
~ :", ~3~

trimethylolpropane trig]ycidyl etherO

(5) Novolak type polyepoxy compounds.-Polyglycidyl ether of phenol formaldehyde novolak /0\ ~0~
CH~-CH-CH~-O OH ~ CH~-CH-~I2 R-CH2-CH~ 2 o ~ CH ~ CH~ CH2-} - t ~ H20~I)C

~ ' ' (a= O - 8~ b= O - 8~ c= O - 1) ..
Polyglycidyl ether o~ o cresol--formaldehyde novolak CH-CH2 C~ H2 7 I H ICH2 1 2 :;
O O ~ O
C~3 ` ~ ~ ~' ~ OX3 ::i (a= O - 4, b= O - 8) : (6) Alicyclic polyepoxy compou~ds~
Vinyl cyclohex~ne dioxide limonene dioxide~
.
~ dicyclopentadiene dioxide9 ~- ~
~, . .. :
2.2 bis(3 9 4 epoxycyclohe~yl)propane, ; bis(2,3 epoxycyclopen-tyI)ether~ and 15~ bisepoxy dicyclopenty:L~ ether of ethylene glyGOlo `,' (7) Polyglycidyl esters of polycarboxylic acids or their condensates ~.
Diglycldyl phthalate, diglyc:idyl isOphthalate, diglycidyl tetrahydrophthalate, ~ :
diglyc:idyl ester of dimeric acid9 ~: .

~3~

dlglycidyl hexahydrophthalate, and diglycidyl aster of a co:ndensate of terephthalic acid (or isophthalic acid) and e-thylene gl,ycol (po yester) having -t'ne following formula H2C-HC_CH2_0 tC ~ C00 CH2 ~H2-0 ~ C ~ C~0-CH2~C~I_CH2 0 0 m o 0 0 (m~ 1) (8) Polyglycidyl amine compounds~

(C 2~CH-CEI2)2-N-~R

(in which R is a hydrocarbon group with 1 to 25 carbon atoms, such as alkyl, arylg aralkyl or alkaryl) (eOgO diglycidyl methyl a~ine9 diglycidyl ethyl amine9 diglycidyl propyl amine9 and diglycidyl aniline)g trlglycidyl p-aminophenol, '~
triglycidyl isocyanurate, and : tetraglycidyl aminodiphenylmethaneO , :~' (9) Methyl epichlorohydrin-type polyepoxy com-pound5~
: 20 Di(2~-methyl)glycidyl ether of ethylene glycolg di(2-methyl)glycidyl ether of bisphanol A, ~ ,~
di(2~methyl)glycidyl ether of bisphenol ~9 di(2 methyl)glycidyl phthalateg and -`':` -di(2-methyl)glycidyl isoph-thalateO

Among -these polyepoxy compoundsg the polyglycidyl :, ''.

:

~:~3~

ethers of polypheno].ic compour.ds and novolak -type poly-- -epoxy compounds are used conveniently in the p-reserlt in-ventionO Above a].l9 bisphenol A diglycidyl ether, arld bisphenol F di~lycidyl ether are preferredO
The epoxy equivalent and molecular weight of the polyepoxy compound -that can be used in thi~ i.nvention are not cri-tic~19 and can be varied wldely according to the use and properties of the final polyepoxy resin compositior Generallyt it has an epoxy equivalent of at most 59~009 preferably 4~ -to 395009 more preferably 80 to ~90009 and a molecular weight of 86 to 2090009 preferab].y 130 to 1090009 most preferably 150 -to 59000O Those which are liquid or solid at room tempera.ture can be usedO Preferably~ solid polyepoxy compounds are used as a solu-tion in a sui-table solventO
Any curing agents which are genera].ly known as cur~
ing agents for epoxy resins can be used in the polyepoxy resin composition provided by -this inventionO ~hese curing : agents are poly~unctional compounds cont~.ining a-t least two ,, functional groups per molecule9 such as primary9 secondary or tertiary amino groups9 acid anhydride groups9 mercapto groups9 or phenolic hydroxyl groupO Typical examples are given belowO It should be understood that the scope of the invention is in no way limited by -these examplesO ~ ::
(1) Linear aliphatic primary polyamines ~.
Di.e-thylene triamine, triethylene te-tramine9 tetra-e-thylene pentamine9 dipropylene diamine9 and cliethylamino- -propyl ami ne O '~
(2) Alicyclic primary polyamines ,: . . . . .. . . ...

~34~

N-aminoethylpiperazine~ methanedi~lmine, lg3--diaminocyclohexaneg isophoronedia~in.e, bis(4 amino 3-methylcyclohexyl)me-thane, 3g9-bis(~) aminopropyl)^2,498710 tetroxaspiro~5g5)undecane, and 19 3 diaminocyclohexaneO
~3) Modified aliphatic primary polyamines (i) Amine epoxy resin adducts:--3ie-thylene triamine--bisphenol A glycidyl ether adduct (ii) Amine ethylene oxide or prop-ylene oxide adducts:
N7M~-bis(hydroxyc-thyl)die~thyl.ene -triamineg N~N~-bis(hydroxypropyl)die~thylene -triamineg N-(hydroxypropyl)diethylenetriamine~
N.-(2-hydroxy~ 2g494-trimethylphenyl)diethylene triamine, N-(2-hydroxyethyl)diethylene -triamine~ and N~NON~N~ tetrahydroxy~ropylene diamineO .
(iii) Cyanoethyla-ted polyamines ~
Cyanoe-thyl~ted diethylene triamine, cyanoethyl~-ted triethylene tetramine, and ~; cyanoethyla-ted tetraethylene pentamineO
(iv) Ketone blocked polyamines~
Re~ctio.Ll product between diethylene triamine and a ketone having the ~ormu].a ;~

~2C=N~C~2~ NH~~CH ~ N=CR2 (R = Cl_10 alkyl group) (4~ Aroma-tic primary polyamines `- ~-o~, or m Phenylenediamineg diaminodiphenyl ether.
~: ~
- 2~ --. '- ' .

~,. . .;

494' me-thylenedianilirle, diaminodiphenyl sulfone9 dimethyl diphenyl methane9 m~-xylylene diamine9 t-l94' bis(o toluidine)~
tetrachloro--p--xylylenediamine9 494'-thiodiani]ine9 494' bis(o-toluidine)9 dianisidine9 294 toluenediamine9 methylene-bis(o-c,hloroaniline)9 m--aminobenzylamine9 a eutectic blend of aromatic amines (e~gO9 a eutectic blend of m-phenylene diamine and 494'-methylenedianiline)9 and an adduct of an aromatic amine with styrene oxide or phe~nylglycidyl e-ther (5) Tertiary amine type curing agents (i) Aliphatic tertiary amines~
N9N9N'9N' Tetramethyl~193 blltarlodiamine9 tetra methylgua~idine9 triethanolamine9 2-dimethyl~mino-2~hydro~J--propane9 and trialkylamines such as trimethylamine and trie-thylaminen (ii) Alicyclic tertiary amines:-N9N'-dime-thylpiperazine9 N-methylmorpholineg and` ~' 194~diazabicyclo(29292)0ctaneO
(iii) Heteroaromatic ring-containing tertiary -.
amines - - .~' ~: 20 Picoline9 pyridine9 pyrazine9 and quinoli.neO
(iv) Aromatic ring-contraining a].iphatic tertiary ~, amines~
Benzyldimeth~lamine9 ~--methylbenzyldimethylamine, 2-(dimethylaminomethyl)phenol9 and 29L~96 tri.s~dimethylamino methyl)phenol

(6) Mercaptan-type curing agents I

3 6 n 2 , 2 )3 ' (n= l - 2~ R= aliphatic hydrocarbon group) : --- 25 - ~ , Exa~ples are Thiokol (a -trP~de~P~rk for c~ pro-duct o~ Thiokol Company) and Epi Cure 861 (a trademark for a- product of Cel~rlcse Corporatiorl)O

(7) Acid anhydride type curi,ng agents Phthalic anhydride, maleic anh~Jdride, trlmellitie ~nhydride9 pyromellitic ~,nhydride, hexahydrophthalic an- ' hydride9 ~adic Methyl hnhydride (met'hylbicyclo(2O2~
hep-tene-2,3-dic?.rbox~lic anhydride) 9 dodecerl91succinic anhydride, ethylene glycol bi,s-trimelli-tR-te9 glycerol tris-trimelli.tate, and tetrahydrophtha.lic anhydrideO

(8) Phenolic hydroxyl--containing compouncls Phenol-form~ldehyde precondensc~tes (novolak and resol types)9 resorcinol9 phloroglueinol9 195-naphthalene diol, and 494'~dihydroxydiphenyl~qulfoneO

(9) Other compounds (i) boron trifluorine-amin.e com~lexes9 (ii) dicyandiamide9 (iii) melamine resins9 (iv) urecl resins, (v) 2-ethy], 4-methyl imidazole, ~: ~ (vi) polysulfide resins9 ';~' (vii) polyamide resins9 (viii) amide polyamines9 and (ix) polyamide aminesO
~he reac-tion produc-ts of ~atty acids and poly-amines (eOgO, diethylene triamine9 triethylene tetramine and tetraethylene pentamine).
: CH3(C:H2)nCONH(CH2)~NH(CH2)2 2 3( 2)nCONH(CH2)2NH(CH2~2NH(CH2)2NH

^ 26 ~
, ~:

~3~

(n= 1 - 20) ~hese curing agents can be used sing].y, or if ~-desi.red, two or more of them may be usea as a mixture ~he curing agent to be used in a par-ticular composition can be chosen according to the desired. rate of curing and proper-ties of the fina1 composition, Rnd those skilled in the art can m~ke such a choice very easily by preliminar-~routine experimentsO
Preferred curing agents for use in the present -~
1~0 invention are linear aliphatic primary polyamines such as diethylene triamine, triethylene tetramine~ tetraethy].ene pentamine, dipropylene diamine and diethylam no propane;
adducts of aliphatic polyamines with epoxy resins~ adducts f aliphatic polyamines with ethylene oxide or propylene ~15 oxide; modified ~l1phat1c prim~ry polyamines such as CyanO~
ethylated aliphatic primary polyamines; ~mide polyamines;
aromatic primary polyamines., and acid anh-gdride-type curing agents~
In the present composition, the proportions of the 0 modified~polymer~ th~ polyepoxy compound and the curing ` ~
agent are not strlctly restricted~ and~can be varied widely ~ ~ :
according~ for cxample,~ to~the proper-ties required of the final compos1tionO ~Generally9~the modified polymer can `
;; be used in an amount of ~ to 700 parts by T~eight, prefer~
~25;~ ably 4 -to 660 parts by~weight, most preferably 5 to 500 ~ ; :
parts by weight~ per 100 parts by weight of the polyepoxy compoundO On the other~hand~ i~t is ad~antagaous to use ; ~ the curing agent in~an amOunt of 3 to 500 parts by weight9 preferably 4 to 300 parts~;by weigh-t 9 most preferably 5 to~

.

~ 27 ~

-., :.

- ~ "

250 parts by weight, per 100 parts by weight of the ~oly- -epoxy compoundO .: -~he polyepoxy resin composi-tion provided by the present inven-tion may further contain optional ad-ditivesO ~xamples of the aclditives are phenolic resins, alkyd resins, petrole~m resins~ pigments (eOgO9 tit~nium oxideg antimony oxide9 cadmium red, toluidine red, phthalo cyanine blue)9 fillers (eOgO~ talc 9 silica9 ~.ca, cryo:l.ite9 clay, calcium carbonate, ~lumina9 por-tland cement9 gr~phite)9 reactive diluents (eOgo 7 s-tyrene oxide9 allyl glycidyl ether, butyl glycidyl ether, vinylcyclohexane monoxide9 dipentene ~ -:
monoxide9 glycidyl methacryla-te), flexibilizers (eOgO9 polyamides9 polysulfide resin.s, polyurethane elas-tomers)9 ~ and solventsO ~he amounts of such additives &re9 for ex- ;~
:;- 15 ample3 0 to 1000 parts by weight for the pigments and ~: fillersj 0 to 50 parts by weight for the reactive diluents and ~.lexibilizers; and 0 to 2000 parts by weight for the ;.
solvents, all per 100::parts by weight o~ the polyepoxy com-p ound O
~he polyepoxy resin compos1tions provided by the present invention include:both room -tem~eraturevcurable type compositlons whioh cure at room tempera-ture, and hea-t~
: curable type compositions which cure only when heated at : a -temperature of about~50 to about~200C 9 depending upon ~ the -types of the poIyepoxy compound and curing agerlt to be included ln the compositionsO ;.
he e~oxy~resln composition cf this invention can ~ ~-be prepared by a~y conventional me-thodsO ~or exampIe, the .~: :
modified;pol~mer ls mixed first with the polyepoxy compound ..
~: .. :.
::: ,: , , : .

: . ~ , - -,.. . .

~3~

or the curing agent9 ~nd just prior -to use i.n applications to be described below9 the mixture is unifor~ly mixed with the curing ~.gent or the polyepoxy compoundO Or just prio:r to use in the applications to be d.es~ribed below, the modified polymer, the polyepoxy co~pound and the cur-ing agent are simult~neously mixed to form a uniform blendO
Additives such ~s pigments9 fillers, reactive diluents and solven-ts can be added simultaneous].y with the addition of .: i the po].yepoxy compound or curing agent to -the modified pclyme.rO But advan-tageollsly9 -the addi-tives are fully mixed with the polyepoxy compound beforehand, and then the mix-ture is mixed with the modified polymer and/or the curing agentO
:~ The modified polymers employed in this inven-tion .
have superior compatibility with epoxy resi.ns and curing ~ :
:~ 15 agentsO ~ence9 epoxy~resin compositions including the ~:~ : modified polymers according to this invention Call be stored stably over long per1ods of -timeO In comparison with tar- ~:
containing epoxy resin compositions9 the epoxy resin com~
positions of this inve~tion have reduced bleed out and~.
superior mechan1cal~strength (eOgO9 compression or im~act :
strength)9:~abrasion resistance9 water resistance9 and : ... ;
: chemica1 resistance (eOgO9 alkali resistance)O: ~herefore9 these compositions can be suitably used in fields which ~: :
: ;: use tar-COnt~ining epoxy resin compositions9 for example 25~ as paints, road repa.iring materials, or slip pre-venting ; ~ ~ .
fIoor materialsO~
~ ,-., Furthermore~ in comparison ~th cQmpositlons ~:
: of epoxy resins and curing agents not containing the modified polymers of this in.vention9 the epoxy resin co~positions;:

": : ~ :

~3f.~

of this invention have superior adhesion9 mechanical st~
rength (e~gO~ comprescion or impact strength)9 water resistance, chemical resistance (eOg~, nlkali or solvent resist~nce) 7 and thermal stabilityO ~hese epoxy resin compositions can also be used in a wide range of appli-cations as7 for example, cast articles9 adhesives and laminated boardsO
: Since the modi~ied polymer in accordance with this inven-tion is availabl~ in a relatively light to color-less co].or, the epoxy resin composition o~ -thi~, invention can be obtained in a ligh-t colorO Accor~ingly9 i-t can be used advantageously also in applications which permit only light-colored colorationO ..
,:
~ he following ~xamples speci~ically illustrate :~ 15 the epoxy resin composition of this i~ventionO ~ -:
x.~m~LQ~L ~, (l) Preparation of phenol-modi~1ed po1y(~-methylstyrene3 .
A I-liter glass reactor e~u1pped with a thermome-ter9 :~
a reflux condenser9 a feed opening and c~ stirrer was charged : - :
with a mixture consisting of 170 g of a~ml3thylstyrone9 30 g ; ~.
of phenol and 200 g o~ tolueneO lhe m1xture was stirred to . :
form a so1ut1onO~ To the resulting solution was added drop~
w1se 2 g of a boron trif1uorlde/phenol complex, and the : polymerization~was~perfcrmed in a nitrogen a-tmosphere at : : ~ .-25 ~ 30C o ~for 2 hoursO~ 'r'o the resul-ting polymer1zation pro~
duct was added~l50 ml of a 00~3N aqueous solution o~sodium~
s h~droxide~ ~nd:the mixture was~s-t1rred ~or 30 minu-tesO
he aqueous lay~er was separated9 and~the resldue w~s repeat~
edly waQhQd with~wQter until -the QqUeOUQ layer became~neutr21 _ -, ~ .

:
~.~3 l'he~ aqueous :Layer was separated9 and ~the residue WQS con-centrated at 200C, and 5 mmHg f`or 30 minute.s to afford 195 g of a modified polymerO The pIoperties of the~ polymer are sho~Jn in Table 2~
(2) Preparation o~ an epoxy resin composi-tion A blend consisting of 40 parts by weight of bis^
phenol A diglycidyl cther (~POMIK R-lL~47 ~ -tradema.r.k for a product of Mitsui ~etrochemical Epoxy CoO 9 Ltd~) 9 e~o parts by weight of the phenol-modified poly(~me-thylstyrene) prepared in section (1) above9 100 parts by weight of -talc 30 parts by weight of ti-tanium white and /~0 parts by weight of ethyl cellulose was passed through a three roll mill three times to disperse the talc unifor~ly in the blendO :
Then, 30 parts by weight of a polyamide a~ine curing agent (EPOMIK Q--6719 a trademark for a produc-t of ~i.tsui Petro~
; chemical Epoxy CoO, Ltdo) 9 and the viscosity o~ the result ing mixture was adjusted tc 2500 centipoises (measured by ~-a B-type viscometer) with a 1:1 by weigh-t ~ixture of xylene .
and tert butanolO Tile resulting composition was coated .. ~
on a mild steel plateO .:
: (3) Test for the perform~.nce of the coated ~ilm The coated film obt~ined was -tested for perform~
ance by the method described hereinbelowO The results .
are shown in Table 20 : - -25 ~ ~ 9 The procedure:of ~xample~ 19 (1) was repeated except ~ -that 170 g of each of the polymerizable materials shown ln T~ble 2 w~s used instead of 170 g of the a--methylstyrene ~ -in ~xample 19 (l)o ~hus, pheno]~modlfled polyme s having ~.~`

: 31 -~
~: :` ~ :; ',"' the characteris-ti.cs shown in 'rabl.r 2 were preparedO
'rhen9 the procedure of Example l, (2) was re : :
peated except u~ing each of the phenol--modified polyme~s obtained above in the amounts shown in ~able 2 instead of .
the phenol-modified poly(a-methylstyrene)q each of -the poly-~
: epoxy compounds in the amounts shown in 'rable 2 inste~d o~
the bisphenol A digl-gcid~l ether9 and each of the curing agent.s shown in 'rablr_ 2 instead of -the polyamide amine curing agent in ~xample l~ (2)o r~hus9 epoxy resin compositiorls were pre~
,10 paredO
'rhese composltions were tested for the performarlce, of coated fil.ms in the same way as in ~xample 1, (3)O ~he .~;
results are shown in '~able 20 . ;-.
C~ , ""~
:15 ~An epoXy~resin composition was~prepared by re~
peatlng the~prooedure o~ Example l~ (2) except that 40 parts ..
by we~ight o~ a coal~:~tar (~ARCR0~ ~tlaO);~was used instead of ; /~ parts b~ weig~lt of the~phenol modi~ied polyt~mo3thyl~
styrene)::in Exa~mple 1~ (2)o~
20~ The composltion was tes-ted:for coating performanor~
in the~s~me~way~a.s in~xample 1~ (3)o 'rhe:results are : sum~arized in~'r~ble~2 belowO : :
xampl:es lO~nd:ll Preparation~o~a phenol-modi~ied polymer~
- 25~ A~ ter glass reartor equipped wi-th a~thermo~
meter~a~renux~::oondens~r~a feed opening and;a stirier;
was charged wl-th d mix*ure~consistlng of 185 g o~ a me-thyl~
styrene~l5 g of~el~the~r ~-;n~phthol~::or~re~sorclnol and 200~g~
of tolur-~ne, ~and:~ the :mixture wàs~ sti~ed.: ~ lo the result~lng ~ ~3~

solu-tion was added d:ropwise 2 g of a boron trifluoride/
phenol complex9 and the polymeri.za-tion was performed in a nitrogen atmosphere at 50Co for 2 hoursO '~o the result ing polymerization product was added 150 ml of a 003N
aqueous solution of sodium hydroxideO '~he mixture was stirred for 30 minutes9 and the aqueOus l~yer wa.s sepa-ra-tedO ~he residue was repeatedly washed ~ith water until the aqu.eous layer became reutralu '~he ~qUeOUS layer was .
separatGd9 and the residue was concentrated a-t 200C. and 5 m~Ig for 30 minutes -to afford a modified polymer having the properties shown ln lable 20 - :
(2) Preparation of an epoxy resin composition ::
A blend consisting of 72 parts by weight of bis-~: phenol A diglycidyl eth~r (~POMI~ R 1409 a txademark ~or a ~-product of Mitsui Petrochemical ~poxy Co~.g ~tdo)9 8 parts : by weight of the modified poly(~-methylstyrene) prepared in section (1) Pbove9 lOO parts by weight of talc9 20 parts by weight of titanium white and 40 parts by weight of ethyl ~-~:~ cellulose was passed through a three-roll miIl three times~
'~hen9 50 parts by weight of a polyamide amine curing agent (EPOMIK Q-6719 a trademark for a product of Mitsui Petro~
; ChQmical Epoxy Co.g Ltdo) was added. '~he viscosity of : the mixture:was adjusted to 2500 centipoises (measu ed by a B--type viscometer) with a 1:1 by weight mixture of xylene and~sec--butanol '~he resu].ting composition was coated ; ~ on ~ mild steel plate , (3) '~est for -th~e performance of coated film '~he ooated fllm obtained was tested. for perform-: ance by the method described hereinbelow 'The results are :
., - -'~ , ~3~?0 ~
shown in ~able 20 E~,~c~m~E ~e~s 2 to _21 (1) Pr~p~ration of a phcnol modified polymer A l liter ~lass reactor equipped with a thermo-me-ter, a reflux condenser, a feed opening and a stirrer was charged with a mixture consist.ing of 170 g of a naphtha ; cr~ckir.g hydrocarbon fracti.on hav:ing each of the compositions A to a shown in ~able I below and 30 g of a phenol 9 and the mixture WflS stirredO ~0 tha resul.tirlg solution was added , dropwise 2 g of a boron trifluoride/phenol complex, and the polylnerization was performed in a nltrogen atmosphere ;
at 30Co for 2 hoursO To the resulting polymorization pro~
duct was added 150 ml of a 003~ aqUeOUS solutlon o~ sodium ;
hydroxide, and the mixture was stirr~d for 30 minutesO The ; ~.:
~: 15 aqueous layer was separated~ and the residue was repeatedly ~ ~.
: , washed with water until the aqueous la~er became neutr~lO
The aqueous~layer was~separated~ and the residue was concen-t~
rated at 200C. arld 5 mmHg for 30 minutes -to e~fford a modi~ied pol~mer having the~properties shown in Table 2O

~:: : ~: . .:
-- 34- ~ ~ `

, .
.

. '' ` i'`' ': :` ` :` ` ! 1` ` " ' ;

L3L34~
, qle b~t,3 Con-tent Comnonent ,,(3~0 ,b,~ wti~;ht ba~ed or t:he :~ractlon) A B C

Styrene 208 007 108 a-Methyl styrene 201 ~0O 105 ,B Methyl~;tyrene 20 3 3o 2 1 o 4 Vinyltolue:!le 1800 2505 1400 Indene 1201 160 3 901 " '.
Methylindene 402 1~,0 300 ~rimethylbenzent 1200 2000 lOoO
~,~ Naphthal ene 501, oOo Other C,-C 7 arOmatic~;0 5 22 7 40 5 - ~;~
s~turate~d ~drocarbons ~ ' '-P~raffins ~nd uniden ';
tified components 1009 8nO 1404 " ~"

Total of the aromatic L~l 5 L~9 7 3()o8 unsaturated hydrocarbons .,~

fOalctiiognr'(gg-)of~ the; ' ~ 140-240 ~160-200 ~ 140-280 ;

( 2) ~ ~ Preparatlon of an epoxy resln composi~tion A~ blend ~consisting Or 40 parts by wei.ght of bis~

5 ~ pherol A digl~Tcid;~ eth~er (EPOMIK R-1449 a -trademark for a product ;o~f~Mitsul~Petrochemlc~gl l~po~y COo9 ~tdo)9 40 parts ~
by wel~;ht of~ths palymer obtalnsd in (1) above9 100 parts ;;
by wslgh-t of~ talo,~:30~parts by wsight of t:itanium whlte and 40 parts~ by ~ws1~ht:~of ethyl cellulose was passed ~through lQ~ thIss-rol~l~ m~ three -tlmss to disperse the talc- uniformly~
n ths blsndO ~hgn7 a~polyamide~ am~ns curing agent (EPOM CK
Q^671) w~s added in~an~ amount OI 30 parts by weight, a~d ,'.
the~viscosity o~:E~ths mixture was sdJusted to 2500 centipoises ~

:

(me~su.red by a B~type viscometer) with .a 1:1 by weight mixture of xylene and sec-butyl a:LcoholO The resulting composition was coated on a mild steel pla~eO
(3) Test for the performance of the coated film The resulting coatod fi:Lm was tested for per~
formance by the method -to be desc:ribedO Tho results are shown in Table 20 _ ~m~
~; (1) Prep~r~tion of a phenol modified polymer A l-liter glass reactor equipped with a thermometex, :~ a reflux condenser, a feed opening and a stirrer was charged ::
with a mixture oonsisting of 170 g of ~ naphtha--cracking hydrocarbon fraction having the composition (C) shown in :
~able 1 and 30 g of a phenol9 and the mixture w~s stirred To the resulting solutlon was added 2 g of a boron tri nuoride/ ~.
phenol complex9 and in & nitrogen atmo~phere? the polymeri~
æation was performed~at 0Go for 2 hours. 150 ml of a 003N
aqueous solution~o:f sodium hydroxide was added to the result~
ing polymerization pr;oduct, and the mix-ture~was stirred for 20 ~ 30 minutesO The aqueous layer was separated, and the residue : was repeatedly washed:until the aqueous layer becc~me neutralO .
The aqueous:l~yer was:~separated9 and the~residue Was concent~
:ra-ted at 200Co and 5 I~mHg~for 30 ~inutes to afford a modified : polymer having the properties: shown in ~able 20 25~ (23 . Prsparation~of an epoXy rssin compositlon :A blend~consisting of 20 parts by weight of bis~
phsnol A~dlglycidyl e-ther (EP~MIK R~lLI49 a trademark for a product~of Mltsul Pstrochemlcal Epoxy CoO~ ~tdo), 60 parts: : :~
by wslght~:of~the polymsr~obtaIned ln ssc-tion (1) above9 6 ;
. ~

,, .
. ., ~3~3~

10() parts by weight of talc9 30 pa:rts by weight of titanium white and 40 parts by weight of eth-,yl cellulose was p~ssed through a thre~-roll mill three times to disperse the talc ~ ;
uniformly in the blend~, Then, a polyamide amine curing agent (~POMIK Q- 671 ) was added in an amOUnt of 20 parts by weight, and the viscosi-ty of the mixture was adjusted to 2500 centipoises (measurea by a B--type viscometer) with a 1:1 by weight mixture of xylene and sec--butanolO The result ing composition w~s coated on a mild steel plateO
( 3) ~est for the performance of coated film ~'hc resulting coated film was tested for per.form~nce ~: by the method described hereinbelowO ~he resul ts are shown in Tabl e 2 0 i:~
.

:

-.;

.-, 37 ~
, "j .: :

~b~le~2 Example . ~ ~ ~ ~ ~ :
~ ~ ~ ~_. ~ ... ~_ ~ _ _ , . ~_~.~._ .. , ~.. _~ __ .. ~. .. : ~
Modi~led ~ol~mer Polymerizable material styrene s-tyrene tolPre Phenol or naphthol phenol phenol phenol So~tening point (CO) 7.5 52 41 Color (Gardner number) L~ ~ 3 ~:
Content of the phenol or naphthol 14 12 13 :: :(% by weight) Hydroxyl content .
(millimoles/g) 105 102 loO ~
Amount used : .
(parts by weight) 40 40 4G ~
, ~ ~._ __.~_ . :.-: (PE ~ ~ cotmpound ) X 144 (40) R~144 (40) R~144 (L~O) ~
, . . . ,~ ,__, _~_. ., - . - _ . _ ~ ~___ ~__ _.
~ (Curing agent ( POMIK) Q 671 (30) Q~671 (30) Q~671 (3G) ~ .
, _ __ ._ ~ ~ . ___ __ .. ~
Properties of the coated : : ~ .
fllm ~ : : "
Pot life (hr9 20Co ) ~ ~ 24 ~ 24 24 ~:~
inge(htouchOdrying 8 o S 8 ~ 0 8 0 0 Curing tlme (hr9 20Co)~ ~ 3~ ~ 34 35 : :
On te9t for ~ :lOO/lOO : : lOO/100 lOO/100 ~ -al hpray)test :~ ~ o chanee ; No change ~ No ~heLge~
~Acid resis-tance test : No change for No change for :No:change for ;~ ~10% H2S04) ~ one month : one month~ : one month ;~
: ~Alkali resistance : : ~ : -.::`
~~ l0%~NaOH)~ ~Dltto : Ditto :~ Ditto : : ~Water reslstance~ ; Ditto Dltto Ditto ~ ~ n~-~&xane reslstance ~ :Ditto ~ : Ditto Ditto :: ~ ~ :;.: '.:
~Strength : ~ ~ : ~ HB H HB
Color ~ ~ White hite White :: , : . ' . :, ~3~

~ lQ~? ~o-t~-ln~ue~d Example 4 5 6 ~odlf ~ o~ mer~
Polymerizable material vinyltolllene1) indene a-methylstyrene Phenol or naphthol phenol phenol phenol Softening point (CO) 55 130 35 Colo:c (Gardner number) 2 5 4 Content of the phenol or rlaphthol 1 L~ 1 L~
(% by wei.ght) Hydroxyl content ~ -(millimoles/g) lo 3 104 105 Amount used (parts by weight) 40 40 40 ,: __~. . .~. __ ~. ~.. ~_ _~_ Polyepo ~ compound R-144 (40) R~144 (40j R--144 (40) uring agent ( POMIK) Q~671 (30) Q-671 (30) Q~6074) (35) ____,. . . . ~ ,~. ___. _~ ._._ _ _.~
Properties of the coated ~

~Pot li~e (hr, 20Co ) ~ ~ ~ 24 23 24 ~inger touch drYing ~;;tlme (hr, 20Co~ ~oO 705 805 ~Curlng time (hr, 20C~) ~32 30 34 Crosscut test~for ~ ~ 100/100 100/100100/100 OO hours) ~ ~ No~c~a~ge ~o changeNo change Ac~id resistance -test ~ No change for No change for Mo change for ~ ~;
%~ H2SOL~ :: ope~month one month one month - ~Alkal reslstanoe~ ~ Ditto Dlt-to Dltto -; ~Wster reslstance~ ~Dltto ;~ ~Ditto Dltto ~n-H&xa)e~res1slano~e ~ ~itto ~ ~ Ditto~ ~ Ditto ~
~Strength ~ ~ ~ ~ H ~; 2H HB ; -Color ~ _ White White White ~ ,, _ __ . _ ~ .~. : :., ~ 39 ~

: ~

~L~..34~

I~3~1e 2 ~conti.nued) ~xample 7 8 9 Modified~~ me~r :.;.
Polymerizable material a-methylstyrene styren.ea methylstyrene Phencl or naphthol phenol phenol ph~nol : :
Softening point (CO) 35 52 ~5 Color (Gardner number) 4 3 4 :
Content of the phenol or naphthol 14 12 1 L~ ::
(% by weight) Hydroxyl conten-t1 5 1 2 1 5 (millimoles/g) .0 O. O :~
~ Amount used ;~ (parts by weight) 8 25 40 . ~ .~ _~ _~.. __ ~ ., ~ (olyepo~ compoundR--144 (72)R--144 (55) R~-~013) (40) ~ ~
~: ~ ~ . __ __ ~. ~ ___ :-' ~ (Urlng agent (~POMIK) Q 671 (50) Q 671 (20) Q~671 (30) ~
~ i __ _~, , . . . ____ ~ _~
: Properties 0~ the coated .:~
Pot life (hr 9 20Co) 24 24 24 ~ing ~ 80 5 Bo 5 8~ 5 ;~
~Curing~time (hr,-2000) ; 36 ~ 36 35 i~

drhesSion~ ~ ;~ ~100/100 :100/100 ~lOOi100 St ~ No change ~ No change ~No change ..

~Acid reSiStance t:est No change ~or No change for No:change:~or " :
`~ ~(10% H~S04)~ ~ one~month one month one month ~ .; .... -~
%]N OH)lSta~~ ~Ditto: Ditto Ditto:
~:Water re6ista~lce ~ :~ ~ ~Ditto ~ Dltto Ditto ~: ;~
n-~&x ne resi~tsnoe;~ ~ ~Dhtto ;~Ditto Ditto;

Strength ~ ~ B HB : H ~ . ,~
;Color _ Whl te White hite ~: . .",~,,~,, , , .,~,, ___._ __ ~ 40 ' ~'`1 ' :: ~
::

a ,b,,l~Q ~','~,~,c,o~t~,i" nuei,d ;~, Example Comp~ Ex~ 1 lO ll Modified E~l~mer ,~
Polymerizable material ~ARCRON ~180 ~-methylstyrene a--methylstyrene Phenol or naphthol . ~ aphthol resorcinol Softening point (CO) -_ 63 68 Color (Gardner number) .. 7 ~ :~
Content of the phenol or naphthol 7 7 : -, (% by weight) , Hydroxyl content 5 1 2 (milllmoles/g) Amoun-t used (parts by weight) 40 8 8 ~ ~ ~ ~ _~_.~ , -, Polyepoxy compound R~144 (40) R~140 (72) R-140 (72) ~ ~ .
~ (uring agent (EPOMIK) Q--671 (30) Q~71 (50) Q-671 (50) ~ ~

~: ~ ~ ~ , , __ ~ Properties of the coated -~
:~; . ._ . . .
Pot life (hr, 20Co ) 24 24 24 ~'inger touchOdrying~ ~ 900 800 800 ::

Curing time:(hr~ 20Co) 40 35 30 :
test fo~r : lOO/100 100/100 lOOilOO

~(3QO hour~ Pe llng by rust No change No change ~Acid resistance test Blister occur- No:change for ~o change for ~1(lo% H2S04)~ red in 20 days one nth one month ~ :
;:Alkali resistance :Blister occur-- D
(10% Na~ red~in 22 days lttO Ditto . ~ .
:Water resl~tance~ ~ No ohannge for: Ditto Ditto ~ : .
~n-Xgxa e reslstance red in 20 day6 Ditto Ditto Strength l 2B 2H ~

: Golor BlaCk brown White ~hite .:
.. ~ ~ :.

. .

4~

~able 2 ~continued) Examplc 12 1~ 14 ~ :
Modifled~E~ol~m~e~r . Polymerizable material C9 fraction A C9 fraction B C9 fraction C
Phenol or naphtholphenol phenol phenol : ~
Softening pvint (C0)57 70 65 ~ :
: Color (Gardner number) 15 13 16 : Content of the phenol ~
(yO by welght) 24 22 31 Hydroxyl content (millimoles/g) 2~0 108 206 , P . _ . Y _ _ .g ~ ._ ~ _.,, y., ,.~. ___ ._ ";
(~POMIK ~ parts by weight~ R-144 (40) R-144 (40) R-144 (40) ~ :
_ _ _ _ ~ ~ _ ~ ~ ~
~:~ (parts b-.y weight)Q^671 (30) Q-671 ~30): Q 671 (3~) ~ ~ _~_ ~ .~ Y ,~ ~ ~
Properties of the coated :
~ilm ~ _ ; : :;~
Pot life ~hr, 20Co) : ; ~;24 24 23 ~ ~ :
inger touch drying 7 ~tlme (hr, 20Co ) ~ ; o 5 70 5 705 Curing time (hr1 20Co ) ~ 3~2 32 29 ~ -Crosscut test for : ~ lO0/100 lO0/100 100/100 ~

alt spray)~test ~ ~ No~ change ~No:change No change ;~ :-:`
Acid resistance test: :: No~change ~or No change for No change ~or :
(lO%~H2S04) ~; ; ;one~month~one month one month : ~ j ~.. "
Ikal e~lstance ~ ~ Dltto ~ ~Dltto Dltto ;:

::; Water resistance~ ~Di-tto ; ~Dltto Ditto ; ;~ n-H&xane resistanoe ~ :~; Dltto~:Dltto Ditto ::~St~rength ~ ~ 2H 2H

Color ~ Light yellow ~
, ~ 42 , ~L3~ h~
,~ .
'~bl,e_2 _~.Qt~ nued?~

Example 15 16 17 ModifiQd po~ymer~
Polymerizable materi~l Cg fraction A Cg fraction A Cg fraction A
Phenol or naphthol cresol2) phenol sec-butyl phenol Softening point (CO) 60 60 65 Color (Gardner number) 15 14 14 Content of the phenol or naphthol 20 24 23 (% by weight) ::
Hydroxyl content (millimole~/g) 1~7 104 1~2 Amount used (parts by weight) 40 L~O L~O ~ :
~ _ ~ ,,, , , Polyepoxy compound R-~144 (40)~ 144 (40) R 144 ( 40) uring agen-t (~POMIK) Q-671 (30)Q-671 (30) Q--671 (30) ~ :
, ~ ~ . .~.. __ ."~ ,~, . .
; Properties o~ the coated :
film : : ;.
: __ , Pot li~e (hr~ 20Co ) ~ ~ ~ 24 : 24 24 time ~hr, 20Co~ ~ ~ 800 ~ 800 800 ~ : ~
~Curlng tlme (hr, 20C.) ;~ 33 32 32 ~ ~ -CroSscut test~for ~ ~ ~ 100/100 100/100 100/100 ~" ~ Salt 6pr6~)test~~ No change Nc ch1nge ~ ~No chang6 A:cid resis~ance test ~: ~No change ~or No change for No change for `~ ;~(10% H2S04):~: ~:one~month one~month ~one month ~(l;O/alN OH)l6tan0e~ ~ ~ ~; itto ~ : ~ Dltto ~: Dl~tto ~ ¦
Water~re6l6t ~oe~~; Dltto :IDitto; :~ Dltto ;~n-H&xane~resi6t6nce~ Dltto ~ Ditto ~ ~ Dit~to ;~

;~ Streng~th : ~ ~ I ~ H ; : ~ ~ ~
~:~ C~olor ~ ~ ~Yel~1ow ~lght ~ellow Li3bt ~I}:~ , -r ~ ~ ~ . .,''~ `' ~ . .

, ;

~'able 2 ~continued) Exa~ple 18 ~ ~
Modif _ d ~o,~l~er, Polymerizable material Cg frac-tion A C9 frac-tion A Cg fraction A
Phenol or naphthol tert--butyl octyl phenol nonyl phenol So~tening point (C,) 70 63 61 Color (Gardner number) 14 15 1~ : -Content of -the phenol or naph:thol 23 21 20 (% by weight) ,~
Hydroxyl content 1 8 0 8 '~
: (millimoles/g) o2 00 O .'.
Amount used L~O 40 40 :: (parts by welght) ~ ~ .. . ~ ~_ ...... _ .~ ~ ~ .,~_ .~ ~
~ Poly po ~ compound R 144 (40) R 144 (40) R-144 (40) ,', : -- _~ ~............ _ ~_ ._~--- --- ~ -~1 - - '::
: (Curitng bgenti(~Pt)MIK) Q--671 (30) Q 671 (30) Q--671 (30) - .
~ ~ . ~ ._ ~__ : :, }-rp:~t~cs ~' t~ e.~ :

: Pot life (hr, 20Co ) 24 24 24 tlmege(rhtrU20Cd ~ing 705 800 800 , Curing time (hr, 20Co) 31 33 ~2 Crosscut test~for ~ 100/100: 100/100 10~/100 ~ :

: (~00 hours) ~ No change No change No change : Acid resistance test No:change for No change for No change for ~(10% H2SOL~ one monthone mon-th : one month (10% NaOH) ~ Ditto Ditto Ditto Water resis-tance ~ Dltto Dltto Ditto ~ -~
~H&xa e~resistance ;: Ditto Dl-tto Ditto ~ : ,,~
Strength : ~ 2~I ~ H H ~ . :
: Color ~I~Lb ~ Yellow Yellow , -~ ` ' ' ' fl) ~`
,~:
,, blQ 2 ~contin~ue~d) Example 21 2?
_ ~_ ~ ~ .~
Modi~fied ~o~
Polymerizable material Cg fraction A C~ fraction A
Phenol or naphtholdodecyl phenol phenol Softening point (CO) 62 115 Color (G~rdner number)15 14 C~n-tent of the phenol . ~
or naphthol 20 23 :;
.~; (% by weight) i Hydroxyl con-tent 0 7 1 8 (millimoles/g) ~ O
Amount u~ed 40 60 (parts by welght) -:
~ ~ ~.~ __~ ,__ __~_ ::
~; ~: ~`h ~ ~1 ;r',~ ~ w~ ~bt) R 144 (4C) R144 (20) ~-Curing agent (~POMI~)Q-~671 (30) Q~671 (20) : ;
(parts by welght) l ~ ~ ~ ~
Proper-ties of the coated fllm __ Pot life~(hr, 20C o ) ~ 24 2L~
Finge(r touchOcdrylng~~ 800 800 ,"
Curing~time (hr~:20CO)33 29 Crosscut test for :lO')/lOO 100/lOO .
' adhe sl on , ~ ,.
Salt spray~test~ ~ ~o change ~o change (300 hours) ~ :
: Acid resistance test No change for No change for~
; (10% H2S04~ ~one month one month :~

(lh NaOH) ~ ~ Dit-to ~ Ditto Water reslstance ~ Ditto :Ditto : ~-n-H&xane~resistance D Blis-ter occur-(30 CO): ~ lttO red in 28 days Strength H :~ H :
Colcr ; Yellcw Light yellow ~ ~ ~ ______~_~
:: : 45 .~ :
`~
:

39L9~O

1) m~/p- weight ratio=6/4 2) ~-/p- ratio=6/4 3) R-301~ bisphenol A glycidyl ether, a product of Mitsu:i Petrochemical ~poxy CoO 7 ~tdo 4) Q-6079 modified aliphatic polyamine, a :~
product of Mitsui Petrochemical ~po~y CoO, ~td o r~he properties shown in r~able 2 were measured by the following methodsO
(i) So~tening point of the copolymer Measured by the ball and ring method in ASr~M ~ ~-, 2858r~ 0 ,, (ii) Color (Gardner number) ~
Measured by the method of AS~M D1544 680 ~- ;
(iii) r~he coated:test plate was prepared by c0ating the compositi.on on a mild steel plate by the method described in JIS:E-5400O~ r~he thlckness of -the coated~film upon drying ;~ ;
was 150: + 5 mlcronsO~
; (lV) ~he pot li~e~of the epoxy resin composition~ the 20 : finger touch drying time of the coated ~ilm~ the curing tlme,~and the acld reslstance, alkall resistance and water ;reslstanoe:~of the oo~ate~d film were measured by the method of JIS K~-54000 ~
(v) ~ ~he salt:spray test was~performed by the method ~;.
25~ of JIS E-2371 (vi) :~he strength of;the~co~ated:~fllm was measured by::: ;~
the method~o~ JIS~K-5651. ~ ~ -(vii:)~ ~ r~he co~lor~of the~coated film was observed visuallyO
(Vlli) ~he crosscu~ te:st was per~ormed by providin~ 11 ` `
parall~el~ cuts in a~substr~ate~:at an l~t~e~val of 1 mm, and ~ :

46 ~
~: , :: :
: :
~: :

~l349~

another se-t of 11 cuts at righ-t angLes to them9 applying an adhesive tape to the substrate, pulling it aw~Y~ a~d counting the number of remaining squaresO
(ix) ~he resistance to n hexane was performed by dip~
ping the test sample in an n~hexane solution at 30~0, and then observing -the state of the coated film visually~

' ,':
::
`' : , ., . ~ :~ : ', ' ' ,;

: : ::

: : - :

'

Claims (16)

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 poly-merizing a polymerizable material selected from the group consisting of (a) cationically polymerizable hydrocarbon-con-taining fractions having a boiling point in the range of from 140 to 280°C. obtained by distillation of a cracking or reforming product of a petroleum, (b) a cationically polymerizable aromatic un-saturated 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 l 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, .alpha.- and .beta.-methyl styrenes, o-, m- and p-vinyltoluenes, 0-, 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 an integer of 1 or 20

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 to 50% by weight, preferably 4.5 to 50% by welght.

9. The composition of claim 1 wherein the polymer (A) is a liquid at room temperature, or a solid with a soften-ing point of not more than 200°C.

10. The composition of claim 1 wherein the polymer (A) has a number average molecular weight of about 250 to about 3,000.

11. The composition of claim 1 wherein the polyepoxy compound has an epoxy equivalent of at most 5,0000.

12. The composition of claim 1 wherein the polyepoxy compound has a molecular weight of 86 to 20,0000.

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

14. 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.

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

16. 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.