AU6097773A - Preserving grain and animal foodstuffs - Google Patents

Description

I 1.0~;;i1iv8 Min

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TEST CHART RESOLUTION MICROCOPY OFSTANDARS 963 BUREAU NATIONAL

1~r~ic- 5274

THREE DOLLAR_ S IT REE CUARS APPLC2 2

,Wte _CELANESE CORPORATION, a corporation organized and existing

under the laws of the State of Delaware, located at 522 Fifth Avenue, Npw York, New York, United States of America

hereby ppnv grant I"AiP tbcL ftrt inverticn z.irlec tor PRESERVATIVE COMdPOSITION

v;hich desrib,2d i the accomrpan-, 'wm--pec~acatlon.

00* 2. his alpplic.tion ii a C~ pplication and isbhasci ou titt appoicadin'i s for 2 Serf', or IC'. 2 1 0 0 V,,Or~i'.fl p .t .nt or imnibr pratt .'ior nia c in UNITED STATES OF ANERICA o 0 9

0 0 on October 30, 192 nmber.3 3O?,388 0 0 .4 m:nicered ,and

uunerr 00 0 0 0 0 3. My/'rur ss r ser-v. i C,;&,eo-C.\'E.TfcSN :j i Pxv o Attorneys, of DEAKIN, A.C.T, 260 7 0 0000 DATED t2IiS 'th clay of September 1973 0

CELANESE CORPORATION 0 0 0

7i~~ 41 Marvin Turken Assistant Secretary

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27 GAVVI.ER 7EAKIN, A.C.T. 260() c- 52741 aou 8 F~t~,7 t*t~Ytt.a 'LE R

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In I;up))'rL C' th. C);uenrio-, ilt :iti tn ii- t f p1 :1 for an -toflr.tlCtrtt

irwen trun eni~ PRESERVATIVE COMPOSITION

Marvin Turken, Assistant Secretary Celanese Corporation, a corporation organized and existing under the laws of the State of Delaware located at 522 Fifth Avenue, New York, New York, United States of Amrerica it i .d wtcecl~y dt~u rztastUtA I. the mplicaotf) f- t Cie~ 'at cn

,'or in the ca..c of an aplilicat.rn by -I hod:, corrp.nate) 1. 1 am authot-ked by CLNSE CORPORATION the arippicant for th,: Paltent to rnalk this cccainn on its b-.%h~uif.

St.a k ,IrN. 2.The baic applitcatio's) as define~l hy sc~k.n 141 of the ALt mado a, in United States 'of Am e on the 30th day of October 9. 72 ,No. USSN 0,8 and flo InC &tly of 19 1 c by on he day of 19. ,No. by

3. 1 amr e icIIk *ua! of tGe in\-eil on. .9

(or, wherc a ptrsfl Otht2-t than the inventor k tlie aplicant) 3. Bobby Joe Bland and Arthur Lewis Gross, both citizens of' the U.S.A. of 620 Philomena and 5621 Safari, C orp us Chr isti, T ex a s, Uni t .ed S tate .s of America respectively

)f thit inv-enic't ,ir,,4 the faet- arche i tual it 'n q:Lthe.... %JA CEL[AMSE CORPORATON ctifl-I to niakr-tke e~ti, "s~ fl1owse- by virtue of a deed of' assignment dated October 23, 1972

atI. rtPe,.4. 1.Thle ic 1:,ii rl £auc''0in v.;rajr iph 2f tz.Is DcclarnaC.,n ~sr i C~ U t ti~w~to~ j in 7,11C a t 0irr.tior Ixn :sxtuf th., invc-on the subjetot tlf he

7.I New York, New York D!"(r..k7ED NT U.S.A. 20th d .y 'f om-cfT September 1. 73 C1UANESE CORPORATION

Marvin turken, Assistant Secretary

Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-1969

SPECIFICATION COMPLETE (ORIGINAL)

FOR OFFICE USE Class _5 (i 2 tnt. Class 7' c+ Application Number: 60 7 3L't Lodged: -S 10-7

Complete Specification-Lodged (C 7 Published: D0 7 r Priority:

Related Art: /7 2-7 y

TO BE COMPLETED BY APPLICANT ::Name of Applicant: T ~V

:.Address of Applicant: "2 2 "vp

Actual Inventor:

COWIE, THOMSON CARTER/ .Address for Service: 27 GAWLER CRES. DEAKIN, A.C.T. 2600

Complete Specification for the invention entitled: pt g g VVrln~ V/

the best method of performing it known The following statement is a full description of this invention, including to me:-*

'Notc The descril -ion is to be typed In double spacing, pica type face, in an area not exceeding 9j" In depth and 61" in width, on tough white paper of good quality and It Isto be inserted Inside this form. Printer, Canberra F. D. AtKINSON, overnmcent L1

Abstract of the Disclosure

A mixture of propionic acid, acetic acid, and formaldehyde is used

to prevent the formation of mold growth on grain and animal feedstuffs. The

formaldehyde enhances the anti-fungal properties of the fatty acid mixture

and is preferably present in an amount of from about 15 to 25% by weight of

the total mixture, computed on the water-free basis.

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BACKGROUND OF THE INVENTION The problem of mold formation in animal and vegetable

matter is well known to the agricultural community.

Approximately 5% of all food grains that are harvested are lost d-e to spoilage before they can be consumed. This

loss deprives one half billion people of 100 pounds of grain per person per year. Grain spoilage also plays a

significant role in the economics of meat, milk, and

poultry production. The primary cause of grain spoilage is the growth of microorganisms, including molds, yeast, and

bacteria. The growth of these organisms reduces the

nutritive value and palatability of the grain, and may form

toxic materials that are injurious to animals and to humans that consume the animal products.

In order to obviate the problem of spoilage of grain or feedstuffs including forage or fodder, it has long been

known to dry grain (to 14% moisture or below, at which level

the growthof most fungi and bacteria is strongly inhibited).

Certain additives have also been employed to reduce the

degradation of human or animal foodstuffs, many having been

known for centuries. Vinegar, table salt, sugar, nitrates, benzoates, and certain salts of lower fatty acids are widely

known especially for preserving human foodstuffs. For

animal feeds the usual practice has been to reply on drying

or ensiling, but there has in more recent years been an increased interest in preservation through the use of lower

fatty acids and their salts, as will be discussed more

fully below.

-2-

I

Of the lower fatty acids and their salts, propionic

acid and its salts were found to be particularly effective

as fungal inhibitors. The particular propionates tested

were propionic acid. propionic anhydride, calcium propionate,

sodium propionate, propionamide and propionanalide. It has

been found that the addition of propionic acid and propionic

anhydride at a level of 0.1% inhibited the growth of molds

and controlled the heating in corn meal containing appro; imately

moisture. The same meal without the propionate inhibitors started to heat in seven days and reached a maximum temperature

of 120°F in ten days. Further, it has been well documented

that propionates are more effective inhibitors of the growth

of molds in an acid environment.

The discovery of propionic acid and its derivates as

being inhibitors of mold growth enhanced the study of short

chain fatty acids of the same homologous series as preserv- atives. These studies resulted in the conclusion that

formic and acetic acids can also be used with grain or

foodstuffs to prevent mold formation. Acetic acid in the

fcrm of vinegar has Leen known for centuries, of course, as

a food preservative. In addition, various mixtures of the

lower chain fatty acids and their acid salts have been used

as antifungal agents. While these preservative compositions

find utility in the preservation of foodstuffs, there is a

continuing need to develop antifungal compositions which are

not only useful in food preservation but which are effective

for a longer period of time than compositions previously

known.

In U.S. Patent 3,595,665 to Huitson et al.there are

described various combinations of lower alkyl fatty acids in

the preservation of crops. On composition cited includes

from 10-30% acetic and from 70 to 90% propionic acids.

Also in German Offenlegungsschrift 2,052,625, opened

to public inspection on Tune 24, 1970, there is disclosed a

composition comprising formaldehyde and propionic acid. While

the particular compositions disclosed therein have good

preservation qualities, there is a lack of full appreciation as to the preservative effects of formaldehyde in mixtures

of lower volatile fatty acids. Specifically there are no

enabling teachings regarding the unexpected properties of

mixtures of formaldehyde with acetic acid-propionic acid

mixtures in certain proportions.

Brief Description of the Invention

It is surprisingly found that certain mixtures of

volatile fatty acids (VFA) containing formaldehyde have greater effectiveness in preventing mold formation than

simple fatty acids, alone or in combination, or formaldehyde

alone. More specifically, the present antifungal composition is based upon the mixture of acetic acid, propionic acid, and

formaldehyde in certain specific ranges of proportions to

effect a preservative activity far greater than that expected from a simple additive effect of each component. As an illustration, a solution containing, on the anhydrous basis,

16% by weight of acetic acid, 64% by weight of propionic acid,

and 20% formaldehyde (added as a 37% aqueous solution) applied

to grain has a preservative effect, measured by the number of

days elapsing before the appearance of mold, which is greater

than that of the acids, singly or taken together, or that of formaldehyde alone.

Detailed Description of the Invention

As described above the present invention relates to

the use of formaldehyde along with volatile fatty acids in

a grain 1.reservative composition. Specifically, it has been found that the addition of from about 15 to 25% formaldehyde

to certain volatile fatty acid preservative compositions enhances the entire microbial action of the compositions

thereby giving them greater preservation effect. Optimum results occur with the addition of from about 18 to 22% by

weight of formaldehyde to a fatty acid composition of

parts by weight acetic and 80 parts by weight propionic acids. The unexpected synergism arising out of the

formaldehyde re,'lts in a preservative composition having

and increased preservation time of from 50 to 100% over

volatile fatty acid compositions used previously. Another particularly effective composition within the purview of

the present invention is a mixture containing on the anhydrous

basis 36% by weight acetic acid, 24% by weight propionic

acid and 40% by weight of formalin (a 37% aqueous solution

of formaldehyde). Water content is not critical; water is

present usually only because 37% formalin is a convenient

formaldehyde source.

In the context of the instant invention any combination

of volatile fatty acids which are known to have antifungal

properties may be used. For example, mixtures of formic,

acetic, propionic and sorbic acids may be used in combination

with formaldehyde to effect a preservative composition having

enhanced preservation times. However, particular effective- ness has been found with the mixtures of propionic and acetic acids with formaldehyde discussed above.

The formaldehyde which is used in conjunction with the volatile fatty acids to make up the instant preservative

compositions may be in any form. Therefore, the formaldehyde

may be added to the organic acids in aqueous forms such as

a formalin solution or by means of adding paraformaldehyde

to the fatty acids. Therefore, the ultimate preservative

composition may be aqueous or anhydrous. While the formal-

dehyde may be in any form to obtain the desired synergistic

effects, it is pmreferred that formalin, a 37% aqueous solut- ion of formaldehyde, be added to the volatile fatty acids

thereby ultimately resulting in an aqueous solution of the composition. As mentioned above, the optimum solution

within the purview of the instant invention contains, on the

anhydrous basis, 16% by weight acetic acid, 64% by weight of propionic acid and 20% by weight of formaldehyde. The

preservative action of this mixture is at least five times better than a mixture of acetic and propionic acid and twice

as good as propionic acid alone, as measured by the time

elapsed before the appearance of mold in grain or fodder

after treatment with the preservative.

Description of the Specific Embodiments

The practice of this invention is further illustrated

by the following typical examples of the application of

the instant composition to food products.

A laboratory jar p;reservation test was conducted using

the following six formulations of volatile fatty acids and

formaldehyde:

Pure acetic acid and formalin

80% acetic, 20% propionic, and formalin

60% acetic, 40% propionic, and formalin 40% acetic, 60% propionic, and formalin

20% acetic, 80% propionic, and formalin

100% propionic and formalin Each of the above compositions is varied as to the amount of formalin being used in combination with the

volatile fatty acids. Each of these compositions is then applied at three different levels to high moisture (24%

moisture) mold spore-contamiinated cor:n. The particular

application levels are and 0.4% by weight of

corn and each level was applied at a constant volume of

milliliters, using water as the diluent. One hundred

grams of corn were used per test, being hand mixed and stored

at 750F.

Ten replicates of each mix and of each application level were prepared in the manner described above. The treated

corn was incubated at room temperature in the tightly sealed

jars and observed daily for visual signs of mold growth. The raw data results of this process are outlined in Table

1 where the elapsed time before mold appears is set forth

in days. A statistical average of the replicates is outlined

in Table II.

As can be observed from the data in Tables I and II

the addition of formalin to either or both fatty acids results

in some preservative activity. However, the most dramatic

results are shown in Table II with respect to the addition of

about 20% formaldehyde (40% formalin and 60% acid) to all the

acid compositions, and, in particular, the 20% acetic and propionic mixture. This data indicates an unexpected synergistic preservation effect resulting from the additionof from about 18 to 22% to mixtures of acetic and propionic acids. Note also the excellent results obtained in adding from 18 to 22% formaldehyde to propionic acid

(Test F).

It is to be understood that the statistical data

obtained are gathered from experiments utilizing contaminated

corn. Therefore, the fact that some of the replicates lo engengered mold within a relatively short time should not

be misleading in the overall statistical analysis of the data. For example, a mold contaimated control with no

preservative would be expected to show signs of mold in 2

or 3 days. A difference of a few days between a control jar and a test jar is statistically significant in establish-

ing the strength of a particular preservative.

In the following Table I the numbers (1 to 10) across the top line identify replicates of the preservative formul-

ations identified in the left-hand columns of the tables. The letter-number combinations in the left-hand columns

identify individual acid-formaldehyde mixes used in the tests,

and the percentages in the left-hand columns are weight

percent of the individual additive mix incorporated into

the moist corn for each set of ten replicate tests. Pairs

of numbers separated by a slash mark 40/60) designate

weight ratios of the named components of the treating mix- ture, and numerical expressions written as fractions in the

left-hand part of the table designate weight-ratio of fatty

acid to formalin in the mix. For example, the expression* rjo n hali40/0Mx 6 01 means 60 parts by weight of an 80/20 acetic acid-propionic acid mix added to 40 parts by weight of 37% formalin. TABLE I 1 2 3 4 5 6 7 8 9 A-1 HoAc 0.2% 5 5 5 5 5 5 5 5 5 0.3% 5 5 5 5 5 5 6 6 6 6 0.4% 6 6 7 7 7 7 7 7 7

A-2 Acetic/ Formalin 80/20 0.2% 6 7 8 9 10 10 10 10 12 12 0.3% 10 14 16 16 16 16 16 16 16 16 0.4% 19 23 23 23 23 23 24 26 27 27

A-3 Acetic/ Formalin 60/40 0.2%6 3 5 6 6 8 8 9 10 10 0.3% 6 8 8 8 10 12 14 14 14. 0.4%o 8 8 12 14 43 50 50 50 50

A-4 Acetic/ Formalin 40/60 0.2% 5 5 6 6 6 6 8 8 8 8 0.3% 8 8 8 8 8 8 8 9 9 19 0.4% 8 8 8 8 12 12 12 12 12 19

A-S Acetic/ Formalin 20/80 0.2% 5 5 5 5 5 5 7 8 8 0.3% 8 8 8 8 8 8 8 9 9 19 0.4%O/ 8 8 8 8 9 9 10 10 iS

A.-6 Formalin 0.2% 5 5 6 6 8 8 10 10 12 12 0.3% 6 6 6 8 8 b 8 8 8 8 0.4Y6 8 8 10 10 12 12 14 14 19

TABLE I (contid) ACID MIX HoAc/HoPr 1 2 3 4 5 6 7 8 9 B-1 80/20 Mix 100 Formalin 0 0.2% 4 4 5 5 5 5 5 5 5 0.3% 5 5 5 5 5 5 5 5 6 6 0.4% 5 6 6 6 6 6 6 6 7 7

B-2 80/20 Mix Formalin 0.2% 4 5 6 7 7 7 7 9 9 11 0.3%o 7 7 8 8 11 11 13 14 14 0.4%o 8 11 11 11 14 14 15 22 26 26

B-3 80/20 Mix Formalin 7U 0.29/ 4 4 5 5 7 7 8 8 13 14 6 7 7 8 8 9 11 13 13 14 0.4%

B-4 8/0Mix Formalin 0.2% 4 5 5 5 5 5 5 6 7 8 0.3%N 6 7 8 8 8 9 11 11 14 0.46 7 8 8 8 15 22 22 25 50

B-S 80/20 Mix Fomialin 0.2% 4 4 4 4 4 4 4 4 5 0.3% 4 4 5 5 6 6 6 8 8 8 o.4% 5 5 6 7 8 9 9 11 11 11

C-1 60/40 Mix 100 Formalin0 0.2% 5 5 5 5 5 6 7 7 7 13 0.396 5 5 6 6 6 6 6 8 13 13 0. 4% 6 7 7 7 7 7 8 8 8 9

C-2 60/40 Mix Formalin 0.2% 4 7 8 9 9 9 11 11 15 0.3% 9 13 13 13 14 14 15 15 15 0.4% 13 15 22 22 22 22 22 22 25 26

TABLE I (cont'd) 1 2 3 4 5 6 7 8 9 C-3 6o/40 Mix Formalin 770 0.2% 7 7 7 7 8 8 13 13 13 14 0.3% 13 13 13 18 18 26 33 50 50 0.4%o 13 13 22 32 50 50 50 50 50

C-4 60/40 Mix Formalin 0.2% 5 6 7 8 8 8 9 11 22 26 8 8 9 11 11 11 13 13 22 0.4% 13 13 14 14 14 14 14 50 50

60/40 Mix Formalin 0.2% 7 7 7 7 7 8 9 9 11 0.3% 7 7 7 8 8 11 13 13 22 22 0.4% 8 8 8 8 22 50 50 50 50

D-1 40/60 Mix 00 Formalin 0 0.2% 5 6 6 6 6 8 11 11 13 13 0.3% 6 6 6 6 6 6 7 7 11 18 0.4% 7 7 7 7 8 8 8 9 11 11

D-2 40/60 Mix Formalin 0.2% 7 7 8 9 9 11 11 11 13 13 0.-3%o 11 11 13 13 13 13 18 18 18 18 0.4%o 13 22 22 22 22 25 25 25 25 26

D-3 40/60 Mix Formalin 0.2% 4 8 8 8 9 1"5 18 18 18 18 0.3% 8 11 13 50 50 50 50 50 50 0.4% 11 26 50 50 50 50 50 50 50

D-4 4o/60 mix Formalin 0.2% 5 5 7 7 8 9 9 9 11 11 0.3% 9 11 11 11 11 50 50 50 50 0.4% 11 22 22 22 33 50 50 50 50

TABLE I (cont'd)

1 2 3 4 5 6 7 8 9 40/60 Mix Formalin

0.2% 3 4 5 6 6 8 10 10 10 17 0.3% 4 7 10 10 10 10 12 12 17 17 0.4% 10 10 10 10 12 12 12 17 17 17

E-1 20/80 Mix 100 Formalin 0

0.2% 7 7 7 7 7 7 7 7 7 0.3% 7 7 7 10 10 12 12 12 12 14 0.4% 10 14 14 14 17 26 31 32 32

E-2 20/80 Mix Formalin

0.2% 7 10 10 10 10 10 10 10 12 12 0.3% 14 14 14 14 14 17 17 17 21 21 0.4% 14 14 26 26 26 26 26 26 30

E-3 20/80 Mix Formalin '4

0.2% 5 5 7 7 7 7 12 13 13 13 0.3% 13 21 25 26 50 50 50 50 50 0.4% 14 32 5C 50 50 50 50 50 50

E-4 20/80 Mix Formalin 6O

0.2% 7 7 8 8 8 10 10 12 12 13 0.3% 7 7 8 10 10 12 12 12 13 17 0.4% 13 13 21 21 25 32 50 50 50

20/80 Mix Formalin

0.2% 4 5 5 6 6 7 8 10 10 0.3% 6 7 7 10 10 10 12 12 21 0.4% 10 10 10 10 10 12 12 14 14 14

F-1 0/100 Acid mix 100 Formalin 0

0.2% 10 14 14 14 14 14 14 14 17 0.3% 210 14 14 14 17 17 21 26 50 0.4% 12 21 26 32 32 50 50 50 50

TABLE I (cont'd)

1 2 3 4 5 6 7 8 9

F-2 0/100 Mix Formalin

0.2% 10 10 10 12 12 14 14 14 14 32 0.3% 14 21 21 24 24 24 24 25 25 26 0.4% 14 26 31 32 32 50 50 50 50

F-3 0/100 Mix Formalin 0

0.2% 7 7 8 8 10 14 14 21 21 21 0.3% 14 17 17 25 26 50 50 50 50 0.4% 31 50 50 50 50 50 50 50 50

F-4 0/100 Mix Formalin '0

0.2%Y 7 7 8 8 8 10 10 10 14 21 0.3% 10 12 14 14 14 17 24 25 50 0.4% 12 24 25 25 50 50 50 50 50

0/100 Mix Formalin

0.2% 4 4 5 5 7 8 10 10 14 14 0.3% 6 7 7 7 7 10 10 10 14 21 0.4% 12 12 14 14 17 25 50 50 50

TABLE II

Acid Ratio Acid/Formalin Level,Wto HoAc/HoPr 37% 0.3 0.4

A 100/0 100/0 5 7 80/20 16 24 60/40 11 32 /O 11 20/80 8 0/100loo 7 12

B 80/20 100/0 6 20 16 60/40 no mold/error in mix !.0/60 19 20/80 8

C 60/40 100/0 6 7 7 80/20 10 14 21 60/40 10 28 38 10 12 24 20/80 8 11 28

D 40/60 100/0 8 7 8 80/20 10 15 23 60/40 12 39 47 40/60 8 28 47 20/80 7 11 13

E 20/80 100/0 7 10 22 80/20 10 16 60/40 9 39 47 40/60 9 11 33 20/80 7 11 11

F 0/100 100/0 14 22 37 80/20 12 23 39 60/40 13 34 60 9 22 39 20/80 8 9

While the invention has been particularly shown and

described with reference to preferred embodiments thereof,

it will be understood by those skilled in the art that

variations in form may be made therein without departing

from the spirit and scope of the invention.

Claims (1)

1. The claims defining the invention are as follows

   1. An antifungal preservative composition comprising

   a lower fatty acid mixture comprising about 20% acetic

   acid and 80% prcpionic acid by weight and formaldehyde.

   2. The composition of claim 1 wherein the formal- dehyde is present in a concentration of from about 15 to

   by weight computed on the anhydrous basis.

   3. The composition of claim 1 wherein the formal- dehyde is present in a concentration, computed on the

   anhydrous basis, of from about 18 to 22% by weight.

   4. The composition of claim 1 which additionally includes water.

   The composition of claim 4 wherein the water is present in a concentration such that the water:

   ±ormaldehyde ratio is approximately that obtaining in a

   37% aqueous formaldehyde solution. 6. The composition of claim 1 wherein the com-

   position contains, en the anhydrous basis, 16% acetic acid,

   64% propionic acid and 20% formaldehyde.

   7. A method for preventing the growth of mold in grain and animal feedstuffs comprising treating the materials

   with a composition comprising a mixture of acetic acid and

   propionic acid in a weight ratio of 20:80, together with

   formaldehyde.

   8. The method of claim 7 wherein the materials are

   treated with a compsotion comprising from about 15 to

   formaldehyde on the anhydrous basis and the remainder a

   mixture of acetic and propionic acids.

   9. The method of claim 7 wherein the composition comprises a volatile fatty acid mixture of 20% acetic and

   propionic acid admixed with formaldehyde in a quantity

   such that the resulting mixture contains on the anhydrous

   basis, about 18 to 22% formaldehyde by weight.

   The method of claim 7 wherein the composition

   is 16% acetic acid, 64% propionic acid and 20% formaldehyde.

   DATED this 17th day of October, 1973

   CELANESE CORPORATION r