Note: Descriptions are shown in the official language in which they were submitted.
23~9
The present invention relates to a new type of pa-int
product, namely, a solid paint having dimensional stability based on
ion bonding.
Various resin compositions consisting of homo-
polymers and co-polymers having partially neutralized carboxylic acid
groups are known. These contain between 3% and 20% of carboxylic acid
residues of which less than 50% of the carboxylic acid groups are
neutralized with monovalent, divalent or trivalent cations. The prior
art resins, known as ionomers, are desirable in ;ndustry because
they combine the utility of a thermoset polymer with the mobility and
` workability of the thermoplastic resin. Ionomers have lower densities
than vinyl or cellulosic plas~ics and because of their similarity to
- polyethylene find use as protectiv~ films in the food packaging industry.
Ethylene-methacryljc acid co-polymers are discussed in U.S. Patents
3,266,272 of William Fredericks issued on August 16, 1966, 3,338,739 of
Richard W. Rees issued on August 29, 1g67, and in Belgium Patents
674,595 of Dunlop Rubber Co. issued December 31, 1965 and 600,397 of
Barnes Engineering Co. issued February 20, 1961. Ethylene-sodium acrylate
copolymers are described in Netherlands Patent 6,511,920 of Stamicarbon N.V.
issued March 5, 1967. Many of the desirable properties of these polymers
such as stress-crack resistance, transparency, grease and abrasion resistance,
.
~ low permeability, high elongation, high tensile strength, and low modulus
~., 1
' are attributed in part to a type of ionic bonding.
It has now been discovered that solid paints having
effective gel properties necessary to provide dimensional stability
can be prepared by cross-linking certain react;ve polymers with "ion -
clusters" having polar molecule components. This type of ion bonding
~ ~ : 1 3~
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dlf:Eers substantially from the solvent-free ionic bonding
of the prior ~rt compounds.
The present invention provides a solid paint
composition having a gel strength ranging from 100 to 200
millimeter penetration and a dimensional stability based
on ion bonding comprising the admixture of (a) a solution
of a curable polymer having a molecular weight ranging
from 1,000 to 7,000 and sufficient reactive functional
groups selected from the group consisting of carboxylic,
sulfonic and phosphonic to provide an acid number from
20 to 80~ said resin dissolved in a non~polar solvent to
provide a 25 to 90 weight percent solution; ~b) an
ionic cross-linking agent selected from the group con-
sisting of metal hydroxide, metal oxide, metal alkoxide,
.. 15 ammonium hydroxide, or an organic cation former dissolved
!~1 or suspended in a polar solvent of high dielectric strength
to provide a 10-50 weight percent solution, said metal
hydroxide, preferably selected from the group consisting
of sodium, potassium, lithium, barium, calcium, manganese
and magnesium; ~c) a metallic drier in amounts from
:. about 0 to 5 weight percent based on the total weight
~;. of pol~mer7 and (d) an opacifying pigment or colorant,
wherein said composition contains from about lO0 to 600
mole percent of ionic cross;linking agent per mole of
aci.d functional group.
The invention further provides a process for
- preparing a solid paint having dimensional stability based
on ion bonding and a gel strength from about 100 to
. 200 millimeter penetration which comprises ~a) dissolving
the curable polymer resin to form the solution thereof
in such proportion to provide sufficient reactive acid
: functional groups necessary for the indicated dimensional
stability when cross-linked by ionic cross-linking agents;
(b) mixing pigmentS, fillers, or colorants and 0 to 5 ~r~
weight percent of a metallic drier into the resin solution
. or dispersion; ~c) adding thereto under ~igorous stirring
a 20 to 30 weight percent solution or suspension of an
~ I
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--3--
ionlc cross-linking agent as deirled above in a polar
solvent of high dielectr~c strength to provide a 10~15
weight percent solutlon or suspension containing 100
to 600 mole percent of the amount o~ ionic cross~linking '!.
agent required 'o r.eutralize said reactive acid groups
of the resinO The process may be ~ollowed by aging
the mixture for 3 to 25 hours at a temperature between
15 and 70 degrees CentigradeO
' The invention further provides paint sticks
encased in a removable skin or bars based on the above
compositions and processes.
Solid paint compositions having dimensional
sta~ility and desirable paint characteristics result
from the interaction of certain polymers, having reactive
functional groups, with certain cross-linking agents
formed by dissolving an ionic cross-linking agent in
a high dielectric polar solventO Cross-linking of the
polymer chains takes place through "ion clusters" com-
posed of multiple ions associated with polar solvent ,
molecules~ By the term solid paint is meant a paint
which has sufficient d~mensional stability under
storage conditions, iOeOI is self-supportingl yet could
be utilized as a stick of paint (analogous to a segment
of hard butter or cheese3. Such solid paint can
advantageously be applied hy hand to the surfaces ,
usually protected by paint and coating products,,without
the use of a brush or roller~ For practical and pro
tective purposesl such stick of paint will generally
be contained in a skin or covering suitable for storageO
Advantageously such protective cover will have a
closeable opening, said covering being distinct from
the nature of an applicator in the usual sense~ The
solid paint can be used by placing the paint stick in
contact with the surface to be painted followed by
the usual vertical and lateral movements across the
substrate whereby a non-sagging, air-curable paint
film is deposited thereon~ The shear provided by
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drawing the paint s-tick over the surface -to be painted
is sufficient to cause the solid paint to deform to a
flowable coating at the point of contact~ Such a solid
paint coating is one that possesses the desirable prop-
erties of adhesion, flow and uniform coverage, o~ thesurfaceO It is assumed that the solid paint of the
present invention will contain the usual pigments,
fillers, driers, bonding agents, and other additives
to pro.~ide films having deslrable properties of gloss,
color~ and hiding powerO It is anticipated that such
a ~olld paint could be fabricated in blocks or sticks
having widths ranging from 1/8~ to about 8 feet or
larger~ thus, also allowing use in industrial applications
such as, for example, coil coating o metalO
1 15 The resins useful in the present invention
; include homopolymers and co-polymers and mixtures thereof.
having appropr~ate functional groups either builk into
the polymer chain or grafted thereto by the usual
graft techniquesO Useul resins include but are not
limited to polyethers, polyesters/ unsaturated polyesters,
: polyurethanes, polyolefins, polyacrylates, polyhydro-
carbons derived from aliphatic and aromatic hydrocarbons
having ~,B unsaturation, vinyl resins and chlorine-
substituted vinyls as well as other combinations known
-~ 25 to the artO The particular reactants and quantities
are chosen to produce resins having pendant and/or
:: terminal functional substituents which are capable of
further reaction with ionic reagents to form gels of
propèr dimensional stability and gel strengthO Desirable
application properties result when the gel strength
is from about lO0 to 190 and preferably from 135 to
180 when measured 25 hours after gelling~ Gel strength
is recorded in millimeter units using a Universal
: , Penetrometer* - the l~wer the penetrometer xeading,
the higher the gel strengthO
Regardless of the type of resin used in the :: -
practice of this invention~ it is essential that the
~ * Trademark ~:.
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particular resin be s~luble in a non-polar solvent and
that the resin have pendant and/or terminal functional
reactive groups which are readily ionizable. Such ion-
izable groups include both cationic and anionic reactive
unctions. Preferably, anionic functional groups used
~ to modify the resin ale the sulfonic, phosphonic and
- carboxylic tnypes. The carbox~lic acid functionality is
espe~ially preferred since a variety of polymers having
such reactive ionizable groups can be readily purchased
or synthesized. Preferred reaction produats are those
ohtained from the co~ination o aarboxylic aaid sub-
stituted polyesters an~ alkyd polyesters having molec-
ular weights in the range of from about 1000 to 7000
which contain from about 1 to 4 reactive functional
groups per each 2000 unit of molecular weight. Poly-
- esters and polyethers having molecular weights in the
range of 400-2000 and which yield solid paints o~ de-
sirable gel properties are e~pecially preferred. Alkyd
;; xesins modi~ied with fatty acid groups and having
terminal aarboxylic functionality are exemplified in
the best mode Examples. In the case of polyolefins,
polyacrylates and other systems where no air-curing
will occltr, a higher molecular weight of the order of
~ 100,000 is usually necessary. However, 1 to 4 reactive
;; 25 functional groups are still required per 2000 unit of
- molecular weight. The alkyd resins useful in the
practice of this invention are prepared by polymeriz-
ing the polymer monomers and other intermediates in a
fusion cook at a temperature of a~out 400-6a0F. to
yield resins having an acid value ~A.V.~ ranging from
~; 30 to 55 and preferably 41 ~ 2. Certain 'longer' oil
~ resins as exemplified hexeafter in Examples 1 and 2 are
;~ polymerized at 450F. to an A.V. of 43.0~
.;
The above described polymers having ioniz-
able reactive ~roups are dissolved in sufficient non-
polar solvents to provide solutions having non-volatile
- (N.V.) contents of from about 10 to 90 and prefexably
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23~3
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from 35 to 60 weight percent. Especially preferred
are solutions of 50~ N.V. Suitable non-polar solvenks
for dissolving the polymer include both aromatic and
aliphatic--type hydrocarbons and are selected based on
the particular resin us~d, the functionality on said
resin, and the nature of the ionic reactant. In
gsneral, suitable solvents are hydrocaxbons having a
- bo.iling point of about 125 to 400~F. and which con-
tain up to twelve carbon atoms. These include hex-
ane, heptane, ootane, nonane, decane and mixtures
thereof. Preferred hydrooarbons are the various
octanes because of their suitable evaporation rates.
Mineral spirits is an especially preferred solvent
beoause of its availability and the desirable prop-
erties of the resultant solid paint. In certain case~
:~ aromatia hydrocarbons such as toluene and xylene can
advantageously be used and are especially valuable
in dissolving the higher molecular polymers~
It is understood that the solvent, resin
and proportions o~ each will vary and depend on thetype of resins, the types of solvent, the fillers and
other additives needed for a particular end-product
solid paint. The additives, driers and other usual
dispersant aids can be blended with the resin solu--
tion using a Cowles* agitator. The order of additionis usually not critical~ If desired, the pigments
and other additives may be blended with the resin
material prior to the solution of the resin in the non-
polar solvent~ After the additives are thoroughly mix-
ed, the resulting composition is advantageously allowedto age for 12 to 20 hours before reacting with the
; ioni~ component.
The solution of polymer in a non-polar solv-
ent is next combined ~ith the ionic cross-linking
agents dissolved in a high dielectric polar solvent.
Suitable ionic cross-linking reactants are
usually of the inorganic salt variety which produce
: .
*Trademark
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on soluti.on speci~ic ca~ionsor anions capable of combining
with th~ termillal reac~ive qroups of the resin to form
ion clusters responsib].e for gel ~ormation. Such clusters,
whicll contain the high dielectri.c polar solvent molecules,
act as reversible cross-links to join the reactive resin
molecules in webs thus impartin~ cfel strength and dimen- :
sion~l stability to the resultant solid paintO When
the reactive terminal sites on the polymer are carboxylic
acid groups ~-COOH)~ the preferred cross-linking reactants
are alcoholic solutions of mono, di and trivalent metal
hydroxidesO Such cross-linking reactants include the
: oxides and hydroYides ~f sodium, pota~sium, lithium,
:~ barium, calcium, manganese and magnesium Equally effective
cross linking agents are the corresponding metal alkoxides
: 15 i~e sodium methylateO In some cases ammon um hydroxide
: and organic cation formers such as tetramethyl-ammonium
hydroxide can be used as cross-linking reactantsO The
cross~linking gelation derived by reacting sodium hydroxide
with the above described resin molecules having terminal
or pendant carboxyl groups is espec.ially preferred
.: 20 Suitable gels result when an effective amount of the
:: cationic base combines with the free carboxylic acid
functionalityO In every case an amount of ~ase substan-
tially in excess of the amount required for neutralization
. is necessary to be effectiveO. By substantial excess is
~`: 25 meant f~om about 100-600 mole percent of ionic reac-tant
. dissolved in the polar solvent. Although the amount
of excess varies with each particular resin system
-.~ and depends upon the molecular weight of the resin, the
number and type of the ionizable functional group and
on the valence of the metal hydroxide, satisfactory
gels result when the ionic reagent is used at 100-6~0
. mole percent excessO When amounts less than 100 mo].e
:.: percent are used the resins do not exhibit the required
dimensional stabilityO When amoun~s greater than 600
mole percent are used the resins do not exhibit the
desired flow and surface characteristicsO For gèl
formation the metal hydroxide or other ionic cross-
' ,
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--8--linking reactant is added as a 10-50 weight percent solu-
t:ion in the high dielectric polar solvent to the polymer
resin formulations. Preferred solid paints were obtained
by using lOO to 250 mole percent sodium hydroxide based
on the molar content of the reactive functional group
i.e. moles free COOHo
The polar solvents useful in dissolving the
ionic cro~s-linking agents are generally those solvents
having a dielectric constant greater than lO, include
aliphatic alcohols containing one to ten carbon atoms and
one to two hydroxy groupsO Although Cl 8 aliphatic
.- alcohols are usually preferred, glycols containing the
similar carbon chains are sometimes useful in producing
~: desirable gel properties in the resultant solid paintO
-~ 15 Useful alcohols include methanol, ethanol, isopropanol,
n-propanol, the normal and isomeric butanols, pentanols,
hexanols, heptanols, octanols~ as well as the corres-
: ponding glycols derived therefromO Methanol is the pre-
ferred alcohol because of its costs, availability and the
: 20 favorable solubility of the ionic reagents thereinO In
: certain applications it is preferred to use glycols or
mixtures of glycols and alcohols as the plasticizer carrier
for the ionic reactantc Preferred glycols are ethylene ~-
glycol and propylene glycol although for certain resins
: 25 the higher glycols such as pentanediol and hexanediol :
~ act in the nature of a plasticizer and provide desirable
.;~ lubricity~ Additional high dielectric polar solvents
useful in the practice of this invention include, water,
formamide, dimethylformamide, and dimethylsulfoxideO
The metal driers suitable for the instant
. solid paint compositions are those known to the art and
include the metal salts and/or esters of various organic
carboxylic acids containing up to 30 carbon atoms and
mixtures thereof O The metal sal~s of cobalt, zinc,
zirconium, magnesium, aluminum and manganese prepared
from branched chain C8 12 carboxylic acids are preferred
driersO The typical paint formulations, as described
herein, re~uired usually high amounts o~
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23~9
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metal drie~ of the order oE about o. 5 to 5 percent based
on the weight of the resin. The amount of drier needed
depends to some extent on the oil or othar source o~
double bonds us~d in the paint system i~e. number and
type of double bol~ds available.
A further aspect of this invention includes
the use of resins having pendant and/or terminal func-
tional reactive groups other than the acid or carboxylate
groups. When the ionizable group on the polymer is a
- 10 cationic group precursor instead of an acid or carboxylate
group, the ionic ~ross-linking reactant will be an
anion precursor. Examples of cation formers are (1)
primary, secondary/ tertiary and cyclic amines, which
react with hydrogen halides and h~drocarbon halides to
give quarternary halides to give quarternary salts; (2)
~ substituted phosphines which combine with halides to give
- phosphonium salts; (3) sulfides which react with alkyl
halides give sulfonium salts; ~4~ cyclic ethers which
react with acids give oxonium salts. Examples of
~- 20 anion sburce cross-linking agents include acetic acid,
~ nitric acid, hydrochloric acid, sulfuric acid, and
-~ relatively short chain organic multibasic acids such
~ as oxalic, malic, succinic, maleic, adipic acids are
; corresponding anhydrides.
For industrial coating purposes, the block
of solid paint is advantageously contained in con~
- ventional holding and applicator devicesO Such devices,
;~ which will vary with the nature of the substrate to be
:;,
coated and will be adaptable to contin~ous applicatlon,
usually include a device for holding the solid paint
and a mechanism for adjusting the pressure placed on
the paint block to allow proper deformation to provide
a fluid coating and ilm of re~uired thickness. In-
creasing the pressure applied to the Colid paint
will result in the deposit of a heavier coating.
Although the instant solid paints are capable of air
drying, it is contemplated that for industrial coating
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applicatic,ns curlng of -the ~ilm may be accelerated by
the used of heat~ and other energy techniques known to
the art.
The following specific examples illu~trate
only a limited number of embodiments; accordingly, the
invention is not limited thereto. All parts and per-
centages being by weight unless otherwise indicatedO The
driers used were commercially available conventional
driers. The "mineral spirits" and the "odorless minéral
spirits" had a boiling range of 300 400F. and 345-410F. respec-
tively. Molecular weights reported are n~r average molecular weights
unless otherwise specifiedO E~LE 1
Resin A was prep~Gq~r~r polymerizing a mixture
lS (in amounts shown below) of trimethylolethane (TME), de-
hydrated castor fatty acid ~DCOFA), Azelaic dimer acid
(AZELAIC 1110*) and dimer acid (EMPOL 1014*) at 460F.
as a fusion cook to an acid value of 41 ~41 ~ 2 normal
range)~
Resin B, a "longer" oil resin, was prepared
ln a fashion similar to Resin A ~y polymerizing at 450F~
to an acid value of 42.0~
Resin C~ prepared using Pentaerythritol (PE) ~,
in place of trimethyloleth~ne ~TME)~ was polymerized
at 460~F. to an acid value of 4200.
Resin D, prepared using a combination of DCOFA
and Tung Oil instead of simply DCOFA, was polymerized
at 460F~ to an acid value of 43O0
TABLE I
, 30 Acid
Material Mols Wt. Value,
Resin A TME 2,46 295 41
DCOFA 2O46 690
AZELAIC 1110 1.78 340
;~, 35 EMPOL 1014 0~74 423
Resin B TME 2,0 240 43
DCOFA 2O4 672
AZELAIC 1110 1,42 270
~, ~ EMPOL 1014 0.59 337
Resin C PE lo0 136 42
DCOFA 2.0 560
-~ AZELATC 1110 0.72 135
EMPOL 1014 0O29 168
*Trademark
~I~JB23~g
~ Acid
Material Mols Wt~ Value
; _ _ __
Resin D TME 1,0 120 43
DCOFA 006 168
TUNG OIL Ool9 16805
AZELAIC 1110 0,48 91.6
EMPOL 10140,97 555
EXAMPLE i
The polyester Resin A (25 parts) was formulated
into a hydrocarbon solution by mixing with 12 parts tung
10 oil, 13 parts mineral spirits, 200 parts of a cobalt
drier (1200 percent metal), 200 parts manganese drier
(9.O percent metal) and 3.5 parts zirconium drier (12.0
:~" percent metal) and the resultant composition was allowed
to mature at room temperature for 16 hoursO Titanium di-
oxide ~40 parts) and calcium carbanate (10 parts) were
blendea with the resin solution under Cowles agitation
to yield a ~6 ~egman grindO Various weights of sodium
hydroxide were then added as a 25 weight percent
~; solution in methyl alcohol to form the solid paints
identified in Table II. Solid Paint 2A exhibited a
: streaky film appear.ance, the paint was slightly too hard
` requiring tco much effort to apply i~e. exhibited too
:~- much drag on application, and application characteristics
:'-' which were too hardO The solid paints 2B and 2C with
25 gel strength of 147 and 161 respectively exhibited
satisfactory application characteristics and film
appearance i~eO the paint didn't require too much force
~`' to apply and the resultant film was uniform~ All three
solid paints exhIbited dimensional stability and gave a satisfactory
dry coating on application to a te,st panel surface,
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rrABLE II
Parts Percent Neutralization Gel
NaOH Calculated on Moles Strength*
Exp. No. Resin Added Carbo~ Acid _ (24 hours)
2A A 6.65 225 119
2B A 6~35 215 147
2C A 6.05 205 161
3A C 7 2 240 160
3B C 7O2 240 155
3C C 6O0 200 178
4A C 4~75 160 176
4B C 5 O0 170 138
8A C 6O1 200 165
8B C 6 5 220 155 :~
:: 15 Average of three ~etermlnatlons
EXAMPLE 3 `:
Resin C was formulated into paints 3A and 3B using :~
the procedure outlined in Example 2 and the same relative
amounts of resin, tung oil, mineral spirits, cobalt drier,
manganese drierl zirconium drier, titanium dioxide, and
calcium carbonate A third paint formulatlon 3C was s`imil-
. arly prepared from Resin C but contained 1 3 parts of
cobalt drier ~12% metall~ ~D5 parts manganese drier ~9O0%
metal], 3O~ parts zirconium drier C12% metal~ and 0 19
: 25 parts aluminum stearateO The solid paints fcrmed on the
addition of 25~ methanolic sodium hydroxide identified :~:
: as 3A, 3B and 3C each exhibited satisactory gel strengths t
application characteristics, film appearance and drying
: quality~
; 30 EX~4PLE 4
Polyester Resin C ~25 parts) was ~ormulated into
: a hydrocarbon solution by mixing with 12 parts tung oil,
13 parts mineral spirits, 0~95 parts cobalt drier and 2 1
parts zinc drier ~16 percent metallO A second resin
formulation for Resin C was identical to the above except
it contained only 0.9 parts of cobalt drier and additionally.
contained 0O45 parts of manganese drier, These resins
and paints made there~rom whlch contained 5Q parts :~
~~
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: :
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tltdnium d~.oxide and no calclum car~onate are identifled
respectlvely as 4A and 4B in Table I~, It is ~een that
paints 4A and 4B with neutrali~ation values o~ 160 and
170 exhibit gel strengths of 176 and 138 respectivelyO
The application characteristics of 4A were slightly
inferior~ the solid paint tended to be too softO The
~ilm appearance and drying quality of ~oth pa.~nts were
acceptable.
EX~MPLE S
Repeating the experiments 2A, 2B, 3A, 3B and
3C ~ut adding the driers subsequent to the addition of
: pigment to the resin will result in essentially similar
acceptable gel strengths, application characteristics
and drying rates,
EXAUPLE 6
: Paint blocks ~ approximate size 4" x 6" were
stored using a thin SARAN CTrademark of the DQW Chemical
; Companyl envelope for a period o~ six monthsO Applica-
tion of these paints to a test panel after the storage
period showed no detectable deterioration of the appli-
catlon and film characteristicsO Addltionally~ solid
paints prepared from the same resins but having acid
values in the range of from 30 to 60 gave acceptable
solid paint characteristics. E~ually good results
were obtained when oiticica fatty acid~ safflower fatty
: acid, soya fa,tty acid, or linseed fatty acid was used
instead of dehydrated castor oil fatty acid, The
:~ best application properties were obtained w.hen the
gel strength as measured by the Universal penetrometer
was between 130 and 180 mm~ Gel stren~ths o~ ~rom lO0
to 130 and 180-190 gave effective solid palnts with
somewhat less desirable characteristlcsO
. EXAMPLE 7
Resin D was prepared ~y first esterl~ying
.~ 35 the dehydrated castor fatty acld ~168 parts~ with
trimethylo.lethane ~12Q paxts~ at a temperature xa~ging
up to 480Fo to yield a product ~f acid value 4O~o
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Thereafter an ester exchange was ef~ected by furthex re
action with tung oil (168~51 in the presence o~ 200
parts of litharge catalyst until the pr~duct wa~ com-
pletely miscible in methanol~ The resulting product
was combined with Azelaic 1110 (9106 partsl and Empol
1014 ~555 parts~ and cooked to an acid value of 43000
The resulting resin had an approximate molecular weight
of 1300,
A cationlc Resin E was prepared ~y condensing
Resin D ~1040~4 partsl with N,N-diethylaminoethanol in
the presence of litharge ~0 paxts~ catalyst using
reaction conditions such that the predomlnant reaction
: was esteri~ication rather than amide formationO After
removal of water and excess N,N-diethylaminoethanol,
Resin ~ had a molecular weight of 15000
Gelation of Resin E was ef~ected ~y neutralizing
U00 and 300%) a 50/50 weight percent solution of Resin
E in mlneral spirits with 37% hydrochloric acidO The
~ resultant solid paints had propertles lnferior to those
;, 20 of a corresponding gel neutralized to 200 percent with
32 N~sulfuric acid and ~esulting in gel strengths of
from 1~0 1500 '
: ExaupLE 8
'; Polyester resin C ~25 parts~ was formulated
- 25 into a hydrocarbon solution by m~xing with 12 parts
,~: tung oil~ 13 parts mineral spirits, 006 parts cobalt
drier ~2 0 ~ percent metal~, 0 o 6 parts manganese drier
: ~900 percent metal~ and 600 parts zirconium drler
12~0 percent metal~, and the xecultant composition
:.' 30 was allowed to mature at room temperature ~or 16 hoursO
: Titanium dioxide (40 parts) and calcium car~onate
~10 parts~ were blended with the resin solution under
Cowles agitation to yield a #6 ~egman grindO Various
weights of sodium hydroxide were then added as a 25
weight percent solution in methanol under reduced
. pressure in a ~vacuum Cowles~ to form a solid paint
CTable II~o This manner of addition diminishes the
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~0~3~39
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chance of entrappiny air into the Ifinal' solid paint.
Paints ~A arld 8B ~o~ Table II) exhi~ited superior film
appearance and application properties. soth paints
were dimensionally stable and exhi~ited good dry on
application to a test panel surface,
EX~MPLE 9
Resin F was prepared under ~ree radical
conditions as follows: 10 parts methacrylic acid, 90
parts lauryl methacrylate, 1 pa.rt Bis ~4-t-butylcyclo-
hexyl~ peroxycarbonate Cinltiator~, and 300 parts
mineral spirits ~ere added t~ the kettle~ Polylnerization was accomplished ~y heating to 60C, and holding
at this temperature for 2 hours while the mass in the
kettle was being agitatedO Conversion Gf 99% was
:. 15 achieved; acid value of the polymer was 65~0O Approximately
100 parts of the mineral spirits ~ere removed by
vacuum distillationO
Various weights of sodium hydroxide were addedas a 25 weight percent solution ln methanol to 75 part~
of the 33 percent N/V resin with agitation as shown:
Percent Neutralization
Ex~ NoO Parts NaO~ Added Calculated ~n CarbQxvIic Acid
: A 609 150
B 9~2 200
The two ~clear~ paints can ~e described as follows:
Experiment A resulted in a product that was just barely
dimensionally stable and exhi~ited poor application
characteristics, iOeO on applying the paint laid down
too thick a film and too much force (relative to the
. 30 previous examples~ was required to draw the sample across
the test panel,
Experiment B resulted in:a stronger pr~duct that
: exhibited good dimensionalstabi-lity (gel strength of ap~o~Lmately
160 mm penetration~ and good application characteristics.
Paint B exhibited very little drag on application~ Both
these 'products ~esulted in a ~dryl film on the test panelO
. EXAMPLE 10
. Resin G; a 100 percent N~V dicar~oxypoly~utadiene
:;
~,.,
,
, ~ ~
. .
238g
-16-
havin~ a molecular wei.c3ht a~ 1410 and an acld value o~
65.0, was formulated into the following solid paint
systems:
No~ A B C D
5 Resin G ~parts~ 50 50 50 17
Resin A - - - 33
Mineral spirits 50 50 50 50
Cobalt drier ,5 O5 5 ~5
(12 percent metal~
10 Zirconium drier 1O7 1O71.7 1.7
~12 percent metal:)
Titanium dioxide - 130110 90
Calcium carbonate - 70 50 40
NaOH (25 parts in 18O0 20O2 36 24
15 methanoll
Percent Neutralization 200 300 400 350
Gel Strength (mmOI 250 180 110 160
~ Paint A having a gel strength of 250 did not exhibit di-
- mensional stabilityO Paints B, C and D were dimensionally
stableO Under application action Paint B tended to put
: down too thick a film and was a little too elastic, i.e.
` tended to be slightly taffy likeO Paint C was too hard
and for this reason it resulted in poor quality applica-
tionO Paint D exhibited dimensional stability and
;~ 25 acceptable applicationO All the paints resulted in a
. dry film on the test panel.
EXAMPLE 11
` Alkyd Resin H was prepared by polymerizing
:~ a mixture of 146 parts trimethylolpropane, 146 parts penta-: 30 erythritol~ 908 parts dehydrated castor oil fatty acid,
and 413 parts Azelaic dimer acid (AZELAIC 1110) at 480F,
as a fusion cook to an acid value of 42 The resulting
resin exhibited a viscosity of Z2 as determined using
. the Gardner-Holt Bubble Tube Test method ASTM D 1545.
Alkyd Resin I was prepared by polymerizing
a mixture of 116O5 parts trimethylolpropane, 116O5
parts pentaerythritol, 296 parts dehydrated castor oil
fatty acid, and 821 parts Azelaic dimer acid (AZELAIC
1110) at a temperature of 460F~ to an acid value of 30.
`~ 40 The resulting resin exhibited a viscosity of Z2
(Gardner-Holt~O
`~:
. .
.~ '
: - : - , . : , , ~ ~.
- .: . . ' `- ' : :
: : . .
8;~ 389
1 7
13_ MPI,E 1 2
Solld palnts were prepared from Resins H and I
accordiny ~o the procedure of Example 2 with the exception
that driers were allowed~ to mature at room temperature
for 1/2 hour, the order of addition of ingredients being
as given in the following table with blending to a #5
1/2 Hegman grind.
Material Parts
Experiment No. 1 2 3 4
10 Resin I ~ ~ ~ 50
Resin H 50 50 37
AC 100 a~ b 30 30 54 30
Dramatone Blue tinting bas~ ) 2.5 - -
Titanium ~ioxide 100 100 100 100
15 Min-u-Sil lp* 10 lG 10 10
Celite 499d) 10 10 10 10
Rheox le) -loO ~ L~O l~O
Odorless mineral spirits 50 55 44 50
Cobalt drier ~120 percent metal~ 0.3 003 0.3 003
20 Manganese drier (900 percent metal)0~15 0015 0015 0.15
Zirconium drier ~12.0 percent metal) 3~0 300 3rO 300
Methyl ethyl Ketoxime 002 _ 0.2
sodium hydroxide - methanol 300 8.0 8.0 8.0
(24 percent sodium hydroxide)
25 % neutralization 130 130 l~O 160
gel strength ~mm~ 170 170 160 180
.
.. a) a diluent alkyd resin not capable of direct participation
. - in ionic bonding Reichold Chemicals (Canada) Ltdo
b) DRAMATONE i.s trademarked product of GLIDDEN~DURKEE,
Divison of SCL~ Corporation~
.; c) Crystalline silica product of Pennsylvania Class Sand
: ,
:. Corp~
:~ d) Diatomaceous silica product of Johns~Manville CoO
e) Bodying agent product of N~Lo Industries~
The solid paints 1, 2 and 3 exhibited dimensional
stability and characteristics equivalent or superior to
: the solid paint products of the pxevious Examples. When
: applied to a substrate by contact and hand pressure desirable
surface films were obtained whlch air cured overnight~
.~ * Tradem~rk
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_,
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