Note: Descriptions are shown in the official language in which they were submitted.
This invention relates to new~ water~soluble or water-
dispersible resinous salts, to aqueous compositions
coDtaining them, and to surfaces coated with such compositions.
To ob~ain a corrosion-resistant coating for metal
containers it is conventional to coat the metal surface
with a crosslinkable resin formulation dissolved in an organic
solvent and then to heat the coating to evaporate the solvent and
to crosslink the resin. Crosslinking the coating converts it into
a tough, adherent, flexible, and protective film. During heating,
the solvent is usually evaporated into the atmosphere. Since
or~anic solvents are relatively expensive, inflammable, and
usually en~ironmentally objectionable, there e~ists a need for
coatings which may be applied using minimal proportions of such
solvents, particularly useful being coating compositio~s which
contain a high proportion of water.
We have now found that stable, aqueous compositions which
cure to give coatings having excellent mechanieal properties
and chemical resistance may be prepared from new resinous
salts. These salts are prepared fr~m a phenol-terminated
2~ resin~either by thioalk~lation ~ith a mercaptocarboxylic acid
and an aldehyde followed ~y at least par~ial neutralisation
of the carboxylic acid group(s~ introduced by the ~ercapto-
carboæylic acid, or by sulphoalkylation with sulphurous acid
(or a water soluble salt thereof) and an aldehyde followed,
if necessary, by at least partial neut-ralisation of the sulphonic
~3~
acid group(s~ introduced b~ sulphLIrous ac~d or its salt. They may be
used with an aminoplast, a phenol~formaldehyde resin, or a blocked
polyisocyanate as aqueous surface coating compositions. In
cer~ain cîrcumstances the addition of such a coreactant is not,
however, necessary.
The use of YariouS reactions to obtain from phenols or
epoxides water--soluble or water~dispersible resins ~or use as
coatings has previously been described.
For ~xa~ple, British Patent Specifica~ion No. 1 254 528
discloses carboxyl group-co~taining polyethers said to be suitable
for use in water~d;lutafile coating compositions and which are
obtained by reaction of a glycidyl e~her, a phenol-aldehyde
condensate containing methylol groups, and a hydro~ycarboxylic
acid. The product ;s a polyether phenol~aldehyde resin etherified
with the hydroxycarboxylic acid. Use of a mercaptocarboxylic acid
to give a thioether-carboxylic acid is not enYisaged. United
States Patent ~o. 4 153 586 describes producing a water-dispersible
resin by reaction of a polyepoxide with a mercaptocarboxylic acid
in the presence of a tin-containing catalyst.
Reaction between a phenol, an aldehyde, and an alkali
metal bisulphite is also known (see, for example, Suter et al.,
J. Org. Chem., 1945, 10, 470-478) but, so far as we are aware,
has not been carried out hitherto using a phenol-tipped advanced
polyepoxide.
This invention accordingly provides new, water~soluble or
water-dispersible resinous salts of formula
~ 4 ~
lP ~ X ~ _
where
R represents either
a group of formula
-S Rl COO- II
or a group of formula
~S03 III
wherein Rl represents an aliphatic, aromatic, or araliphatic divalent
group of 1 to 10 carbon atoms which may contain a further group
of formula -CCO M ,
R represents a hydrogen atom or an alkyl group of 1 to 4
carbon atoms,
! one of R and R3 represents a hydro~yl group and the other
represents a hydrogen a~om, a halogen atom, an alkyl group of 1
to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms,
each -R4, which may be the same or different, represents
a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon
atoms, or an alkenyl group of 2 to 4 carbon atoms,
R represents an atom or a group bonded to a ring carbon
atom which is ortho or para to the group R3 or R13 that represents
~ s ~
a hydroxyl group, and is a hydrogen atom, a halogen atom, an
alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4
carbon atoms, a group of formula -('H(R )OH, a group of formula
-CH(R )oR8, or a group of formula
-CH-R M IV
R2
R6 represents the residue of a polyepoxide after removal
of (m-~) 1,2~epoxide groups,
each oE the substituents R , which may be the same or
different, represents either a hydrogen atom or a covalent bond linked
to the group R6 to form a cycloaliphatic ring which may be
substituted by one or more aliphatic,cycloaliphatic and/or hetero-
cyclic g~oups,
R8 represents either an alkyl group of from 1 to 6 carbon atons or
an alkoxyalkyl group wherein the alkoxy group and the alkyl group
each have from 1 to 6 carbon atoms,
R9 represents the residue of a monohydric phenol, a secondary
monoamine, or a monocarboxylic acid after removal of the hydrogen
atom of the phenolic hydroxyl group, the carboxylic acid group,
or the secondary amino group 9
m represents 1, 2, 3, or 4,
n represents zero or 1,
p represents zero or 1, such that ~m~p) is at least 2 and
at most 4,
X represents an alkylene or alkylidene group of 1 to 3
carbon atoms, a carbonyl or sulphonyl group, an oxygen or sulphur
D ~5
~ 6
ato~ or a valency bond, and
M represents a hydrogen ion, a cation derived from an alkali
metal9 ammonia, or an amine, including quaternary ammoni~n cations,
or one ~alency of a polyvalent catlon, with the proviso tha~ at
least 25% of the ions M are a said cation.
Preferred salts of formNla I are those wherein, wherl R represents
a group of formula II, R represents an alkylene group of 1 or 2 carbon
atoms~ those wEIerein R6 represents a residue having an average
molecular Yeight of fro~ 1000 to 5000, and those wherein (m~p)
represents 2. C~lorine and ~romine are tEle preferred ~alogen
atoms within t~ definitions of R3, R31, R4, and R5.
Prefera~ly the salts of formula I are further of formula
- 5 R3
R3 ~ X ~ OCH2CHCH2 - R CH2¦HCH2
M R - CH 4 (R )4
Rl /
R3 ~ X ~
R2 (R4)4 V
o~
- 7
R 3
Rl OH OH
R ~ 4 ~ X ~ ~ CH2CHCH2 -R - CH2~HCH2R
* M R ~ CH R (R )4
VI
where
R , R2, R3, R3 , R4, R5, R9, X, and M are as hereinbefore
defined and
R10 represents the residue of an aliphatic, cycloaliphatic,
or aromatic diglycidyl ether or ester after removal of both
glycidyl groups.
It is further preferred that R10 in the compounds of formula
V or formula VI is itself of formula
~: _ _
~ ~ X ~ OH ~ ~ -O-
(R )4 (R4)4 (R )4 (R4)4 q
VII
where
R and X are as hereinbefore defined and
q is zero or an inte~er of from 1 to 20, and is preferably
from 2 to 10~
Salts of formula I, V~ and VI wherein the group R r,epresents
a hydroxyl group are part.icularly preferred, as are those in which
R2 and R4 both represent a hydrogen atom.
.
Another aspect of this invention is a process for the preparation
of water~soluble or water-dispersible resinous salts which comprises
~eac~ion oE a phenol-terminated resirl of formula
R -CH-CH ~ R6 ~ CH - C~10 k ~ X ~ oa l
(R4)4 ~n (R )3 J m
VIII
wherein R4, R6, R7, R~, ~, ~, n, and p are as hereinbefore
defined,
wi~h the proviso that at least ~ne of the two carbon atoms
ortho, or the one carbon atom para, to the carbon atom bearing
the indicated phenolic hydroxyl group is unsubstituted, by thio~
alkylation in the presence of a source of M (where M is as
i previously defined) ions with an aldehyde of formula
R CHO IX
where R2 is as hereinbefore defined,
and a mercaptocarboxylic acid of formula
15HS-Rl-COOH X
where Rl is as hereinbefore defined for Rl but may contain
a carboxylic acid (-COOH) substituent instead of a -COO M
substituent.
_ 9 ~
This reaction is preferably effected by heating the reactants,
usually in an inert solvent, in the presence of sufficient of a base
at least partially to neutralise the mercaptocarboxylic acid. The
reaction temperature is preferably within the range 60 to 180 C,
especially 75 to l40C, and the reaction is usually complete
within 15 minutes to 8 hours. Suitable inert so1vents include
hydrocarbons, ethers, alcohols, and esters; amongst these toluene,
xylene, tetrahydrofuran, butanols, ethyl acetate, and especially
2-butoxyethaDol and 2-etho~yethanol, are preferred.
A fu~ther aspect of t~is inYenti`on is a process for the
preparation of water-solub~e or water~dispersihle resinous salts
which comprises reaction of a phenol~terminated resin of formula
VIII (whe~e R4, R 9 R ~ R ~ X, m, n~and p are as hereinbefore
~eflned~ with an aldehyde of formula IX (wherein
R is as hereinbefore defined) and sulphurous acid or a water~
soluble salt of sulphurous acid,such as sodium or potassium sulphite,
bisulphite, or metabisulphite, This reaction is preferably effected
by heating the reactants, usually in an inert solvent, if necessary
in the presence of sufficient of a base at least partially to
neutralise any free acid, and optionally in the presence of a
surfactant. The preferred reaction temperatures and suitable
sol~ents are as described above for ~he reaction with a
mercaptocarboxylic acid.
Suitable bases for the at leas~ partial neutralisation include
sodium hydroxide, sodium carbonate, potassium carbonate, ammonia,
triethylamine, and triethanolamine. 2-(dimethylamino~-2-methylpropan-
s
~ 10 ~l-ol and 2~Cdlmethylamlno~ethanol are particularly preferred.
Usually 0.3 to 2.0 moles of the mercaptocarboxylic acid of
formula X or of sulphurous acid or its salt are employed per mole of
phenolic hydroxyl groups in the resin of formula VIII. An excess
of the aldehyde of formula IX is usually employed, especially
1.1 to 4~0 moles of the aldehyde per mole of the mercaptocarboxylic
acid of form~la X or of sulphurous acid or its salt, since t~e
products then exhibit greater stahility to storage at room
temperature.
The preferred aldehyde of formula IX is formaldehyde;
conveniently this is generated in situ from paraformaldehyde.
Preferred acids of formula ~ are 2- or 3-mercaptopropionic
acid, thioglycolic acid, and thiomalic acid.
The phenol-terminated resins of formula VIII used as starting
materials are themselves prepared by the reaction of a polyepoxide,
preferably a diepoxida, with an excess of a dihydric phenol using
known methods. This reaction results in adYancement of the
polyepoxide through reaction with ~oth hydroxyl groups of the
dihydric phenol. There must be at least as much dihydric phenol
present as there is polyepoxide, on a molar basis, in order to
give a product having at least one terminal phenolic group. The
lar ratio o~ polyepoxide to dihydric phenol is usually within the
range 1:1.02 to 1:1.6, and especially 1:1.1 to 1:1.5. The preferred
method of advancement is ~y heating the reactants at 100~200C, and
in the presence of a base, which may be a tertiary amine but is
preferably an alkali metal hydroxide. An inert solvent may be
present if desired.
The dihydric phenol used for advancement may be mononuclear,
e.g., hydroquinone, but is preferably a bisphenol, especially one
of formula
HO ~ X ~ _ OH
(R4~4 CR4~4
where X and R4 are as hereinbefore defined, such as bis(4-hydro~y~
phenyl)~ethane and 252-~bis(4~hydroxyphenyl~propane.
Polyepo~ides preferred for adYancement to form the starting
material of formula VIII are those containing two terminal groups
of formula
~0
CH~C~-~I2 XII
directly attached to an atom or atoms of oxygen, nitrogen, or
sulphur.
As examples of such resins may ~e mentioned polyglycidyl
esters obtainable by reaction of a compound containing two
carboxylic acid groups per molecule with epichlorohydrin or
glycerol dichlorohydrin in the presence of an alkali. Such
polyglycidyl esters may be derived from alipha~ic polycarboxylic
- 12 ~
acids, e.g.g oxalic acid, succinic acid~ glutaric acid, adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
and dimerised linoleic acid; from cycloaliphatic polycarboxylic
acids such as tetrahydrophthalic acid, 4~methyltetrahydrophthalic
acid, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid;
and fr~m aromatic polycarboxylic acids, such as phthalic acid,
isophthalic acid, and terephthalic acid,
Further examples are polyglycidyl ethers obtainable by reaction
of a compound containing at least two free alcoholic hydroxyl or
phenolic hydrox~l groups per molecule with epichlorohydrin or
glycerol dichlorohydrin under alkaline conditions or, alternatively,
in the presence of an acid catalyst and subsequent treatment with
alkali. These ethers may be made from acyclic alcohols such as
ethylene glycol, diethylene glycol~ and higher poly(oxyethylene2
glycols, propane-1,2-diol and poly(oxypropylene~ glycols,
propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene~
glycols, pentane-l,S-diol, and polyepichlorohydrins; from
cycloalipha~ic alcohols such as resorcitol, quinitol, bisC4~
hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane,
and l,l-bis(hydroxymethyl)cyclohex-3-ene; and from alcohols
having aromatic nuclei, such as N,N-bisC2~hydroxyethyl~aniline
and p,p'-bis(2-hydroxyethylamino)diphenylmethane. Or they may
be made from mononuclear phenols, such as resorcinol and
hydroquinone, and fro~ polynuclear phenols, such as bis(4-
hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxy-
phenyl) sulphone, 2,2-bis~4-hydroxyphenyl)propane, 2,2-bis(3,5-
- 13 ~
dibromo~4-hydroxyphenyl~propane and 2 9 2-bis(2~allyl-4-hydroxyphenyl)-
propane.
Poly(N-glycidyl) compounds include, for example, those obtained
by dehydrochlorination of ~he reaction products of epichlorohydrin
with amines co~taining two amino-hydrogen atoms such as aniline,
n butylamine, and bis(4-methylaminophenyl)methane; and N,N'-
diglycidyl derivatives of cyclic aLkylene ureas, such as ethylene-
urea and 1,3~propyleneurea, and of hydan~oins such as 5,5
dimethylhydantoin.
Examples of poly(S-glycidyl~ compounds are di-S-glycidyl
derivatives of dithiols such as ethane-1,2-dithiol and bis(4-
mercaptomethylphenyl~ ether.
Polyepoxides having the 1,2-epoxide groups attached to
different kinds of hetero atoms may be employed, e.g., the
glycidyl ether-gl~cidyl ester of salicylic acid, N-gly~idyl-N~-
(2-glycidyloxypropyl)-5,5-dimethylhydantoin, and 2-glycidyloxy-
1,3 bis(5,5~dimethyl-1-glycidylhydantoin-3~yl)propane.
Polyepoxides containing non-terminal epoxide groups may
also be employed, such as ~i~ylcyclohexene dio~ide, limonene
dioxide9 dicyclopentadiene oxide, 4-oxatetracyclo [6,2,1,02'7,0 ' ~-
undec-9-yl glycidyl ether, the bis(4-oxatetracyclo [6,~,1,02'7903'5~-
undec-9-yl) e~her of ethylene glycol. 3,4-epoxycyclohexylmethyl
3'~4'-epoxycyclohexanecarboxylate and its 6,6'-dimethyl derivative,
the bis~3,4-epoxycyclohexanecarboxylate~ of ethylene glycol, and
3-(3,4-epoxycyclohe~yl)-~,9-epoxy-294-dioxaspiror5~5]undecane.
~ 14 ~
Also, if desired, a mixture of diepo~icles ~ay be used.
Polyepo~ides containing more than ~wo epoxide groups ~ay be
advanced but, as those skilled in the art of epo~ide resi~s are
aware, advanc~ment of such polyepuxides is more difficult, there
5 being a risk or gelation.
Preferred diepoxides are d;~lycidyl ethers and diglycidyl
esters. Specific preferred diepoxides are diglycidyl ethers of
2,2-bis(4-hydroxyphe~yl)propane or bis(4-hydroxyphenyl)Dethane,
having a 1,2-epoxide content of more than 1.0 equivalent per
kilogra~
The dihydric p~enol ~y be used alone or, if desired, i~
the presence of a compound which reacts with an epoxide group
of the polyepo~ide ~ut will not ~eact further, so preventing
further chain~length~ning reaction. Suitable such Ichain~
terminators' are secondary monoamines, monocarbo~ylic acids
and, more especially, nohydric phenols, p~tert.butylphenol
being particularly preferred. If a chain terminator i5 added
it must be in such a quantity that at least one epoxide group
per average molecule of the polyepoxide is left free to react
with the dihydric phenol.
As already stated, the salts of this invention may be used,
in the form of heat-curable compositions, to form surEace
coatings~
3~
~- 15 ~
This in~e~tion accordingly further provides heat-curable
composition~ comprisin~ 100 parts by ~eight of a salt o~ formula
I~ calculatet o~ its ~olids co~te~l: (as here;nafter def;ned) and
2 to 200 parts, pre~er~hly 23 to 150 part~, by weight, calculated
oa its solids co~tent~ of an smi~oplast~ a phe~ol-formaldehyde
resin, or a blocked p~lyisocy~nate1 ~he aminoplast or phenol-
for~aldehyde resi~ ha~i~g at les~t 2 groups of formula
ca o~ll XIII
attached directly to an amidic nitrogen ato~ or atoms or
direc~ly attached ~o carbon atoms of a phenolic ring, where R
represents a hydrogen atom or a~ alkyl group of from 1 to 6
carbo~ ato~s.
Such compositio~s i~ a form suitable for application ~ill
u~ually also contain ~ater a~d a mQnor proportion, compared with
the volume of water, of a~ organic solvent, such as a~ ether,
alcokol, k~one,or ester, esp~cially 2-~u~7ethanol or 2-
ethoxyethanol. ~Iethylolated compouuds which may be used to form
the coDpositions include urea.-fon~aldehyde condensates, æmino-
triazine-formaldehyde condensates, especially mela~ine-
formaldehyde and benzoguana~i~e-formaldehyde condensates, and
phenol-formaldehyde condensatesO These may be etherified
if desired, e.g., the ~butyl ethers may be used. In
many cases the methylolated compo-lnds and their ethers are not
the~selves water-soluble or water-dispersible. Tncorporation
of a compound of formula I aids the dispersion or solution of such
~ 16 ~
m~erials in wate~ giving stable solutions or dis~ersio~s of the
mix~ures.
Examples of suitable blocked polyisocyanates (i.e., those
which are stable in the aqueous dispersion at room tem~erature but
which react with the compound of formu]a I on heatîng) include di~
and poly-isocy~nates blocked with caprolactam, an o~i~e (e.g.,
cyclohexanone oxime), a monohydric phenol (e.g., phenol itself,
p-cresol, and p~tert,~utylphenol~, or a monohydr;c aliphatic,
cycloaliphatic, or araliphatic alcohol (e.g., methanol, n-butanol,
decanol, l-phenylethanol~ 2-ethoxyethanol, and 2-n-butoxyethanol).
Suitable isocyanates include aromatic di-isocyanates such as
m-phenylene, 1,4-naphthylene, 2,4- and 2,6-tolylene, and 4,4l_
methylenebis(phenylene) di-isocyanates, and also their prepolymers
with glycols (e.g., ethylene and propylene glycol), glycerol,
trimethylolpropane, pentaerythritol~ diethylene glycol, and adducts
of alkylene oxides with these aliphatic di- and polyhydric alcohols.
The compositions may be cured by heating at lOO C to 275C,
preferably 150C to 225 C, for from 30 seconds to 1 hour, preferably
from 2 to 30 minutes.
Other water-soluble or water-dispersible film-formin~
substances may also be included9 such as alkyd resins and acrylic
resins. The amount of such materials may vary between wide limits,
but should not be so great as to mask the advantageous properties
of the compositions of this invention. Typically, additions of up
to 50%, and preferably not more than 30% may be used, these
- 17 ~
percentages being based on t}le solids conteat of the materials.
By the term "solids content", as used throughout the present
specification and the clai~s thereto, is meant the percentage
residue left after a 1 g sample of the material has been heated
i~ a 5 cm diameter open dish in an oven at 120C for 3 hours
a~ atmospheric pressure.
Ne ~e further found that if, in formula I, R5 denotes a
group of formula -~M(R2)0~ the salts may be heat-cured without
including an aminoplast~ a phenol-formaldehyde resin~ or a blocked
polyisocyanate.
A further aspect of this invention accordingly provides a
method of coating a surface ~hich comprises applying thereto a
salt of formula I w~erein ~5 denotes a group of ormula -CH(R2)0
and heating the coated surface ~o a temperature within the range
15 100 C to 275 C, preferably lSO C to 225 C, for from 30 seconds
to 1 hour and prefera~ly for ~rom 2 to 30 minutes, to cure the salt.
Surfaces to ~e coated with a composition of this invention
are preferably of primed or unprimed metal, especially a ferrous
~etal, hut ~ay~be, e~., g~ w~od ~ a ~eat~esistant synt~etic ~ater-i`al.
The compositions may be applied by immersion, brushing,
rollering, spraying (including electroctatic spraying~, by
electrodeposition, or by any other conventional means. They may9
if desired, include pigments and dyes. Other materials which may
~ 18 ~
be ;ncorporated ;nclude e~tender~ ~uch as calcium carbonate,
çalcium s~lphate, barium sulphate, and magnesium silicate, surface-
active agen~s, flow additives, and plasticisers. They may
also contain a strong acid, e.g., an aromatie sulphonic acid or
its salt with an amine or a~monia, as catalyst.
This invention is illustrat~d by the following Examples
in wh;ch all percentages are by weight.
Starting materials used in the F.xamples were prepared
as ~ollows:
lQ Phenol I
Epoxide resin I, i.e., a liquid glycidyl polyether of 2,2-bis(4-
hydroxyphenyl)propane~(760 g; epoxide group content 5.25 equiv./kg),
2,2-bis(4-hydroxyphenyl)propane (684 g), and 10% aqueous sodium
hydroxide solution (1.6 g~ were stirred and heated under nitrogen
to 160 C. The mola~ ratio of epoxide .esin to bisphenol was
1:1.5. An exothermic reaction commenced and the temperature
of the ~ixture rose spontaneously to 197C. The mixture W25
cooled to 180C and stirred at this temperature for a further
3 hours to gi~e Phenol I, a phenolic hydroxyl group terminated
resin having negligible epoxide group content (not more than
0.02 equiv./kg) and an average molecular weight of 1370.
henol II
Epoxide resin I (35.9 kg), 2,2-bis(4-hydro~-yphenyl~propane
(24.6 kg~, p-tert.butylphenol (2.0 kg), and 10% aqueous sodium
hydroxide solution (39 g) were stirred and heated under nitrogen
to 180 C. The molar ratio of epoxide resin to bisphenol to
~ 19 -
monoh~dric phenol was 1:1.14:0.14. AQ e~othermic reaction commenced
and the temperature of the mixture rose spontaneously to 207C. The
mixture was cooled to 180 C and st:irred at this temperature for
3~ hours to give Phenol II, a phe~olic hydroxyl group~terminated
resin having a negligible epo~ide group content and an average
molecular weight of 1880.
Phenol III
~
3,4-Epoaycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate
(200 g; epoxide group content 7.00 equiv./kg), 2,2-bis(4-hydroxy-
phenyl)propane (199.5 g), and 50% aqueous ~etramethylammonium
chloride (2.4 g) were stirred and heated to 120C. The molar
ratio of the epoxide resin to bisphenol was 1:1.25. An exothermic
reaction commenced and the temperature of the mixture rose
spontaneously to 132 C. The mixture was cooled to 120C and
stirred at this temperature for a further 2 hours followed by 3
hours at 160C to gi~e Phenol III, a phenolic hydroxyl group-
terminated resin having a negligible epoxide group content
(0.08 equiv./kg) and an average molecular weigh~ of 1220.
Phenol IV
Epoxide resin I (114.3 g), hydroquinone (44 g), and 50%
aqueous tetr~methylammonium chloride (l g) were stirred and heated
to 130C. The molar ratio of Epoxide resin I to hydroquinone was
1:1.33. An exothermic reaction commenced and the temperature of
the mixture rose spontaneously to l90 C. The mixture was cooled
to 160C and stirred at this temperature for 3~ hours to give
20 ~
Phenol Xv9 a p~enolic hydroxyl group~terminated resin having a
negli~ible epoxide group content (no~ mo~e than 0.02 equiv./kg) and
an average molecular weight of 152C)o
Phen~l V
_ .
. 5 Epoxide resin I (256.0 g), 2,2-bis~4-hydroxyphenyl) sulphone
(254.0 g)~ and 50Z aqueous tetra~ethylammonium chloride (3.3 g)
were stirred and heated ~o 1~0C. The molar ratio of Epoxide
resin I ~o the bisphenol was 1:1~5. An exother~ic reaction
c~mmenced and the tempera~ure of the mixture rose spontaneously
to 170C. The mix~ure was heated further to 180C and held at
this temperatur~ for 2l hours tp give Phenol V, a phenolic hydroxyl
g~oup-terminated resi~ having a negligible epoxide group content (not
more than 0.02 equiv~/kg) and a~ average molecular weight of 14G0.
Phen~l VI
Epoxide resin II, i.e,, a solid glycidyl polyether of
2,2-bis~4-hydro~yphenyl~propane ~100 g; epoxide group content
1.40 equi~.tkg2, 2-butoxyet~anol ao g~, and acetic acid (2.1 g;
0.035 mol.~ were stirred and heated to 120C and maintained at
120C for 4 hours by which ~.ime the epoxide group content had
20 fallen to 0.58 equiv./kg. There were added 2 9 2-bis(4 hydroxyphenyl)-
propane (24 g~ and 10% aqueous sodium hydroxide solution (0.2 g~, and
the mixture was heated under nitrogen to 170C and maintained at
170 C for 6 hours to g;ve a solution in 2-butoxyethanol of Phenol VI,
a phenolic hydroxyl group-termlnated resin having a negli`glble epoxide
25 groupcontent,
~3~
~e~
This is a water-soluble, methylated hexamethylolmelamine ~esin
of 1002 solids content which contains~ on average, 4.0 ~ethoxymethyl
residues per aminotriazine nucleus, and has a viscosity of 10
Pa s at 25C;
Phenoplast I
This is a co~mercially available butylated phenol-formaldehyde
resin~ supplied as a solution (56% sollds content) in n-butanol
containing a small amount of toluene. It is not soluble nor
dispersible in water.
~]ocked rsocyana e r
A mixture C43.9 gg 0.25 mol~ of 2,4~ and 2,6~diisocyanato-
toluene (ra~io 4:1~ was s~irred in a reactor and 2-ethylhexanol
C7l.5 g, 0~55 mol.~ containing 2 drops of dibutyltin dilaura~e
1~ catalyst was added slowly, ~aintaining the reaction temperature
below 60C.
Free formaldehyde ~as determined by the following method:
About 1~5 g of the resin ~as ~ei~het accurately and placed
i~ a conical flask. Distilled water (30 ml~ ~as added and the
contents were mixed thoroughly. Thymolphthalei~ indicator (3 drops)
was adted and the mixture was adjusted to neutrality ~lth N/10
hydrochloric acid or sodium hydroxide if necessary. The mi~ture
was cooled in ice, and ice-cold sodium sulphite solution
(25 ml, 12.5% w/~) ~as added. The mixture was shaken ~i~orously
~ 22 -
and then titrated against N/10 hydroehloric acid until the hl~e
clolour disappeared. The percentage free formaldehyde =
titre (ml) x ~ormality of HCl x 3.001
sample weight (g)
- ~3 -
E~A~IE 1
-
A solutior- of Phenol I C50.0 g; 0,036 mole) in 2-~utoxyethanol
(16.7 g) wa.s mixed ~ith thioglycolic acid (9.2 g; 0.10 mole) and
heated to 100C- After 30 minutes a~ 100C, the mixture was cooled
tD 80C a~d paraformaldehyde (3.6 g; 91% ac~ive content, 0.11 mole~
and 2~(dimethylamano)ethanol ~5.3 g; 0.060 mole) were added. This
soluti~n was then gently heated to reflux at 140C and maintained
a~ reflux for 8 hours by which time the measured free
formaldehyde content had fallen to 0.22~. The produe~
1~ had a solids content o 73.7% and was fully dilutable with
water.
The product is su~stantiall~ of a~erage formula I, where
R denotes a group of formula II, Rl denotes eC~2~, R2, R31, R4,
and P~7 each denote H, R3 denotes ~OH, some ~f R5 denot~ -H and
the remainder denote a group ~ ~S~C~2COO M ortho to R ~ R
denotes a residue co~prising u~its of formula
2 ~ 2 0~ ~ 2 ~ oc~2
CH3 r CH3
XIV
wherein r has an average value 2.3, m is 2, p is zero, n is l, ~
denotes isopropylidene para to ~3, and 60% of the groups M denote
a group o~ formula HOCH2CH2NHCCH3~2, the re~ainder denoting H .
- 24 -
EXAMPLE 2
A solution of Phenol II ~350 g; 0,186 mole~ in 2~uto~yethanol
(191 g~ was mixed with thioglycolic acid (47.9 g; 0.52 mole~ and
heated to 100C. After 30 minutes at 100C the mixture was
S cooled to 80 C and paraformaldehyde (20.6 g; 91% ac~ive content,
0.62 mole) and 2-(dimethylamino~ethanol (46.2 g; 0.52 mole) were
added. This solution was then gently heated to reflux at 130C
and maintained a~ re~lux for S hours by which time the measured
free formaldehyde content had fallen ~o 0.6%. The product had
a solids conten~ of 63.5% and was f~lly dllutable with water.
T~e product is sufis~antially of a~erage ~rmula I, where
R denotes a group of formula rI, Rl denotes ~CH2-, R2, R31, R4,
and R7 each de~ote -H, R3 denotes ~0~, some of R5 denote ~
and the remainder deno~e a group ~SH2-S~CH2COO ~ ortho to R ,
R6 denotes a residue comprising un~ts of formulz XIV wherein r
is of average Yalue 4.0, (m+p2 is 2, n is 1, R deno~es p~tert.~
butylpheno~y~ X denotes isopropylidene para to R , and M denotes
a group of formula ~OC~2C~2NH(CH3~2.
EXAMPLE 3
A solution of Phenol I {50.0 g, 0.036 mole~ in 2-butoxyethanol
(16.7 g~ was mixed with thiomalic acid (15.0 g; 0.10 mole) and
heated to 120C. After 30 minutes at 120C, the mixture was
cooled to 80C and paraformaldehyde ~0 g; 91% active content,
0.30 mole) and 2-(dimethylamino)ethanol (18.0 g; 0.20 le) were
added. .This solution was then gently heated to reflux at 138C
- 25 -
and maintained at reflux for 6 hours hy which time the measured free
formaldehyde had fallen to 0.9%. The product had a solids content
of 67.5% and was fully dilutable with water.
The product is substantially of average formula I, where R
S denotes a group of formula II, R denotes ~~ ~ R2 R3 R4
H2COO'Mt
and R7 each denote -~, R3 denotes -OH, some of R5 denote -H and
the remainder denote a group -CH20H or -CH2-S~CH-COO M ortho to
~ I2COO M
R3, R6 denotes a residue co~prising units of formula XIV wherein
r is of a~erage value 2.3, m is 2, p is zero, n is 1, X denotes
isopropylidene para to R3, and M denotes a group of formula
Hoc~2c~2NH(cH3)2o
E~AMPLE 4
A solution of Phenol I (50.0 g, 0.036 mole) in 2-butoxyethanol
(25 g) was mixed with 3-mercaptopropionic acid ~15.9 g; 0.15 mole)
lS and heated to 80C. To this solution was added paraformaldehyde
(7.2 g; 91% active content, 0.22 mole) and 2~(dimethylamino~ethanol
(13.3 g; 0.15 mole) and the mixture was gently heated to reflux
at 125C and m~intained at reflux for 5 hours by which time the
measured free formaldehyde had fallen to 1.3%. The product had a
20- solids content of 65.1~ and was fully dilutable with water.
The produc~ is substantially o average formula I9 where
R denotes a group of formula II, R denotes CH2CH2-, R , R 1'
R~ a~d R7 each denote -H, R3 denotes ~OH9 some of R5 denote a
group -CH20H and the remainder denote a group
~ ~ -S~CH2-CH2COO M ortho to R , R denotes a residue com~rising
- 26 -
Ullits of formula XIV wherein r is of aYerage value 2,3, m is 2,
.p is æero, n is 1, X denotes isop;ropylidene para to R , and M
denote3 a group of formula HOCH2C~12NH(CH3)2.
E~AMPIE S
S Phe~l III C5~ g; 0.041 mwle2 w~ mi~ed ~ith 2~buto~yetha~ol
(20 ~) and heated t~ 110C. When the phenol had compl2tely
dis~olved the mlxture was cooled to 80C and thioglycolic acid
(9.2 g, 0.10 mole), 2~ methylamlno)ethanol (8.9 g; 0.10 mole),
and 91% para~ormaldehyde C4 g; 0.12 m~le2 were added. The mixture
0 WA~ gently heated to reflux at 133C and maintained a~ this
temperature for Z hours by w~ich time the measured free formaldehyde
conte~t had fallen to 0.9%. The product had a solids content o~
68.62 and wa~ ully dilutahle ~ith ~ater.
The produc~ is substantially of average formula T, w~ere R
denotes a group of iormula II, R denotes ~CH2-, R , R 1~ and R4
denote -H, R deno~es -OH, some of R denote -H and the remainder
denote a group -CH2SC~2C00 ~ or -CH20H ortho to R , R represents
a covalent bond with R6 which, toge~her with the indicated
hydroxyethylene group, represents a group of formula
zO ~C~2Ct,x C~ 20Co~
~ 27 -
(in which every terminal bond of the indicated groups -CH20CO~
is posi~ioned 3~ or 4- to the indicated hydro~yl groups~, m is
2, p is ~ero, n is 1~ ~ denotes isopropylidene para to R3, and
M denotes a group of formula HOC~2CH2N~I(CH3)2.
EXAMPLE 6
Phenol IV (50 g; 0.033 mole~ was m.ixed with 2~butoxyethanol
(25 g) and heated to 120C. When the phenol had completely
dissolved, the. mîxture was cooled to 80 C and thioglycolic acid
(9.2 g; 0.10 ~ole), 91% paraformaldehyde (5.0 g~ 0.15 mole~,
and 2-(dimethylamino)e~hanol (9.0 g; 0.10 mole~ were added.
The solution was then gently heated to reflux at 140C and
maintaiued at reflux for 4 hours, by which time the measured
free formaldehyde conterlt had fallen to 0.44%~ The product had
a solids content of 64.9% and was fully diluta~le with water.
The product is subs~antially of aYerage formula I, where R
denotes a group of formula II, R denotes -CH2~, R , R 1' R4,
and R denote -H~ R3 denotes -OH, s~me of R denote -H and
the remainder denote a group -CH20H or -CH2-S-CH2COO M ortho
to R3, m is 2, n and p are ~ero, R denotes a residue containing
2,2-bis(4-oxyphenyl)propane groups, -CH~CH(OH~CH2- groups, and
p-phenylenedioxy groups, and M~denotes a group of formula
OCH2 2 (CE13)2.
EXAMPLE 7
Phenol V (50 g; 0.036 mole~ was mixed with 2-butoxyethanol (20 g~
and heated to 140C. When the phenol had completely dissolved the
mixture was cooled to 90 C and thioglycolic acid (9.2 g; 0 10
- 28 ~
~ole), 91~ paraformaldehyde (4.0 g; O.:L2 mole),and 2-(dimethyl-
amino)ethanol (8.9 g; 0 10 mole) were added. The solution was
the~ hea~ed ~o reflux at 140 C and maintained at reflux for 4
hours by which time the free formaldehyde content had fallen to
0.40%. The product had a solids content of 68.6% and was flllly
dilutable with water.
T~e product is su~stantially of average formula I, where R
denotes a group of for~ula II, Rl denotes ~H2~, R2, R31, R4, and
R7 each denote ~H, R3 denot~s ~OH~ some of R5 denote ~ and the
remainder denote a group ~CH20H or ~CH2-S~CH2COO M ortho to R3,
R denotes a residue containing 2~2~-~isC4~oxyphenyl~propane
groups9 ~CH2CM~OH~CH2~ g~oup~ and 2,2-bis(4~oxyp~enyl~ sulphone
groups, m is 2, p is zero, n is 1, X denotes ~S02~ para to R39
and M denotes a group uf formula H0CH2CH2NHCCH~2.
EXAMPLE 8
Sodium sulphite (7.3 g; 0.58 mole) was dissolved in water
(20 ml3 and 38~1% formaldehyde solution ~10.5 g; 0.120 mole of
CH20) was added. The mixture was stirred at room temperature
for one hour and then added to a solution of Phenol I (25 g;
0.018 mole) in 2-butoxyethanol (36.3 g) held at 100C. Dioctyl
succinate s~llphonic acid sodium salt (3 g) was added to the
mixture, which was heated to reflux (103C) and held at reflux
for 2 hours. The product had a solids content of 34% and was
ully dilutable with water.
~ 2~ -
The product is substantially of.average formula I, where R denotes
a group of formula III, R , R 1~ R , and R denote ~H9 R denotes
-OH, some of R denote -H and the remainder denote ~CH20H ortho to
to R , R denotes a residue compris~.ng units of formula XIV wherein
r has an average value of 2.3, p is zero, m is 2, n is 1, X denotes
isopropylidene para to R , and M denotes Na .
EX~MPLE 9.
-- ~7_.
The solution C50 g) of Phenol ~I was mi~ed wit~ thloglycolic
acid (4.2 g; 0.046 mol) and 2-(d;methylamino~ethanol (4.1 g; 0.046
mol? and heated to 100C, Uhen the ~i~ture reached 100C,
paraformaldehyde C3.0 g; 91% active content, 0,09 ~ol) was
added and heating was continued to a temperature of 140 C~ The
mixture was ~aintained a~ 140C for 3 hours, ~y which ti~e the
measured free formaldeh~de cont.ent had fallen to 0.5%. T~le
product had a solids content of 64.3% and was fully dilutable
with water.
The product is su~stantially of aYerage formula I, where
R denotes a group of formula II, R de~otes -C~2~9 R , R 1' R ,
and R7 each denote -H, R3 denotes ~OH9 some of R5 denote -H
and the remainder denote a group of formula -C~2-S~CH2COO M
ortho to R3, R6 denotes a residue compris~ng u~its of formula XIV
wherein r is of average value of 3-9, (~+P2 is 2, n is l, R
denotes CH3COO-, X denotes isopropylidene para to R3, and M
denotes a group of formula HOCH2CH2NH(CH3~2.
6~
- 30 ~
~ 0
A solution of Phenol I (64,4 ~; 0.046 mol) in 2~butoxyethanol
(2105 g) was mixed with thiogl~colic acid (5.5 g; 0.06 mol~ a~d
heated to 100C. After 30 minutes at 100C the mixture was
cooled to 80C and paraformaldeh~de t4 g; 91~ acti~e content,
0.12 mol) and 2-(dimethylamino~eth,anol (5.3 ~; 0.64 mol~ were added
This solution was then gently heated to reflux at 140C and
~aintained at reflux for 4 hours ~y which time the measured free
formaldehyde content had fallen to 0.20%~ The product had a solids
content of 74.0% and was ully dilutable with water.
The prod~ct is substantially of aYerage formula I, where R
denotes a group of formula II, R denotes ~CH2~J R , R 1~ R ~ and
R7 each denote -H~ R3 denotes ~OH, some of R5 denote -~120H and
~he remainder denote a group of formula ~CH2-S~CH2COO M ortho to
~ 15 R , R denotes a residue comprising units of Xormula ~IV wherein
; r has an average value of 2,3, m is 2, p is zero, n is 1, X deno~es
isopropylidene para to R , and M denotes a group of formula
HOCH2C~2NHtC~3)2
EXAMPLES 11~13
In thPse Exa~ples car~oxylate salts of this in~ention are
cured by heating with an aminoplast.
Coating formulations were prepared by mi~ing the produc~s
of, respectively, Examples 1, 2, and 4 with Aminoplast I in th~
ratio 80:20 calculated on tne solids contents. The resulting
~5 solutions were dilu~ed with water and applied to tin-coated steel
~3~
- 31 --
plates by spin-coating, leaving a coating 2 ~m thick. The plates
were then he~ted at 215 C for 3 minutes and tested. The results
are shown in Table 1.
~YAMPLE 14
In ~his E~ample a carboxylate salt of this invention is cured
by heating with a phenolic resin.
A coating ~ormulation was prepared by mixing the product
of Example 2 with Phenoplast I in the ratio 72:2~ calculated
on the solids contents. The resulting solution was diluted with
water and applied to tin-coat&d steel plates by spin-coating,
lea~ing a coating 2-4 ~m thick. I~e plates were then heated
at 200 C for 10 minutes and tested. The results are also shown in
! . Table l.
~ 32 -
TABLE 1
Test Exam~le E~a~le E~am~le E~3mple
ll 12 13 14
~___ _
~ r~ ~ Pass Pass Pass
pass at 55~ 80~ 5S~ 88Z
__ ___ ___
Pas~aurlsatlon
in water Pa~s Pass Pass
75~C/45 min.3
___~ __
~ater boil
; l~O~C/l hour3~ail Pass Soite~ed
. .~ ._
3:~ ace~ic aci~
100C/6 hour~3 ~ ~ ~ Pass
_~ _ ~
A dash (w) indicates that the test was ~ot carried out
lThe E~IK rub tes~ comprised givirlg the coated surface 50 double
rnbs ~ith C~ttOIl wool soaked i~ ethyl me~hyl ketone a~d
- e~ami~ing the surface for removal or softening. 'Pass~ indicates
that no P~fect wax obsen~ed
l~e wedge ~e~d test comprised impact~ending the specimens o~er
a mandrel 10 cm long~ having an outside di~eter of 6 mm at one
end a~d tapering to a point at the other. The specimens were then
examined to determine the percentage of the le~gth of the sample
fr~m which ~he coati~g did not flake of~.
3The pasteurisation a~d ~oili~g tests eom~rised heating the
~ ~3 -~
samples in water or aceeic acid for the give~ time a~d t~mperature
and examini~g the coated surface for an~ defects. IPass' lndicated
that ~o d~fects were observed
.
EXAMPI~E ~lS
In this Example a car~oxylate salt of this invention is
cured by heating alone, i.e., in the a6sence of an aminoplast
or phenoplast.
The product of Example 10 was diluted with water as required
to give a viscosity at 25C of 20~30 ~Pa s and applied to tin
coated steel plates by spin coating leaving a coating 2 to 4 ~m
thick. The coating was cured by heating at 215C for 10 minutes.
The coating passed the EMK rub test and pasteurisation in water
test described above.
EXAMPLE 16
In this Example a carbo~ylate salt of this invention is
cured by heating with a blocked isocyanate.
A formulation for coatings c~prising the product of Example
I (10 g~, Blocked Isocyanate I C1.8 g2, and water as required
to giYe a vîscosity at 25~C o 20~30 mPa s was applied to
tin-coated steel plates by spin-coa~ing, leaving a coating
2 to 4 ~m thick. The plates were heated at 180C for 20 ~inutes,
The coating passed the EMK rub test and pasteurisation in water
test as described above~ ,
