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Патент USA US2408175

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Patented-Sept. 24, 11946 i I
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* "2,408,174:
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itssm coa'rmo coluroslrrolvs - ,
Glen H. ,. Morey, Terre “Haute, 'Indg assig'nor to,
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Commercial Solvents Corporation, Terre'Haute, ‘ l
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Ind., a'corporation-of'Maryland"
No Drawing. Application March 20, 1944;
I sensmaszmsi
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(01. 260-32) ~ ,
My invention relates to‘c'oating compositions,’
, I have now discovered,thatthealkyl esters of
and more particularly to coatingcompositions
levulinic acid serve as particularly good vsolvents
containing polymerizedvinyl ‘compounds
e‘Numerous types: and grades of synthetic resins
for certain grades ofvinyl resins, alld'that solu-'
tlons oitheSeresins in the aforesaid solvents
'possess [none of the disadvantages mentioned
abovewhich'were attributable'to the use of prior
solvents. vIn this connection it should be pointed
have been produced ‘by the polymerization of
vinyl compounds. _Among these resinsLlcertainl
typesare particularly adapted for use in coating
compositions, “for example, resins resulting from
out that the vinyl resinssuitable for use in'the 5
~ the,‘ cop'olymerization' 01a vinyl halide with a
coating ‘compositions of my invention are -'those'_
vinyl ester or a'lower aliphatic acid; ‘,These‘res
ins, .ien'l'general, possess very ,"interesting and use-‘‘
having a molecular weight above‘4000and‘which
are insoluble in toluene. These resins are pro
ful ‘properties. particularly "those ‘resulting jirom
duced by thecopolymerizationjcf a vinyl‘halide,
such asjvinylchloride, with a vinyl ester, ‘.ror
the polymerization ‘ofimixtures of vinylechlorlde
vexample, vinyl acetate, and I have found that
chloride. j, Such; resins, have great physical. and 15 such.» copolymers ,cont'ainlng aboutv85% vinyl,
chloride land,15% vinyl acetate are particularly
I chemical-stability'and are'notjreadily ailfected'by;
suitable i'or preparingfthe coating compositions
concentrated ' hydrochloric, or hydro?uoric‘ acids,v '
of ‘my inventiong-The lower molecular'weight,,,
50 ‘per cent‘ sodium hydroxide solution, alcoholsj
oreven'by a mixture offpotassiumnichromate‘ toluenesoluble grades oi the aforesaid type of
and sulfuric acid. 'Because 01 this-superiorsta 20 resins are substantially insoluble in alkyl esters
bility, synthetic ‘resinsloi‘ ‘this type have been ' 0i.’ levulinic acid, yieldinggels when'incorporated
insaid esters.
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suggestedfor numerous usesfinthej'l?nishing and
- and vinyl acetate with’ahigh proportion‘ oi’ the
cosnngznems.
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Itis an object oi myfinvention to provide vinyl"
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resin coating comp0sitions._which employ ‘alkyl.
Although ‘coating compositions, ‘which employ
such resins as the principal'fllm forming .rnate
25 esters oilevulinic acid, either ,alone orin con- .7
junction with suitable diluents. ,
The alkyl, esters of levulinic acid, that I__ use >
as solvents for the.‘ vinyl resins in my improved
jvrial, are capable , of solving numerous] and‘ long
existing problems in the ?nisl'iin‘gvileld, thereex;
ist certain icommonzdei'ects‘which make the use
coating compositions, may be conveniently pre-'
of such resins for coatingpurposes infparticular
‘lines somewhat diilicult. _"For. example, contact
so pared by reacting approximately equimolecular
quantities of levulinic acid with the desired alco
hol in the presence of a catalytic amount or a
at elevated ‘temperatures with: certain metals,
such as zinc, ‘iron, or tin, causes rapid decompo-,
sition of polymerized vinyl compounds'prepared
mineral acid, such as sulfuric acid. Puri?cation
oi the resulting esters may be eii’ected by means
from vinyl chloride with ‘the liberation oihydro
chloric acid. The presence oi’ pigments contain
ing iron or'zinc has‘ thesame eil'ect. [Another 01'
35 of fractional distillation in the customary man- '
ner. Any of thealkylesters of levulinic acidof
vthe important handicaps" preventing ,extensive'
use of vinyl resins incoating compositions, has"
suitable boiling‘ points and rates of evaporation,
maybe used-as solvents for the-preferred form
been the, lack of. satisfactory solvents therefor,‘ ' of .vinyl resinsdisclosed above. :Examples of such‘
and while there‘ha'vebeen found certain mate, 40 compounds are the methyl, ethyl, ipropyl, butyl,
rials which are comparatively good'solventslfor
‘isobutyl, isoamyl,qand;capryl esters of .levulinic
the vinyl ‘resins; boththe solutions asjwell as'the
resulting v?lm "formed, when Iutilizingjsuch‘ sol
vents possess defects‘ which restrict‘ greatly‘the
.acid- Certain ofthese compounds, such as the , a
capryl ester of levulinic acid, possess asu?lcient
1y high boillngpoint, as well as...other desirable
free and general application of such coating come 45 properties, to renderthem useful, as plasticizers
positions. fvF'or example, lacquers prepared from‘
vinyl resins of the type described and materials
previously found to beisatisiac'tory solventsfor
saidjresins possesslvery‘poor color stability. 'Also
the ?lms ‘resulting from" thejapplication ‘of such
compositions, are objectionable‘ because oi’v the
~ disagreeable residualv odor. which .they possess.
Thus the use of vinyl resin coating compositions
in which such solvents =werepemployed, hasbeen
limited considerably.‘ ’
for vinyl resins ‘of. the aboVe-described‘type, particularly, where thelatter are emploxedaslbond
ing agents in the manufacture of laminated glassy.
_In order‘ to cheapenvthe compositions, and fre-_
quently- ior' other reasons? it ‘is ‘desirable not to
use materials’ consisting onlyjof 'a single solvent
or solvent mixture. ‘ Owing to the high tolerances '
of, the levulinic acid esters for they coal-tar hydro-_ _ '
carbons,isuch as, forexample, benzene, and tolu-’
used'as dilu'.
55 ene, large volumes thereof may
2,408,174
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cuts for the levulinic ester solutions of vinyl
resins. Various hydrocarbon mixtures may, of
C., was found to be 95 centipoises, as compared
course, also be used as diluents and other mate
rials ordinarily used in synthetic resin coating
compositions, may likewise be employed in my
improved vinyl resin compositions. For example,
plasticizers such as cresyl phosphate, butyl phtha~
late, butyl phosphate,- or as mentioned above, the
to 180 centipoises for a solution employing a mix
ture of 20‘ per cent ethyl levulinate, and 80 per
cent toluene. Where the viscosity is found to be
. too high for a particular given solvent mixture,
it can be very materially lowered by only a slight
decrease in the concentration of ‘the vinyl resin
incorporated
therein.
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The following examples are illustrative of the
higher alcohol esters of levulinic acid, may be
use of alkyl esters of levulinic acid in unpigmen’red
incorporated in such compositions. Other resins,
vinyl resin coating compositions.
either natural or synthetic, may likewise be used
therein. Also pigments or dyes may be added,
Example I
provided care is taken to avoid the presence of
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Vinyl
resin
copolymer
consisting of approxi
zinc and iron compounds.
mately 85% vinyl chloride and 15% vinyl
The viscosities of vinyl resin coating composi 15
tions, as in the case of most other coating com
acetate.‘ _____________ __grams per 100 00.. 16
positions, are of considerable importance regard
Butyl phthalate __' ___________ __d0 _______ __
less of the method of application utilized. Inas
much- as the character of the solvent mixture em
ployed affects not only the character of the de
posited ?lm obtainable, but also the viscosities
Ethyl levulinate ________________ __per cent__ 20
Ethyl isobutyl ketone ______________ __do_____ 20
Toluene __
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do
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’ Example II
of the liquid coating compositions, the choice of
proper solvents to use with vinyl resins is highly
Vinyl resin copolymer consisting of approxi
solutions with the, vinyl resins, which likewise
damar and mastic, may be incorporated in any
mately>85% vinyl chloride and 15% vinyl
important, and depends to a large extent‘on the
acetate ________ __» ____ __grams per 100 cc__ l6
viscosity characteristics of the solutions obtained 25
Butyle levulin'a'te____ ___________ "per cent__ 20
therewith. The majority of the solvents previ
l-nitropropane ___-____; __________ __do_____ 10
ously suggested for use‘with vinyl resins are un
Toluene _________ _'_ ___________ __y___do___>__ "10
suitable for the preparation of satisfactory coat
ing compositions, because solutions of the resin
If desired, other solvents such as ethyl acetate,
made with such solvents. not only possess high 30 butyl acetate, nitroethane, 2-nitropropane, etc.,
initial viscosities, but in addition, tend to increase
or other diluents or diluent mixtures, such as
in viscosity on aging andultimately set to a solid
xylene, petroleum naphtha, and hydrogenated
gel. While the alkyl esters of levulinic acid form
petroleum» diluents, and. other resins, such as
possess such characteristics to a certain extent, 35 of the above formulas. In adding such materials,
they exhibit these undesirable properties to a
however, care should ordinarily be exercised not
lesser degree than solutions employing the com
mon types of‘ ‘solvent compositions previously
to incorporate substantial amounts of materials
tending to increase the viscosity 0r accelerate the
used. This coupled with the fact that the odor
rate of gelling in the solution, such as, for ex
of the ‘coating compositions‘of my invention‘ is 40 ample, the alcohols, which when present in only
very mild and agreeable, as compared to that of
very small proportions, will increase the gelling
such compositions formerly available, make them
tendency of the solution. I
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much better suited for most types of vinyl coat
This is a continuation-in-part of my copending
ing compositions than those containing the previ
application U. S. Serial No. 465,801, filed Novem
ously available solvents. Another advantage of 45 ber 16, 1942._
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the solvents of my’invention, over those previ
What I claim is: ‘
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ously employed, is the fact that the former have
l. A coating composition possessing decreased
higher boiling points and correspondingly lower > gelling tendencies, comprising a tough and strong
rates of evaporation than the latter.
arti?cial resin insolublein toluene, having a mo
Although it is frequently desired to use a dilu 50 lecular weight in excess of 4000, and prepared by
ent in vinyl resin coating compositions, it should
the copolymerization of vinyl chloride, with vinyl »
be noted that the incorporation of such material
acetate, said resin being dissolved in ,a suii‘icient
ordinarily results in an increase in the viscosity
quantity of a solvent having a low rate of evap
of the‘composition, and under certain conditions
oration to decrease the gelling‘ tendency of the
the viscosity increase with leaner mixtures be 55 composition, comprising an alkyl ester of levulinic
comes very great. This increase in viscosity, in
acid and a liquid coal-tar hydrocarbon, tomake
general, depends upon such factors as tempera
a readily ?owable composition adapted to produce
ture of the solution, the concentration of the
resin in solution, the viscosity characteristics of
resistant, adhesive, and stable protective orbrna
the particular resin employed, etc. Therefore,
mental'surface coatings.
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to obtain lacquers possessing the desired prop
erties. For example, the viscosity of a solution
containing 15 grams of vinyl resin per 100 cc. of
solvent mixture which consisted of 40 per cent
protective or ornamental'surface coatings.
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2. A coating-composition possessing decreased
it will be evident that the proportion of diluent 60 gelling tendencies, comprising a tough and strong
to levulinic ester utilized, in any speci?c coating
arti?cial resin insoluble'in toluene, having a mo
composition, will vary with the particular dilu
lecular weight in excess of 4000, and prepared by
ent, the character and concentration of the resin,
the copolymerization of vinyl chloride with vinyl
the probable length of time before use of ‘the 65 acetate, said resin ‘being dissolved in a suilicient
composition, and other such factors. By proper
quantity of a volatile solvent having a low rate »
selection of the particular alkyl ester of levulinic
of evaporation to decrease the gelling tendency of
acid and the‘ diluent and proportion thereof-1', both
the resulting composition comprising ethyl levu
the viscosity and the rate of evaporation of the
linate, to make a ‘readily ?owable composition
coating composition can be widely varied so as 70 adapted to produce ‘resistant, adhesive, and stable
ethyl levulinate, and 60 per cent toluene at 30°
AA
3. A coating composition possessing decreased
gelling tendencies, comprising a‘tough' and strong
arti?cial resin insoluble in toluene, having a mo
lecular weight in excess of 4000, and prepared by
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the copolymerization of vinyl chloride‘ with vinyl
I lecular weight in excess of 4000, and prepared by
acetate, said resin being ‘dissolved in a suf?cient -.
the copolymerization of vinyl chloride with vinyl
quantity of a volatile solvent having a low rate
acetate, said resin being dissolved in a sufficient '
> of evaporation‘to decrease the gelling tendency
quantity of a volatile solvent having a low rate of '
of the composition, comprising ethyl levulinate
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and a liquid coal-tar hydrocarbon, to make a ,
readily ?owable composition adapted to produce
resistant, adhesive, and stable protective or orna
mental surface coatings.
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a liquid coal-tar hydrocarbon, to make a readily
,?owable composition adapted to produce resist
ant, adhesive, and stable protective orornamental
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4. A coating composition possessing decreased l0
gelling tendencies, comprising a tough and strong
surface coatings.
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. 6. A coating composition possessing decreased
gelling tendencies, comprising a tough and strong
yinylresin copolymer having a molecular weight
, arti?cial resin insoluble in toluene, having a mo
lecular weight in excess of 4000, and prepared
' by the copolymerization of vinyl chloride with
vinyl acetate, said resin being dissolved in a suf
evaporation to decrease the gelling tendency of
the composition, comprising butyl levulinate and
in excess of 4000 insoluble in toluene, and con
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?cient quantity of a volatile solvent having a low
, rate 01’; evaporation to‘decrease the gelling tend
ency of the resulting‘ composition comprising
_ butyl levulinate, to make a readily ?owable com
sisting of approximately 85% vinyl chloride and
15% vinyl acetate, said resin being dissolved in a
sufiicient quantity of a solvent having a low rate
of evaporation to decrease the gelling tendency
of the resulting- composition comprising alower
position adapted to produce resistant, adhesive,
alkyl ester of levulinic acid, to make a readily
and stable protective or ornamental surface coat~
?owable composition adapted to produce resistant,
ings.
adhesive, and stable protective vor ornamental sur
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5. A coating composition possessing decreased
gelling tendencies, comprising a tough and strong
arti?cial resin insoluble in toluene, having a. mo 25
face coatings.
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GLEN H. MOREY.
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