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Патент USA US3075948

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United States Patent O
1
C6
3,il75,§38
Patented Jan. 29, E953
2
3,0753%
AQUEQIUS QGLL‘SiDAL DEPERSEQNS il‘lilJNTAiN
ENG HALQGENATED ACETYLENEC ALCUHGLS
Robert L. loimson, l‘viidlantl, Mich, assignor to The Dow
Chemical (Iompany, Midland, Mich, a corporation of
Delaware
No Drawing. Filed June 25, E959, Ser. No. 822,731
15 Claims. (til. 259-2937)
agents, a relatively high concentration is required which
contributes to the problems ‘of water sensitivity and
spotting which are frequently encountered when ?lms
cast from present latex and latex paints are subjected to
washing, spattering or to conditions Which lead to con
densation of water on coated surfaces. The desirability
of the provisions of improved synthetic latex and latex
containing compositions and of methods for avoiding
the problems inherent in the applications of such com
This invention relates to improved aqueous colloidal 10 positions, is evident.
dispersions. It is particularly concerned with composi
It is an object of the present invention to provide for
tions comprising ‘synthetic latexes and a method for
improved compositions of aqueous colloidal dispersions
making such compositions.
Synthetic latexes have found widespread application
comprising synthetic latexes characterized by properties
of resistance to microbial (attack and degradation. A
in the protective coating ?eld. In such usage, the latex 15 further object is to provide an improved method for
or a composition containing it is applied to masonry,
rendering compositions comprising synthetic latexes re
metal or ‘wood surfaces whereby ?lms are formed which
sistant to microbial attack and degradation. A still fur~
tend to adhere to the solid surface and protect the latter
ther object is to provide a method for producing latex
against marring and Weathering. The latexes comm-only
paint compositions which are resistant to the attack of
are modi?ed by the addition of pigments and other agents 20 microorganisms. Other objects will become apparent
to provide latex paint compositions which have desirable
properties as regards ease of application, ease of
clean-up, self-sealing, alkali resistance and odor. The
from the following speci?cation and claims.
According to the present invention, it has been dis
covered that improved ‘aqueous colloidal dspersions com
prising synthetic latexes are obtained when there is in~v
synthetic latexes are also employed as saturants for papers
to improve such properties as tear resistance or added 25 corporated into the synthetic latex a minor and effective
to other compositions including other synthetic latexes
to impart “sti?ening” or other desirable properties for
speci?c uses.
proportion of halcgnated acetylenic alcohol. 'I‘hese halo
genated acetylenic alcohols are soluble in water and
solvents in the amounts employed and when added to
Certain problems have been encountered in the storage
aqueous colloidal dispersions comprising synthetic latex
and application of synthetic latexes and compositions in 30 impart thereto a preservative action, i.e., a property of
which they are employed. For example, the synthetic
resistance to microbially induced degradation even when
latexes contain stabilizers and emulsi?ers to maintain
added in amounts considerably less than that now em
the polymer in the dispersed state. Many commonly
ploX ed with known preservatives.
employed stabilizers and emulsi?ers are organic in na
Haloge ated acetylenic alcohols suitable for the prac
ture and subject to attack by microorganisms. When the 35 tice of this invention are alkynols containing a hydroxyl
latexes are employed in latex paint formulations, they
group on the carbon atom adjacent to the acetylenic car
are modi?ed with other additaments such as thickeners,
pigment dispersants, other ?lm forming modi?ers and
bon atom and containing a halogen atom on the aliphatic
portion of the molecule.
The preferred halogenated acetylenic alcohols are
organisms. The resultant microbiological activity fre 40 those having the structure
quently results in undesirable alterations in the viscosity
R
of the latex paint system and unfavorably affects its
spreading and odor characteristics.
stabilizers which may also be subject to attack by mirco
Z——OEC—(II—R’
in commercial latex and latex paint formulations, var
ious preservatives have been employed to prevent attack 45
in
by microorganisms. To accomplish such control with
In this and succeeding formulas, R may be hydrogen
phenols and their salts it has been found necessary to
maintain the latex compositions at a pH of 9 or higher.
inclusive, R’ may be hydrogen, alkyl containing from 1
or an alkyl group containing from 1 to 4 carbon atoms,
lytic breakdown of common protein components, prevent
to 4 carbon atom-s, inclusive, 0r phenyl, or R and R’
taken together may be pentamet-hylene and Z may be
detinning of containers and permit general ?exibility in
iodomethyl.
However, to minimize viscosity changes caused by hydro
manufacture and use, it is desirable that latex composi
tions be maintained at lower pH levels. Thus, the
phenols and phenolates do not represent the ultimate as
chloro, bromo, iodo, chloromethyl, brornomethyl or
A number of desirable properties characterize the
aqueous colloidal dispersions provided by this invention.
preservatives. Other preservatives such as organic mer 55 For example, all of the latex and latex paint compositions
cury compounds, on the other hand, are not only hazard
ous becouse of toxicity but unfavorably affect color
stability in certain formulations. Furthermore, certain
preservatives undergo diminution in activity or reduction
of the present invention are found to be resistant to
microbial deterioration and without adverse effects on the
color or other desirable properties of the latex. This
protective action is observed on repeated inoculation of
in killing power upon storage or standing on the shelf. 60 latex compositions with organisms normally present in
This is of particular importance in latex paints which
may be subject to subsequent infection by opening of
containers, insertion of brushes, exposure to dust and
other sources. Certain other preservatives frequently
water, soil and contaminated latex and latex paint. Fur
thermore, this action is observed throughout the acidic,
neutral and alkaline pH range. In addition, the free
?lms and/or coatings formed from such compositions
exhibit stability against degradation such as discoloration,
surface breakdown, peeling and water spotting su?ered
have adverse effects on the colloidal latex system when
an amount su?icient to provide adequate protection is
on exposure to heat, light and/ or Water that is frequently
added.
encountered
in ?lms formed from compositions modi?ed
Many preservatives are unsuitable in latexes and latex
by adding known preservatives. Thus, with latex and
paints since they have been found to affect the ?lms cast
latex paint compositions containing halogenated acety
therefrom or aifect the brushing and spreading character 70
lenic
‘alcohols, ?lms and coatings maybe formed in which
istics. Further, with certain preservatives such as phenolic
the desirable properties of the ?lms and coatings formed
3,075,938
3
from latex compositions containing no preservative are
retained. Furthermore, latex compositions of this inven
tion have the same non-hazardous properties as the latex
compositions containing no added preservative.
The expression “synthetic latex” as herein employed
is intended to mean any aqueous colloidal dispersion of
polymers of polymerizable ole?nically unsaturated mon
omers.
included also are polymers Which have been
4
obtained with from 0.001 to 1 percent by weight of the
halogenated acetylenic alcohol when based on the total
wet weight of synthetic latex, the range of from
0.001 to 0.2 percent by weight is preferred. In preparing
the improved aqueous colloidal dispersion, the halogen
ated acetylenic alcohol is blended with the synthetic latex
by mechanical mixing. The halogenated acetylenic alco
hol is usually ?rst dissolved in water, ethanol, methanol,
50:50 methanol-water or other suitable solvent and there
materials are homopolymers and copolymers of mono 10 after introduced into the latex with agitation in the tem
perature range of from 18° to 45° C. Good results have
ethylenically unsaturated compounds such as styrene,
been obtained by employing water, alcohol-water or alco
acrylonitrile, acrylic and methacrylic esters, tetra?uoro
modi?ed by cross-linking. Examples of such polymeric
ethylene, vinyl halide, vinylidene halide, vinyl alcohol,
and vinyl acetate; and copolymers of monoethylenically
unsaturated compounds such as styrene and acrylonitrile
with conjugated diole?ns such as butadiene and chloro
prene. The synthetic latexes are aqueous dispersions usu
ally containing in addition to the polymer, an emulsify
ing agent and buffers. They may, in addition, contain
other non-polymeric additives such as a plasticizer or
stabilizer. Typical of the synthetic latexes with which
holic solutions containing 10 to 50 percent by weight of
the halogenated acetylenic alcohol.
When the aqueous colloidal dispersion is a latex paint,
good results have been obtained when the halogenated
acetylenic alcohol is employed in an amount of from
about 0.01 to 1.0 percent by weight. This percentage by
weight is calculated on the basis of the weight of the
halogenated acetylenic alcohol and the total wet weight
of thepaint employed. It is preferred that from 0.05 to
this invention is concerned are those described in U.S.
0.2 percent by weight of the halogenated acetylenic alco
hol be added to the latex paint. The incorporation of the
Patent No. 2,498,712. Emulsifying agents which may be
halogenated acetylenic alcohol into the paint may be made
employed include sodium oleate, sodium sulfate esters of
'at
any point in its manufacture. It may be introduced
25
higher alcohols, or sodium sulfonate of alkylated naph
before
or after the addition of the pigment dispersion
thalenes. Buffers which are oftentimes used include
sodium bicarbonate and sodium tetraborate. These syn
thetic latexes are ‘generally ?lm forming but include as
well those which are essentially non-?lm forming but
which may be modi?ed to become ?lm forming or are 30
to the latex or added to said dispersion. Conveniently,
a solution of the halogenated acetylenic alcohol may be
blended into the formulated latex paint.
Representative synthetic latexes may be prepared by
polymerizing mixtures of suitable monomeric compounds
used to impart desirable properties such as stiifness to soft
in aqueous emulsion in accordance with known proce
?lm forming latexes or other materials such as papers,
dures. As described in U.S. Patent No. 2,498,712, the
textiles and the like.
polymerizable compounds, in proportions corresponding
The term “latex paint” as herein employed refers to
an aqueous colloidal dispersion containing ‘a ?lm forming 35 to the desired composition of the polymeric product, may
be mixed with an aqueous solution of an emulsifying agent
synthetic latex composition as above de?ned to which
and the mixture agitated to effect emulsi?cation. The
has been added a pigment. The term “pigment” denotes
emulsifying agent is ordinarily employed in an amount
colored as well as White pigments and is understood to
corresponding
to from 0.5 to 5 percent of the weight of
be inclusive of mineral products used as ?llers and ex
the
polymerizable
organic compounds, but it may be used
40
tenders. Suitable pigment materials are well known and
in smaller or larger proportions. A catalyst such as a per
god results have been obtained when employing the litho
oixde is usually added in an amount corresponding to from
pone, titanium dioxide, barium sulfate, calcium carbon
0.5 to 4 percent of the weight of the compounds to be
ate, clays, mica, talc, silica and the like in various com
binations and proportions depending on the end use for
polymerized, but is not always required. A buffer may
which the paint is designed. Colored pigments and dyes
which have been found compatible in these compositions
include benzylidene yellow, cadmium yellow, iron oxides,
container, generally at temperatures between 50° and
100° C. to effect polymerization. After completion of the
polymerization, the property of the resulting polymeric dis
toluidine toners, sienna, amber and ultramarine blues.
Suitable .pigment dispersants such as tetrasodium pyro
phosphate, lecithin, gum arabic and numerous synthetic
surface active agents such as sodium lauryl sulfate, lauryl
ammonium acetate and glyceryl monolaurate may be em
ployed. In addition, thickeners, colloid stabilizers, modi
?ers, defoamers and other paint-making ingredients may
be present in latex paint. These ingredients and latex
paint compositions containing them are extensively de
scribed in the art, e.g., in U.S. Patent No. 2,498,712.
Colloid stabilizers, thickeners, and modi?ers which may
be used include casein, tar-protein, polyacrylates, alginates,
alkyd resins and Water-soluble cellulose derivatives. De 60
rfoamers include kerosene, pine oil, octyl alcohol, tributyl
phosphate, and numerous others ‘available under trade
names.
be added if desired. The emulsion is heated in a closed
persion may be modi?ed, if desired, by the incorporation
in the dispersion of other additives such as plasticizers or
stabilizers.
An example of synthetic latexes which may be employed
is a GRS type latex.
A representative latex is an ap—
proximately 35 percent aqueous colloidal dispersion con
taining a copolymer of approximately 50 percent buta
diene and 50 percent styrene prepared by emulsion polym
erization. This latex may be prepared by charging a
reactor with the following:
Parts by weight
Butadiene _______________________________ __
18.0
Styrene _________________________________ .._ 18.0
Water __________________________________ __ 64.0
Emulsi?er (soap flakes) ____________________ __
1.54
Catalyst (potassium persulfate) _____________ __
0.09.0
The preferred polymeric materials to be contained in
The mixture is then agitated to effect emulsi?cation and
the synthetic latexes in accordance with the present in~ 65
heated at a temperature of 50° C. for 23 hours to cause
vention ‘are copolymers prepared from 25-75 percent of
polymerization. A post-stabilizer (35 percent solution of
at least one conjugated aliphatic diole?n and 75-25 per
potassium oleate) is added to the resultant latex in the
cent of at least one vinyl aromatic compound. Typical
ratio of 4.71 parts by weight of post-stabilizer for every
conjugated diole?ns are butadiene and isoprene. Typical
90 parts by weight of latex and the mixture then heated
vinylaromatic compounds are hydrocarbons of the hen
zene series having a vinyl group on a benzene or substi
to steam distill the volatiles and recover an approximately
50:50 styrene-butadiene copolymer latex of 35 percent
. solids content.
The halogenated acetylenic alcohols with which the
The synthetic latex thus prepared may be employed
present invention is concerned may be employed in any
antimicrobial amount. While good results have been 75 for the preparation of a paint emulsion. A typical latex
tuted benzene nucleus such as styrene and vinyltoluene.
3,075,938
5
6
paint may be formulated by blending together 69 parts by
EXAMPLE 1
weight of latex with 100 parts by weight of pigment paste
having the following composition:
Ingredient:
A synthetic GRS type latex of 50 percent styrene-50
Parts by weight
percent butadiene prepared as previously described was
modi?ed by adding varying amounts of 3-iodo-2-propyn
Water ________________________________ __ 10.1
1-01 to produce modi?ed compositions containing vary
Sodium pyrophosphate (Na2P2O7-l0H2O)____ 0.5
ing concentrations of the halogenated acetylenic alcohol.
Titanium dioxide _______________________ __ 47.0
Lithopone
Mica
13.4
____
__
These latex compositions as well as a control containing
no 3-iodo-2-propyn-1-ol were then inoculated with a mixed
6.7
tit-Protein (10 percent solution) __________ __ 19.1 10
culture of seventeen organisms consisting largely of
Pine oil _______________________________ __
0.8
Pseudomonas, Bacillus and Proteus species, previously
Tributyl phosphate ______________________ __
2.5
isolated from spoiled samples of latex and latex paint.
Fifty gram portions of the various modi?ed and unmodi
Variations may be made in the above formula as will be
apparent to those skilled in the art.
?ed latex compositions were inoculated with 0.05 milliliter
of a 24 hour nutrient broth culture of the mixed
The halogenated acetylenic alcohols having the struc 15 portions
organisms and maintained at 30° C. At various intervals
ture
' ‘t
Z——CEC—-C——R’
OH
‘
after inoculation, multiple streaks were made from these
samples on poured nutrient agar plates and the streaked
plates incubated at 30° C. for 48 hours. At the end of
20 this period, the plates were examined for microbial growth.
The results obtained are set forth in Table I.
Table I
may be readily prepared by known methods. The chloro
substituted-acetylenic alcohols represented by the struc
ture
25
Microbial growth at
Concentration in percent by
weight
1?
24 hours
o1-oHs-oEo—(l3—R'
OH
None ____ __
.__do
may be prepared by treating one mole equivalent of an
None ____ _.
2 weeks
None.
___do
Do.
___do _____ __ ___d0 _____ __
Do.
___do _____ __ "-010 _____ __
Do.
___do _____ __ ___do _____ __
Do.
Heavy____ Hcayy____ Heavy
acetylenic-diol represented by the structure
It
1 Week
35
HO-CHz-CEC-G-R’
EXAMPLE 2
Synthetic latexes including commerically available In
OH
texes produced from the various monomers were modi
?ed by the addition of 3-iodo~2-propyn-1-ol to give a
with approximately 1 mole equivalent of thionyl chlo 4:0 series of latexes containing 0.1 percent by weight of 3
ride and one mole equivalent of pyridine in an inert sol
iodo-2-propyn~1-ol based on the total weight of latex.
vent such as benzene in the temperature range of from
about 30° to 80° C. for from 3 to 18 hours and there
Fifty gram portions of the modi?ed as well as unmodi?ed
samples were inoculated with 0.05 milliliter portions of a
‘24 hour nutrient broth culture of the same mixed orga
after recovering the desired product by distillation proce
dures. The halogenated acetylenic alcohols represented
45 nisms employed in Example 1, and maintained at 30° C.
by the structure
At various intervals after inoculation multiple streaks were
made on agar plates and the latter incubated at 30° C.
for 48 hours and thereafter examined as described in Ex
ample l. The results are set forth in Table II.
50
Table II
may be prepared by re?uxing the corresponding chloro~
substituted acetylenic alcohol with sodium bromide or
Ooncentration in
Latex
sodium iodide in an alcoholic solvent such as methanol
for from 10 to 24 hours.
weight
The halogenated acetylenic alcohols represented by the
structure
-
Elvacet 81-900 1 ____ __
Do. L.
Lytron 615
130.3"---
Microbial growth at
percent by
_
0. 1
None
0.1
24 hours
1 Week
None ____ __
None ____ __
2 weeks
None.
Heavy____ Heavy____ Heavy.
Trace-.-" Trace____- Trace.
None Heavy____ Heavy__._ Heavy.
60
1 Commercial polyvinylacetate later.
1 Commercial polystyrene latex.
may be prepared by reacting an acetylenic alcohol hav
ing the structure
EXAMPLE 3
Commercially available synthetic latexes were modi?ed
by the addition of 3-iodo-2-propyn-l-ol to give a series of
latexes containing various concentrations of the halo
genated acetylenic alcohol based on the total weight
of latex. Fifty gram portions of the modi?ed as well as
with the appropriate sodium hypohalite solution in the 70 unmodi?ed
samples were inoculated with 0.05 milliliter
portions of a mixed culture of organisms previously de—
from 1 to 3 hours and thereafter recovering the product
scribed and maintained at 30° C. 'At various intervals
by conventional procedures, such as by solvent extraction.
after inoculation, samples were streaked, incubated and
The following examples illustrate the invention but are
observed as described in ‘Example 1. The results are set
not to be construed as limiting.
forth in Table III.
temperature range of from 0° to 10° C. for a period of
e,07e,ese
3
7
EXAMPLE 6
Table III
Latex
Concen-
Interval
tration in
after
Synthetic latexes including commercially available la
percent by inoculation
weight
texes produced from various monomers were modi?ed by
the addition of a halogenated acetylenic alcohol to give
a series of latexes containing various concentrations of a
growth
halogenated acetylenic alcohol based on the total weight
1 week .... _
Naugatuck 2000 1
Do.*....
_____do__
of latex.
___
Fifty gram portions of the modi?ed as well as
unmodi?ed samples were inoculated with 0.05 milliliter
portions of a mixed culture of organisms as previously de
scribed and maintained at 30° C. for 1 week. Multiple
streaks were made on agar plates and the latter incubated
at 30° C. for 48 hours and thereafter examined as de
scribed in Example 1. The results are set forth in
15 Table VI.
Table VI
1 Commercial GRS latex.
2 Commercial ethyl acrylate-methyl methaorylate copolymer latex.
20
EXAMPLE 4
In a similar manner, 3-iodo-2-propyn-1-ol was added to
Concentra
tion in
Halogeneted acetylenic
commercial styrene-butadiene copolyrner latex to produce
alcohol
a modified latex composition containing the halogenated
acetylenic alcohol in varying concentrations. Fifty gram 2
samples were inoculated with 0.1 milliliter portions of
‘i-chloro-z-butyn-l-ol ........ __
0. 1
Do ______ -_
0.01
0.005
0. 1
0.05
0.005
0. 05
..
0.01
Do ..................... -.
0.005
a-(iodoethynyljabenzyl alcohol
Table IV
0.1
DO ..................... --
0.005
None (control) __
Concen
tration in
percent by
Latex
1 week
None
35 4-chlcro-2-butyn-1-o
D0 ___________ .4-i0d0-s-butyn-20L.
24 hours
2 weeks
weight
0. 1
_.
_
3-brcmo'2-propyn-1-ol ....... __
0. 05
_
Do.1 ______ ._
(control).
0.005
.
0.01
-
o ..................... ._
a-(iodoethynybbenzyl alcohol.
0. 05
0.005
_
0. l
-
0. 05
_
Do _____________________ __
0.01
Dow Latex 512-R
Dow Latex 512-112
40
.
_
0.05
0 _______________ _.
0. l
0.1 ____ --
0.005
0.1
Do _____________________ __
4-bron1o-.,-butyn-1»ol._
Dow Latex 512-111
None (control)-
None
None _
4-chloro-2-bntyn-LOL-
0. 1
___________ -.
_
Do.2 ______ __
0.1
L0.3 ____ _-
0. 1
0.01
None
0. 01
o ........... _-
0.005
4-bromo-2-butyn-1-ol.
0. 05
Do _______________ -_
-_
0.005
a-(iorloethynybbenzyla-lco 01.
0. 05
0.3 ____ __
Dow Latex 7 02
0.005
3-bromo-2-propyn~1-cl
45
Heavy. ___
(control).
1 Commercial 60 percent. styrene40 percent bntadiene copolyrner latc x, 50
48 9percent
solids.00 percent styrene~40 percent butadiene copolymer latex,
Commercial
4.8 3percent
solids. 67 percent styrene-33 percent butadicne copolymer
Commercial
latex, 48 percent solids.
EXAMPLE 5
0.1
Do ____________ _.
___
0.005
None (control-.4-chloro-2-butyn-1-ol.
.
-
None
0. 1
0. 05
D0 .......... -_
_
4-i0do-8-butyn-2-ol.
_
Do __________ __
.
0.01
3-bromo-2-propyn-1-0Ll-bromo-Zbutyn-l-ol-..
_
_
0. l
0. 05
0. 05
Do ..................... __
0. 01
a-(iocloethynybbenzyl alcohol-
0. 1
None (control ______________ -_
None
4-chlcro-2-butyn-1-ol ________ _-
0. 005
4-iodo-3-but3m-2-ol __________ __
0.
55
In a similar manner, a synthetic GRS type latex of 50
.
0. 05
o ___________ ..
0.01
None
(control).
Dow Latex 762-Wa
0.005
4-iodo-3-butyn-2-o1__
0. 05
_
growth
0. 01
4-iodo-33Dutyn-2oL
are set forth in Table IV.
Microbial growth at
Microbial
0. 1
0 ____________ -.
a mixed culture of organisms and maintained at about
25° C. At various intervals after inoculation, samples
were streaked, incubated and observed as described in Ex
ample 1. Unmodi?ed latexes were treated in a similar
manner and employed as controls. The results obtained
Latex
percent by
weight
percent styrene-50 percent butadiene of the composition
previously described was modi?ed by adding various halo
genated acetylenic alcohols in varying concentrations.
o _____________________ __
a-(iodoethynybbenzyl alcohol.
Fifty gram portions of modi?ed as well as unmodi?ed 60
None (control) ______________ __
control samples were inoculated with 0.05 milliliter por
tions of a mixed culture of organisms as previously de
1 Commercial GRS latex.
9 Commercial polyvinylchloride latex.
scribed and maintained at 30° C. for 1 week. The sam
ples were then streaked, incubated and observed as de
scribed in Example 1. The results are set forth in 65
Table V.
Table V
Halogenated acctylenic alcohol
Concentration
2-chloro-2-butyn~1-ol ____________________ .-
0. 1
4-io do-3-bntyn-2-ol.__
3-bromo-2-propyn~1~o _
4-bromo-2-butyn-1-ol. _
None (control) __________________ ._
-_ __
EXAMPLE 7
In a similar manner, commercially available styrene
butadiene latexes were modi?ed by the addition of hal
ogenated acetylenic alcohol and inoculated as above de
scribed. The inoculated samples were maintained at 30°
Microbial
growth
None.
0. 01
D0.
_
0.1
Do.
.
._
0. 05
None
Do.
Heavy
None
C. for varying intervals, and then streaked, incubated and
' observed as described in Example 1.
'75
forthinTableVII.
'}
‘
The results are set
‘I
_
_
I
3,075,938
Table VI]
Conccntrotion in
percent by
Halogenated acetylenic alcohol
Microbial growth at
Latex
weight
4-bromo-2-but3n-1-o] ____________________ __
0. 05
Ii-chloro-Zbutyn-l-ol___.
1-iodo-3-methyl-l-pentyn
_
e-iodo-Zmethyl-3-butyn-2-ol_
4—iodo-3~butyn-2-ol____
24 hours
Dow Latex 512—K___
None. _ _
1 week
None. _ _
2 weeks
N one
0.05
_____do ____________ _- _-_do_ _ __ ___do__ __
D0.
0.01
___do___r
Do.
0. 1
___do____
Do.
0. 05
_._do_ _ _.
Do.
exanoL.--
0. 05
0.05
-._do._____oo___.
Do.’
Do.
1-'odo-3,5-dimethyl-l-hexyn-{i-ol_.
3-bromo-2-propyn-l-ol
None (control) _ _ _
0. 05
0. 05
None
___do_ _ _ _
___do_ _ _ _
Heavy- _
Do.
Do.
a-(IodoethynyD-bo
l~(iodoethynyl)-cycl
4-bromo-2butYn-l
___-
0. 05
4-cliloro-2-butyn-l-o1
___-
0. 05
.__do__ _ _
____ _.
0. 1
___do_ _ __
____ __
O. 1
l-iod Q-S-methyl-l-pe
_
4~iodo-2¢methyl-3-but‘74-2-01
4-iodo>3-butyn-2‘o1__
0. 05
a-(IodoethynyD-ben ,
0.05
l-(iodoothynyl)-cyc1ohexanol
1~iodo-3,5-<lirnethyl-l—hexyn-3
0. 05
O. 05
3-bromo-2-propyn-l-QL _ ___
_
None. _ _
Heavy
None
Do.
0.05
None (control) ______ __
None
4~bromo-2-butyn-1-ol_ ___
0. 05
1-iodo~3-mcthyl-Lpentyn-3-ol
4-iodo-2-methyl-3~butyn-2~ol_
0. 1
0. 1
4-iodo-3~butyn-2‘ol ___________ __
0. 05
lz~(iodoethnyl)-benzyl alcohol__
0.05
l-(iodoethnyl) -cyclol1exa.nol_ _ _ _
O. 05
l—iodo-3,5-di-mctl1yl-1-hexyn~3-ol _
0. 05
3-brorno-2-propyn-1-ol _______ n
_
0. 05
None (control) ___________________________ __
None
EXAMPLE 8
These modi?ed latex compositions are resistant to
In a similar manner, commercial polystyrene latex 30 microbially induced degradation.
(Dow Latex 586) was modi?ed by the addition of hal
ogenated acetylenic alcohol and inoculated as previously
Example 10
described. The inoculated samples were maintained at
A latex paint formulation employing a synthetic GRS
type latex comprising a copolymer of 50 percent styrene
30° C. for varying intervals, and then streaked, incubated
and observed as described in Example 1.
as follows:
Tablle VIII
‘
Concen-
I-lalogonated acetylenie
alcohol
3-iodo-2-propyn-1-ol ______ _.
Do ______ __
_-
0.1
described was modi?ed by adding various halogenated
acetylenic alcohols at varying concentrations to produce
modi?ed paint compositions. Each modi?ed paint sam
ple as well as unmodi?ed paint sample was then inoculat
0 ed with a- mixed culture of organisms previously described
and maintained for four weeks at about 30° C., and then
streaked and incubated as previously set forth. The
following results were observed on examination of the
Microbial growth at
tration in
percent by
weight
The results were 35 and 50 percent butadiene and prepared as previously
24 hours
1 week
2 weeks
None.__- None.__- None.
0.05
Do.
0.01
0.1
0.05
0. 01
Do.
Do.
Do.
Do.
Trace-.- ___do..___
Some____ Trace.--
streaks after the period of incubation (Table IX):
45
Table IX
None Heavy__ Heavy__ Heavy
EXAMPLE 9
l-(bromoethynyl)cyclohexanol is intimately dispersed
Halogenated acetylenie alcohol
50
in a 50 percent styrene-50 percent butadiene copolymer
latex having a 40 percent solids composition to produce a
4-iodo-3-butyn-2-ol ________________________ __
Oonccntration in per-
Control of
microbial
cent by
weight
growth
0. 2
Excellent.
modi?ed latex composition containing 0.05 percent by
Do ____ __
_-._
__-__
Weight of l-(bromoethynyl)cyclohexanol.
1-(chloroethynyl)cyclohexanol is intimately dispersed
Do ______________ _-
_-
0.05
Do.
55 4-chloro-2~butyn~l-ol..
__
0.2
Do.
Do ______________ __
3-bron1o-2-propyn-l-ol.
A-brom o~2-but§m~1-ol
in a commercial 65 percent styrene-35 percent butadiene
.copolymer latex having a 48 percent solids composition
to produce a modi?ed latex composition containing 0.01
__
0. 1
Do.
__
0.1
Do.
-_
___
0. 2
0. 2
Do.
Do.
None (control) ____________________________ ._
None
None.
percent by weight of l-(chloroethynyl)cyclohexanol.
l-iodo-3,5-dimethyl-1-hexyl-3-ol is intimately dispersed
60
in a commercial vinylidene chloride-acrylonitrile copoly
EXAMPLE 11
- mer latex having a 515-53 percent solids composition
A latex paint was made by intimately blending in
to produce a modi?ed latex composition containing 0.1
a conventional manner 100 grams of a pigment dispersion
of the following composition: -
percent ‘by weight of 1-iodo-3,5-dimethyl-1-hexyn-3-ol.
l-bromo-3-ethyl-l-pentyn-3-ol is intimately dispersed
Ingredient-
in a commercial polystyrene latex having a 49.5 percent
solids content to produce a modi?ed latex composition
containing 0.005 percent by weight of l-bromo-3-ethyl-1
pentyn-3-ol.
a-(Iodoethynyl)-a-(normal-butyl)benzyl alcohol is in
807
Sodium pyrophosphate (N214P2O71OH2O)
70
‘ timately dispersed in a commercial acrylonitrile-butadiene
copolymer latex to produce a modi?ed latex composition
containing 0.1 percent by weight of ot-(iodoethynyD-u
' (normal-butyl ) benzyl alcohol.
Amount
Water ____________________ __milliliters__
75
grams_.. 43.44
Titanium dioxide____-___________ __do_.___ 3726
Lithopone ____________________ __do____ 1064.4
Ground mica__________________ __do____ 529.8
OL-PI‘OtClII (10 percent) __________ __do____ 1515.6
Pine Oil ___________________ _..';___d0___..
63.3
Tributyl phosphate _____ _a ______ __do____
201
sprees-e
12
11
EXAMPLE 13
with 69 grams of various commercial latex ?lm forming
agents. The latex paint compositions were then modi?ed
In ‘a still further operation, a latex paint having the
to give compositions containing a halogenated acetylenic
alcohol in varying concentrations. Fifty gram samples
of modi?ed paint were inoculated with 0.05 milliliter of
a mixed culture of organisms previously described and
maintained for four Weeks at 30° C., and thereafter
streaked, incubated and observed as described in Ex
2)
following formulation was prepared:
Pigment grind—Pounds/ 100 gallons
ample 1. The results were as follows:
10
Table X
Dibutyl phthalate ________________________ __.
8
Tergitol NP-l41 ________________________ __
5
Lecithin _______________________________ __
‘Potassium carbonate _____________________ __
7
1
Ethylene glycol _________________________ __
18
Diethylene glycol monoethyl ether _________ __
17
Titanium dioxide ______________ __. ________ __ 225
Talc ___
__
__
_____
150
Calcium carbonate ______________________ __ 175
Concen
tration
or’ halo
Halogenated
acetylenic alcohol
Water
genatecl
acetylenic
Latex
________________________________ __ 291
Foamicide 581-32 __________________ __i___..
Control of
microbial
growth
2
Paint reduction
Methylcellulose, 4000 cps., 2 percent ______ __ 175
alcohol in
Celanese 1023 __________________________ __ 266
percent by
weight
20
1 An alkyl phenyl polyethylene glycol ether.
'2 Commercial defoamer.
3Commercial polyvinylacetate homopolymer latex.
ll-iodo-3-buyn-2-ol_____ Dow Latex 762—W__
O. 1
Do _____________ _-
Good.
0. 05
0.2
0.05
0. 1
0. 0'
Dow Latex 512-K___
U. 2
0.1
Good.
0 2
Excellent.
0.1
_ . _ _-do __________ __
Do _____ _-
Do.
organisms previously described and maintained for four
Weeks at 30° C., andthereafter streaked, incubated and
o.
’
0.1
Do.
observed as described in Example 1. The results were
Do.
Dow Latex 762-W
None
Dow Latex 512-K...
None
a composition containing 4»chloro-2-butyn-l-ol in varying
concentrations. Fifty gram samples of modi?ed paint
were inoculated with 0.05 milliliter of a mixed culture of
Do.
0. 2
Do _ _ . _ . _ .
25
__.__do _____________ ._
0
None (control)
Do.
Do.
Excellent.
-.__.do ________ _.V_____
Dow Latex 762-W- _
The latex paint composition was then modi?ed to give
Do.
None.
30 as follows :
Do
Concentration of 4~chloro-2-butyn-1-ol in percent
by weight
Control of microbial
growth
EXAMPLE 12
0.2--..
In a further operation, a latex paint having the fol
lowing formulation was prepared:
Pigment grind-
250
_ _ _ __
.__-.
~
Excellent
Good.
--_
DO.
None (control) ................................... .- None.
40
I claim:
6
75
1. An aqueous colloidal dispersion comprising (1) a
synthetic latex containing in the disperse phase a polymer
dioxide _______________________ __ 210
of at least one ole?nically unsaturated monomer and (2)
Tamol 731 (25 percent)1 ________________ __
Casein (.15 percent, NHgOH) cut __________ __
Clay
. . . . _
Pounds/100 gallons
Water .._
Titanium
0.10.05__
_______ _.. ________________________ __
75
Diatomaceous silica _____________________ __ 35
Calcium carbonate"--- _________________ __ 125
Polyglycol 713-1200 2 ____________________ __
Nopco JMK 3/Water (1/1) _______________ __
.Diethylene glycol _______________________ __
5
6
15
Rhoplex AC-33 ________________________ __ 350
X Anionic surfactant, sodium salt of carboxylated polvelectrolyte.
= Polypropylene glycol, average molecular weight 1200.
from about 0.001 to 1 percent by weight of a halogenated
acetylenic alcohol wherein the amount is based on the
total weight of synthetic latex and wherein said halogen
ated acetylenic alcohols are ailiynols containing a hydroxyl
group on the carbon atom adjacent to the acetylenic car
bon atom and containing a halogen atom on the aliphatic
portion of the molecule.
2. An aqueous colloidal dispersion comprising ("1) a
synthetic latex containing in the disperse phase a copoly
mer of a conjugated diole?n and a vinyl-aromatic com
3 Commercial deloamcr.
pound of the benzene series and (2) from about 0.001 to
The latex paint composition was then modi?ed to give
1 percent by weight of a halogenated acetylenic alcohol
wherein the amount is based on the total weight of syn
compositions containing a halogenated acetylenic alcohol
thetic latex and wherein said halogenated acetylenic al
in varying concentrations. Fifty gram samples of a mixed
cohols are alkynols containing a hydroxyl group on the
culture of organisms previously described was maintained
carbon ‘atom adjacent to the acetylenic carbon atom and
for four weeks at 30° C., and thereafter streaked, incu
containing a halogen atom on the aliphatic portion of the
60
bated, and observed as described in Example 1. The
molecule.
results were as follows:
3. An aqueous colloidal dispersion comprising (1) a
synthetic latex containing in the disperse phase a copoly-_
mer of from 25 percent to 75 percent of butadiene and
Table X1
7
Halogenated acetylenic alcohol
Concentration
of halogenated
Control of
acetylenic
alcohol in
percent by
microbial
growth
weight
correspondingly from 75 percent to 25 percent by weight
of a vinyl-aromatic hydrocarbon of the benzene series,
and (2) from about 0.001 to 1 percent by weight of a
halogenated acetylenic alcohol wherein the amount is
based on the total weight of synthetic latex and wherein
said halogenated acetylenic alcohols are alkynols contain
ing a hydroxyl group on the carbon atom adjacent to the
4-iodo-3lbutyn-2-ol
............. ..
0. 2
Good.
4-hromo-2-butyn-l-
._
0. 2
Excellent.
0 __________ _-
...-
0.1
Good.
None (control) ........................ -.
‘None
None.
acetylenic carbon atom and containing a halogen atom
on the aliphatic portion of the molecule.
4. An aqueous colloidal ‘dispersion comprising a syn
thetic latex containing in the disperse phase a polymer
3,075,938
13
of at least one ole?nically unsaturated monomer having
intimately blended therein from about 0.001 to 1 percent
_ group on the carbon atom adjacent to the acetylenic
carbon atom and containing a halogen atom on the ali
by weight of a halogenated acetylenic alcohol wherein
the amount is based on the total weight of synthetic latex
and wherein said halogenated acetylenic alcohols are
alkynols containing a hydroxyl group on the carbon atom
adjacent to the acetylenic carbon atom and containing a
halogen atom on the aliphatic portion of the molecule.
5. An aqueous colloidal dispersion comprising a syn
phatic portion of the molecule.
10. A latex paint composition consisting of an aqueous
colloidal dispersion comprising (1) a pigment, (2) a
synthetic latex containing in the disperse phase a copoly
mer of from 25 percent to 75 percent by weight of buta
diene and correspondingly from 75 percent to 25 percent
by weight of a vinylaromatic hydrocarbon of the benzene
thetic latex containing in the disperse phase a polymer
series, and (3) from about ‘0.01 to 1 percent by weight
of at least one oletinically unsaturated monomer having
of a halogenated acetylenic alcohol wherein the amount
is based on the total weight of latex paint and wherein
said halogenated acetylenic alcohols are alkynols con
amount is based on the total weight of synthetic latex
taining a hydroxyl group on the carbon atom adjacent to
and wherein said halogenated acetylenic alcohols are 15 the acetylenic carbon atom and containing a halogen atom
alkynols containing a hydroxyl group on the carbon atom
on the aliphatic portion of the molecule.
adjacent to the acetylenic carbon atom and containing a
11. A latex paint composition consisting of an aqueous
halogen atom on the aliphatic portion of the molecule.
colloidal dispersion comprising (1) a pigment, (2) a syn
6. An aqueous colloidal dispersion comprising (1) a
thetic latex containing in the disperse phase a copolymer
synthetic latex containing in the disperse phase a polymer 20 of from 25 percent to 75 percent by weight of butadiene
of at least one ole?nically unsaturated monomer and (2)
and correspondingly from 75 percent to 25 percent by
a halogenated acetylenic alcohol having the structure
weight of a vinyl aromatic hydrocarbon of the benzene
series, and (3) from about 0.01 to 1 percent by weight
of a halogenated acetylenic alcohol wherein the amount
25 is based on the total weight of latex paint and wherein
said halogenated acetylenic alcohols are alkynols contain~
wherein (a) R is selected from the group consisting of
ing a hydroxyl group on the carbon atom adjacent to the
hydrogen, an allcyl radical containing from 1 to 4 carbon
acetylenic carbon atom and containing a halogen atom
atoms, inclusive, R’ is selected from the group consisting
on the aliphatic portion of the molecule.
of hydrogen, an alkyl radical containing from 1 to 4 30
12. A latex paint composition consisting of an aqueous
carbon atoms, inclusive, and phenyl and Z is selected from
colloidal dispersion comprising (1) a pigment, (2) a syn
intimately blended therein from 0.001 to 0.2 percent by
weight of a halogenated acetylenic alcohol wherein the
in
the group consisting of chloro, bromo, iodo, chloromethyl,
bromornet-hyl and iodomethyl and (b) R and R’ taken
together is pentarnethylene ‘and Z represents the above
identi?ed radicals, said halogenated acetylenic alcohol
thetic latex containing in the disperse phase a polymer
35
being present in an amount of from about 0.001 to 1
of at least one ole?nically unsaturated monomer and (3)
from about 0.01 to 1 percent by weight based on the
weight of latex paint of a halogenated acetylenic alcohol
having the structure
percent by Weight based on the total weight of the aqueous
R
colloidal dispersion.
7. An aqueous colloidal dispersion comprising (1) a
synthetic latex containing in the disperse phase a copoly 40
mer or" from 25 to 75 percent by weight of butadiene and
correspondingly from 75 to 25 percent by weight of a
vinyl aromatic hydrocarbon of the benzene series and (2)
a halogenated acetylenic alcohol having the structure
R
z—oEC~t|3—R'
I
OH
wherein (a) -R is selected ‘from the group consisting of
hydrogen, an alkyl radical containing from 1 to 4 carbon
atoms, inclusive, R’ is selected from the group consisting
of hydrogen, an alkyl radical containing from 1 to 4
45 carbon atoms, inclusive, and phenyl and Z is selected from
the group consisting of chloro, bromo, iodo, chloromethyl,
bromomethy-l and iodomethyl, and (b) R and R’ taken
together is pentamethylene and Z represents the above
wherein (a) R is selected from the group consisting of
hydrogen, an alkyl radical containing from 1 to 4 carbon
atoms, inclusive, R’ is selected from the group consisting
of hydrogen, an alk‘l radical containing from 1 to 4
identi?ed radicals, wherein the amount is based on the
total weight of latex paint.
13. A latex paint composition consisting of an aqueous
colloidal dispersion comprising (1) a pigment, (2) a syn
thetic latex containing in the disperse phase a copolymer
carbon atoms, inclusive, and phenyl and Z is selected from
the group consisting of chloro, bromo, iodo, chloromethyl,
of from 25 percent to 75 percent of butadiene and corre
spondingly from 75 percent to 25 percent of a vinyl aro
bromomethyl and iodomethyl and (b) R and R’ taken to
gether is pentamethylene and Z represents the above iden<
matic hydrocarbon of the benzene series, and (3) from
ti?ed radicals, said halogenated acetylenic alcohol being
about 0.01 to 1 percent by weight based on the total weight
of latex paint of a halogenated acetylenic alcohol having
present in an amount of from about 0.001 to 1 percent
by weight based on the total weight of the aqueous col
loidal dispersion.
8. An aqueous colloidal dispersion comprising (1) a
60
the structure
to
synthetic latex containing in the disperse phase a polymer
of at least one ole?nically unsaturated monomer and (2)
3-iodo-2-propyn-l~ol in an amount of from about 0.001
to 1 percent by weight based on the total weight of
aqueous colloidal dispersion.
9. A latex paint composition consisting of ‘an aqueous
colloidal dispersion comprising (1) a pigment, (2) a syn
thetic latex containing in the disperse phase a polymer
of at least one ole?nically unsaturated monomer, and (3)
from about 0.01 to 1 percent by weight of a halogenated
acetylenic alcohol wherein the amount is based on the
total weight of latex paint and wherein said halogenated
acetylenic alcohols are alkynols containing a hydroxyl
wherein (a) R is selected ‘from the group consisting of
hydrogen, an alkyl radical containing from 1 to 4- carbon
atoms, inclusive, R’ is selected from the group consisting
of hydrogen, an alkyl radical containing from 1 to 4
carbon atoms, inclusive, and phenyl and Z is selected from
the group consisting of cliloro, bromo, iodo, chloromethyl,
brornomethyl and iodomethyl and (b) R and R’ taken
together is pentamethylene and Z represents the above
identi?ed radicals, wherein the amount is based on the
total weight of latex paint.
14. A method ‘for rendering synthetic latex composition
3,075,938
15
resistant to microbiological degradation, said synthetic
latex composition containing in the disperse phase a poly
1%
latex paint and wherein said halogenated acetylenic a1
cohols are alkynols containing a hydroxyl group on the
carbon atom adjacent to the acetylenic carbon atom and
containing a halogen atom on the aliphatic portion of the
which comprises the step of intimately blending in the
molecule.
5
composition a halogenated acetylenic alcohol in the
amount of from about 0.0011 to 1 percent by weight based
References Cited in the ?le of this patent
on the total weight of synthetic latex at a temperature in
the range of from 18° to 45° C. and wherein said halo
UNITED STATES PATENTS
mer of at least one ole?nically unsaturated monomer,
genated acetylenic alcohols are alkynols containing a hy
droxyl group on the carbon atom adjacent to the acetyl 10
enic carbon atom and containing a halogen atom on the
aliphatic portion of the molecule.
15. A method of producing latex paint composition
resistant to microbially induced degradation, said latex
paint composition comprising a synthetic latex containing
1,689,008
2,749,377
2,847,392
2,888,421
2,957,761
Biddle _______________ .. Oct. 23, 1928
Johnston ______________ __ June 5, 1956
Eck ________________ __ Aug. 12, .1958
Adams et al ___________ __ May 26, 1959
Davis _______________ __ Oct. 25, 1960
15
OTHER REFERENCES
in the disperse phase a polymer of at least one ole?nically
US.
Dept.
of
Agriculture Tech. Bulletin, #162, March
unsaturated monomer, which comprises blending in the
1929,
pages
‘47
and
48.
latex paint composition during its manufacture, a halo
.McLarnore et al: “Journal of Organic Chemistry,”
genated acetylenic alcohol in an amount of from about
0.01 to 1 percent by weight based on the total weight of 20 volume 20, No. 1, pages 109-110 (1955).
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