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XR 2,899 327
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A. 2,899,327
nited attented Aug. 11, 1959
2
Still another object of the invention is to provide a
flexible animal glue composition having an increased
2,899,327 melting point and an increased rate of set without sub
GLUE SETTING ACCELERATORS stantially increasing the gel strength thereof.
Other objects of the invention will be apparent from
Edward F. Christopher, Chicago, and Harland H. Young, the detailed description and claims to follow:
Western Springs, Ill., assignors to Swift & Company, Broadly, the invention contemplates the addition to
Chicago, Ill., a corporation of Illinois an animal protein derived from collagen, a quantity of
No Drawing. Application December 5, 1955 a substituted ammonium salt of a water soluble poly
Serial No. 550,813 O carboxylic acid whose acid portion of the salt is char
acterized by an additional function selected from the
10 Claims. (C. 106-125) groups consisting of alcohols and ethers. Examples of
such compounds are the substituted ammonium salts of
such hydroxy polycarboxylic acids as tartronic, malic,
This invention relates to the manufacture of new 5 citramalic, hydroxy glutaric, tartaric, citric, trihydroxy
and useful animal protein products derived from col glutaric, mannosaccharic, saccharic, and mucic, and the
lagen, and more particularly to animal glue and gelatin substituted ammonium salts of a water soluble polycar
Spositions which set to produce a tough, non-tacky boxylic acid which contains an ether function in the acid
lm. portion of the salt such as, for example, diglycolic and
This is a continuation-in-part of our abandoned co 20 ethylene bis glycolic.
sing application Serial No. 265,208, filed January 5, The most effective substances within the foregoing
952. broad class of substances for increasing the rate of set
Animal glue and gelatin products which form tough, or melting point of animal glue compositions are the hy
non-tacky films set by virtue of their tendency to lose droxy alkylamine salts of tartaric, citric, and malic acids.
moisture and their tendency to congeal to a gel. The 25 Of the many hydroxy alkyl amines which are suitable we
rate at which a glue or gelatin product sets to a non find mono, di, and triethanolamines, mono, di, and tri
tacky film is generally indicated by the standard Bloom isopropanolamines and mixtures thereof are most readily
jelly test which records the weight in grams required available and suitable for the nitrogen-containing base.
to press a piston into a gel a given distance under stand It has been found, for example, that mono, di, or tri
ard conditions. Normally, the higher the gel strength 30 ethanolamine citrate or mixtures thereof will reduce the
(Bloom test) the faster will the product set. It is also setting time of a conventional glue or gelatin composi
recognized that an animal glue or gelatin product that tion to about from one-half to one-eighth of the time re
has a high rate of set will have certain of the desirable quired by the same glue or gelatin without the alkylol
properties associated with a product having a high gel amine salt. At levels of from about 1 to 10 percent,
strength. Thus, an animal glue or gelatin product which 35 based upon the weight of animal glue preparation, the
has a high rate of set generally has a greater commercial alkylolamine citrates, tartrates, malates, etc., will greatly
value than the slower setting products. enhance the rate of set of a flexible glue, dry glue in
In the manufacture of certain animal glue products solution, and films of liquid glue. In addition, the dried
commonly designated as "flexible glues,” varying amounts film is much more tough and leathery in appearance and
of plasticizers are often added to the glue composition 40 behavior.
where the animal glue product is subjected to dehydra In flexible glue compositions where higher degrees of
tion and desiccation. Plasticizers that are suitable for plasticization are desired, the amounts of the plasticizing
such purposes are glycerine, sorbitol, glycols, sugars, and materials may vary from 5 percent to 75 percent of the
other polyhydric humectants which are compatable with total composition and from 10 percent to 150 percent
animal glue. Thus, by increasing the amount of plas 45 of the dry glue weight.
ticizers, the animal glue may be converted from a brittle The following specific examples illustrate the present
horny substance to a soft, pliable, rubber-like product invention in several of its forms but should not be con
which is known commercially as flexible glue. Inter strued to limit the invention to the precise compositions
mediate amounts of plasticizers produce a very tough, or proportions disclosed:
leathery film. 50
In the manufacture of other animal glue products Example I
which are not classed as flexible glues, the rate of set Percent
of the glue products is frequently much slower than de Bone glue (75 gm. Bloom test) ----------------- 90
sired, as when the slower setting bone glues are used Triethanolamine citrate ------------------------ 10
in substantial amounts. Thus, since there are many 55
applications in which it is highly desirable that the ani The above composition was prepared by adding the
mal glue products set to a tough film more rapidly triethanolamine citrate to a concentrate solution (45%)
than normally, the usefulness and value of animal glue of the bone glue. After mixing thoroughly, the heavy
and gelatin products which set to a tough, non-tacky solution was chilled to strips of jelly and dried by passing
film could be greatly increased by decreasing the time 60 first cold and finally warm air over the strips. The dried
required for the films to set to a gelled, tough, non glue was a tough, leathery flake material which, when
tacky film. reconstituted to approximately a 40 percent solution,
Therefore, it is an object of the present invention to set in about one-half of the time required by the origi
provide animal glue and gelatin compositions with a nal glue.
Example II
substantially increased rate of Set. 65
It is also an object of the present invention to provide Percent
animal glue and gelatin compositions of a given gel Hide glue (200gm. Bloom test) ----------------- 93
strength having a substantially increased rate of set Diethanolamine tartrate ------------------------ 7
without substantially increasing its gel strength.
Another object of the invention is to provide animal 70 This composition was prepared as in Example I.
glue and gelatin compositions which form a tough, leath When reconstituted to a 30 percent solution it set in about
ery film with an increased rate of set. one-third the time required by the original glue.
2,899,827
3 4.
Example III The foregoing ingredients were combined as in the
Percent preceding examples to form a flexible glue composition.
Hide glue (250 gm. Bloom test) --------------- 35 Upon remelting the glue composition and dilution to
Water -------------------------------------- 35 a usable consistency, it was found to have a setting time
Glycerine ----------------------------------- 14 of 1.5 minutes as compared with a setting time of 8
Sorbitol ------------------------------------- 8 minutes for the control sample.
Pentachlorophenol Sodium salt ----------------- 0.5 Example VII
Capryl alcohol ------------------------------- 0.5 Parts
Lithopone ----------------------------------- 2.0 Gelatin --------------------------------------
Diethanolamine citrate ------------------------ 5.0 O Glycerine ------------------------------------ 7
The foregoing flexible glue composition was prepared Diethanolamine citrate ------------------------- A.
by dissolving the glue in the water and adding the re Water ----------------- a as said wit was what am a mom of ur with 3
maining ingredients to the glue solution. The tempera Gelatin is soaked in a cold mixture of water and glyc
ture of the composition was maintained between about 5 erine. When swollen, the gel is melted until uniform
140° F. and 160° G. with agitation until a uniform mix and the diethanolamine citrate is stirred in thoroughly.
ture of the several ingredients was obtained. The mass When cast into a film on a flexible backing, the above
was then poured into molds and allowed to cool to form mixture sets with extreme rapidity and is useful as a
flexible slabs which could be readily remelted. duplicator film or roll (hectograph).
The resulting flexible glue composition had a high rate 20
of set and produced a film having a firm body when set. Example VIII
After dilution to a useful consistency, the setting time Percent
for the foregoing flexible glue composition was found to Bone glue (75 gm. Bloom test) ------------------ 90
be 1.5 minutes as compared with a setting time of 8 Diethanolamine diglycollate --------------------- O
minutes for the control flexible glue at the same dilution, 25 This composition was prepared as described in Ex
having the same composition except for the omission of ample I. When the dry glue composition was reconsti
the diethanolamine citrate and its replacement with tuted to approximately 40% solution it set in about two
glycerine. thirds of the time required for the original glue,
Example IV Percent
Bone glue (Bloom jelly strength 75 gm.) --------- 24 30 Example IX
Hide glue (Bloom jelly strength 250 gm.) -------- 12 Percent
Water --------------------------------------- 30 Bone glue (75 gm. Bloom test) ------------------ 24
Invert Sugar ---------------------------------- 5 Hide glue (250gm. Bloom test) ----------------- 12
Glucose ------------------------------------- 19 Water --------------------------------------- 30
Invert Sugar ----------------------------------
Sugar, brown -------------------------------- 5 35 Glucose 5
Capryl alcohol ------------------------------- 5 ------------------------------------- 19
Pentachlorophenol ---------------------------- 0.5 Sugar, brown --------------------------------- 5
Triethanolamine citrate ------------------------ 3 Capryl alcohol -------------------------------- 15
A concentrated solution of the glue was prepared by Pentachlorophenol----------------------------- 0.5
Diethanolamine ethylene bis glycollate -----------
dissolving the glue components in the water heated to a 40 3
temperature between 140° F. to 160° F. and then adding This composition was prepared as described in Example
the remaining ingredients with agitation until a uniform IV and upon being tested after dilution to useful con
mixture was obtained. The mass was poured into molds sistency, it was found to have a setting time of about one
and allowed to cool.
45
half of the setting time for the control sample of flexible
Upon remelting the above flexible glue composition glue.
and dilution to a usuable consistency, it was found to Example X
have a setting time of 3.5 minutes as compared with a Percent
setting time of 10 minutes for the control Sample of Hide glue (260gm. Bloom test) ----------------- 35
flexible glue. 50
Water --------------------------------------- 35
Example V Percent Glycerin ------------------------------------- 14
Hide glue (Bloom jelly strength 250 gm.) -------- 18 Sorbitol ------------------------------------- 8
Water -------------------------------------- 25 Sodium propionate ---------------------------- 5
Sugar --------------------------------------- 28 Octadecanol ---------------------------------- S
Invert Sugar --------------------------------- 5 s Lithopone ----------------------------------- 2.0
Glucose ------------------------------------- 20 Diethanolamine diglycolate --------------------- 5.0
Octadecanol --------------------------------- 15 The several ingredients were combined as described in
Sodium propionate ---------------------------- 0.5 Example IV. The glue composition was remelted and
Di-isopropanolamine citrate -------------------- 5 diluted to a usuable consistency. It was found to have
The foregoing ingredients were combined to form a 60 a setting time of 5 minutes as compared with the setting
flexible glue composition as in Example II. time of 9 minutes for the control sample.
Upon remelting and diluting to a usable consistency, Example XI
the flexible glue composition was found to have a setting Percent
time of three minutes as compared with a setting time of
12 minutes for the control sample of flexible glue. 65 Water --------------------------------------- 40
Glycerin ------------------------------------- 30
Example VI Percent Hide glue (250gm. Bloom test) ------------------ 30
Hide glue (250 gm. test) ---------------------- 35 The above formula is that of the control glue. Varying
Water --------------------------------------- 35 amounts of 2%, 3% and 6% diethanolamine diglycolate
Glycerine ------------------------------------ 14 O were incorporated in portions of the foregoing composi
Sorbitol ------------------------------------- 8 tion. The three test glues were prepared by adding the
Sodium propionate ---------------------------- 5 diethanolamine diglycoliate to a solution of the glue com
Octadecanol ---------------------------------- 5 position with agitation while holding the temperature of
Lithopone ----------------------------------- 2. the glue composition at 150 F. until a uniform mixture
Diethanolamine tartrate ------------------------ 5.0 75 was obtained, The effect of adding varying amounts of
2,899,827
5 6
the diethanolamine diglycolate salt to the glue composia position. For example, when mono, di and triethanol
tion is set forth in the following table: amine citrate, tartrates, or malates, or mono, di, and tri
isopropanolamine citrate, tartrates or malates are added
Setting Time in to the flexible glue compositions shown in Example III,
Minutes at relative 5
Humidities of - the setting time thereof was altered in the following
ae
Setting
Time,
Control Glue.------------------------------- Concentration of the Alkylolamine Salt Minutes
gontrol glue plus 2%Diethanolamine Salt.
9ontrol glue plus 3%Diethanolamine Salt.
Control Glue plus 6% Diethanolamine Salt-------- Flexible glue control Sample.------------------------------ 8
1% concentration.------------- 6
3% concentration.-- - 3%
Example XII 5% concentration------------------------------------------- 1% to 2
Percent
Hide glue (250gm. Bloom test) ------------------ 30 5 The alkylolamine salts of citric, tartaric, malic, and
Water --------------------------------------- 40 other hydroxy polycarboxylic acids exhibit this same gen
Glycerin ------------------------------------- 30 eral tendency to approximately the same degree so that
A concentrated solution of the glue composition was it is practical to make use of any possible combination
prepared by dissolving the glue component in the water 20 of the amine salts in order to take advantage of cost,
heated to a temperature of 150 F. and then adding the availability and other economic factors. It is obvious
glycerin with agitation until a uniform mixture was that setting times can be regulated along with the degree
obtained. of flexibility desired through the interchangeability of
A second glue composition of the following formula these alkylolamine salts with other plasticizers such as
was prepared in a similar fashion: 25 glycerine and sorbitol.
Percent The setting time of a film of glue containing a substi
tuted ammonium salt of the ether acids of the invention
Hide glue (250gm. Bloom test) ------------------ 30 may be controlled to a considerable extent by varying
Water---------------------------------------- 40
Triisopropanolamine ethylene bis diglycollate ------ 30 the concentration of the substituted salt in the glue com
30 position. The following table contains information illus
It will be noted that the test glue composition differed trating the effect of varying the concentration of a di
from the control in that the triisopropanolamine ethylene ethanolamine ethylene bis glycollate in the flexible glue
bis glycollate was substituted for the glycerin of the con composition shown in Example III.
trol. The effect upon the setting time attributable to the
use of the triisopropanolamine salt is illustrated below 35 Setting
Time,
Concentration of the Alkylolamine Salt Minutes
Setting Time in
Minutes at relative
Humidities of - Flexible Glue Control--------------------------------------
2% Concentration.-----------------
3%. Concentration. -
(SEAT.)
Attest:
KAR, H, AXNE ROBERT C. WATSON
Attesting Officer Commissioner of Patent