Cocoa butter substitutes and their preparation

A cocoa butter substitute comprises sal fat obtained by extracting the fat from the seeds of Shorea robusta and then refining the resulting product. The cocoa butter substitute has a hydroxy value of not more than 16, a solid fat index of not less than 48 at 30.degree. C., a cooling time, at which the maximum point appears in the cooling curve, of not longer than 120 mins. and the maximum point temperature of not less than 17.degree. C.

BACKGROUND OF INVENTION 
The present invention relates to cocoa butter substitutes which are 
suitable for preparing chocolate with tempering. More particularly, the 
present invention relates to cocoa butter substitutes made of sal fat 
which is derived from sal seeds or the seeds of Shorea robusta. 
Sal fat is one of the fats generally categorized as Borneo tallow type fats 
and it is extracted from the seeds of Shorea robusta, a naturally 
occurring tree in the tropics. 
Sal fat is liable to be hydrolyzed in the tissues of sal seeds by the 
action of enzymes present therein. Hot and high humidity climate 
conditions continue for several months after the sal seeds fall off the 
tree in the tropics, and those ambient conditions may also accelerate the 
hydrolysis of fat in the tissues. 
The acid value of the crude sal fat extracted from the seeds just after 
they fall off the tree is 3 to 4, the acid value of crude sal fat 
extracted from the seeds four months after they fall off the tree is 12 to 
16, and the an acid value of crude sal fat extracted from the seeds ten 
months after they fall off the tree is usually larger than twenty. But the 
acid value of crude sal fat, once it has been isolated from the tissues of 
the seeds by extraction, does not increase very rapidly during storage. 
Therefore, in order to obtain crude sal fat of low acid value, or low 
extent of hydrolysis, the fat should be isolated from the tissues of the 
seeds just after the seeds fall off the tree without any delay. But it is 
impossible to gather most of the seeds just after they fall off the tree 
and also it seems to be difficult to subject the seeds to the extraction 
just after they have been gathered, because of lower numbers of workers 
and inconvenient transportation in the districts where the seeds of Shorea 
robusta are produced. Therefore, the level of hydrolysis of available 
crude sal fat varies depending on the storage conditions of the seeds.

SUMMARY OF INVENTION 
The present invention relates to the technology of producing high quality 
cocoa butter substitutes from the sal fat regardless of the differences of 
the extent of hydrolysis of the crude sal fat. An object of the present 
invention is to provide high quality cocoa butter substitutes from the 
point of view of the properties suitable for producing chocolate as well 
as high quality of the final chocolate product. 
The extents of hydrolysis of various crude sal fats are evaluated by 
measuring the acid values of same. In the case of deacidified sal fat, the 
extent of hydrolysis is evaluated by measuring its hydroxy value. There is 
a marked tendency that sal fats having smaller extents of hydrolysis give 
cocoa butter substitutes of higher quality. Unless an appropriate process 
is particularly adapted for refining of the crude sal fats, they can 
hardly be used as cocoa butter substitutes even though sal fats having 
smaller extents of hydrolysis are used. 
Such an appropriate refining process applied to the crude sal fat is as 
follows. The crude sal fat is subjected to phosphoric acid treatment for 
degumming, and then to alkali deacidification, then washed with hot water 
and the water entrained in the fat is removed. The resultant fat is 
subsequently subjected to bleaching with activated clay, and subjected to 
steam distillation for deodorization. 
A more detailed refining process will be described below. The crude sal fat 
is first subjected to the phosphoric acid treatment, in which phosphoric 
acid is added to the crude sal fat in an amount of 0.1 to 0.4% by weight 
based on the weight of the fat and they are mixed for 10 to 20 minutes at 
a temperature of 50.degree.-70.degree. C. Then the aggregated gums or 
mucilaginous materials are removed by press filtration or centrifugal 
separation. The degumming by the phosphoric acid treatment provides the 
refined sal fat with a better flavour. The degummed fat is subjected to 
alkali deacidification. In conventional alkali deacidification, the 
quantity of the alkali added to the crude fat is 1.1 to 1.5 times the 
equivalent amount necessary for neutralization of the free fatty acids 
existing in the crude fat and the alkali is added in the form of an 
aqueous solution. But, such a conventional alkali deacidification can 
hardly be appropriate to the refining of sal fat, because it merely gives 
refined sal fat of worse quality. In order to produce a refined sal fat of 
better quality, the quantity of the alkali to be added must be 3-10 times, 
more preferably 4-5 times, the equivalent amount for neutralization of the 
free fatty acids existing in the crude fat and the alkali is added in the 
form of an aqueous solution in the step of the alkali deacidification of 
the sal fat. Although it has not actually been elucidated why a large 
quantity of an alkali must be used for the alkali deacidification of the 
sal fat, some of the impurities which are not acidic, but have some 
affinities for an alkali, and are liable to become insoluble by contact 
with an alkali seem to be removed from the sal fat in the form of alkali 
foots in the step of deacidification of the sal fat. The deacidification 
can be performed effectively in a stepwise manner, that is, first and 
second deacidification steps can be used. The first deacidification step 
is performed by adding an alkali in an amount of 0.8-1.5 times the 
equivalent amount for neutralization of the free fatty acids, in the form 
of an aqueous solution and removing the formed foots. The second 
deacidification step is performed by adding aqueous alkaline solution 
containing alkali in an amount of 0.1 to 0.8% by weight relative to the 
fat and removing the formed foots. The deacidified sal fat is subjected to 
washing with hot water just after the alkali deacidification. The washing 
is performed by adding hot water in the same quantity as that of the fat 
to be washed and stirring it vigorously at a temperature of above 
70.degree. C., followed by removing the water by decantation or 
centrifugation. The residual alkali and some pigments are washed out in 
the hot water washing step. Such treatment makes the below mentioned 
bleaching with activated clay more effective and more efficient. After the 
hot water washing, the sal fat is bleached with activated clay. In the 
conventional bleaching with activated clay, the quantity of activated clay 
to be added to the oils and fats are 2 to 3% by weight, based on the 
weight of the oils and fats. But the conventional bleaching can hardly be 
appropriate to the refining of sal fat because it provides the refined sal 
fat with a dark colour. In order to produce a refined sal fat with a light 
colour, the quantity of activated clay to be used must be 5 to 20% by 
weight, based on the weight of the fat. After the bleaching step, the fat 
is subjected to steam distillation for effecting deodorization, which is 
the final step of the refining process. The steam distillation is 
performed by introducing steam continuously into the fat at a temperature 
of 220.degree. to 270.degree. C., more preferably 220.degree. to 
250.degree. C., under a reduced pressure of 0.5 to 4 mmHg and removing the 
odoriferous materials from the fat with the steam. 
Among the sal fats refined by the refining process as mentioned above, some 
can be used as cocoa butter substitutes, while others can hardly be used 
as cocoa butter substitutes from the point of view of the properties 
suitable for producing chocolate as well as the quality of the final 
chocolate product. 
The relationship between the chemical and physical properties of the 
refined sal fat and the quality of chocolate made therefrom have been 
widely and intensively investigated by the inventors of the present 
invention. Through the investigation, it have been found that refined sal 
fats which have a hydroxy value of 0 to 16, preferably 0 to 13, a solid 
fat index at 30.degree. C. of 48 to 60, preferably 50 to 60, a cooling 
time, at which the maximum point appears in the cooling curve, of 45 to 
120 minutes, preferably 45 to 100 minutes and a temperature of the maximum 
point of 17.degree. to 28.degree. C., preferably 19.degree. to 28.degree. 
C. can be used as cocoa butter substitutes and they possess better quality 
from the point of view of the properties suitable for the manufacturing 
process as well as the quality of the final chocolate product. However, 
some of the refined sal fats which satisfy the chemical and physical 
properties as mentioned above are difficult to use as cocoa butter 
substitutes. Our further investigation reveals that the total content of 
hydroxy fatty acids and epoxy fatty acids in the refined sal fat 
influences the quality of the sal fat for use as a cocoa butter 
substitute. The refined sal fat which has a total content of hydroxy fatty 
acids and epoxy fatty acids not exceeding 1.5 weight %, preferably not 
exceeding 1.0 weight %, is successfully used as a cocoa butter substitute. 
The refined sal fat which has a total content of hydroxy and epoxy fatty 
acids not exceeding 1.5 weight % in the whole fatty acid composition, a 
hydroxy value not exceeding 16, a solid fat index at 30.degree. C. of not 
less than 48, a cooling time, at which the maximum point appears in the 
cooling curve, of not exceeding 120 minutes and a temperature of the 
maximum point of not less than 17.degree. C. in the cooling curve is 
successfully used as a cocoa butter substitute. In preparing chocolate by 
using the above-mentioned refined sal fat, the chocolate paste is 
solidified at a reasonable rate during the course of passing from the 
tempering step to the cooling step where it is passed through the cooling 
tunnel, and the solidified chocolate cast in a mold can be removed from 
the mold easily without any damage to the surface of the solidified 
chocolate because of its better shrinkability. The finished product of 
chocolate released from the mold, packed and subjected to the aging step, 
which is the finishing step in the production of chocolate, has a good 
luster, a good solidity, a good heat resistance, a sharp mouth-melting 
property, a good flavour, and a good resistance to fat blooming. When 
there is used a sal fat which has a total content of hydroxy fatty acids 
and epoxy fatty acids exceeding 1.5 weight % based on the total fatty 
acids and which does not have the desired values of hydroxy value, the 
solid fat index at 30.degree. C., and the cooling time when the maximum 
point appears and the temperature of the maximum point in the cooling 
curve, many troubles occur in the manufacturing of the chocolate; the 
viscosity of the chocolate paste increases so rapidly in the tempering 
step that the paste cannot be set in the mold because of the formation of 
a large quantity of fat crystals, moreover the solidified chocolate is 
hard to remove from the mold after the cooling step even if one is able to 
set the paste in the mold, and the finished chocolate product has a poor 
luster, an unreasonable solidity, and heat resistance, a poor 
mouth-melting property and a poorer resistance to fat blooming. It is 
considered that the poor properties obtained when such a sal fat is used 
as a cocoa butter substitute arise from the existence of a large quantity 
of the hydroxy fatty acids and/or epoxy fatty acids in it. 
As described above, for producing cocoa butter substitutes of better 
quality by using the refined sal fat, the sal fat should conclusively have 
a total content of hydroxy fatty acids and epoxy fatty acids not exceeding 
1.5 weight %, preferably not exceeding 1.0 weight % based on the whole 
fatty acid composition, a hydroxy value of 0 to 16, preferably 0 to 13, a 
solid fat index at 30.degree. C. of 48 to 60, preferably 50 to 60, a 
cooling time, at which the maximum point appears in the cooling curve, of 
45 to 120 minutes, preferably 45 to 100 minutes and a temperature of the 
maximum point in the cooling curve of 17.degree. to 28.degree. C., 
preferably 19 to 28. 
In case of the refined sal fat which does not satisfy the ranges of those 
values as defined hereinabove, a fractionation step should be included in 
the refining process such as described hereinbefore for producing the 
refined sal fat which satisfies those ranges. The fractionation refining 
as defined hereon includes winterizing fractionation, solvent 
fractionation, fractionation using a surface active agent as well as 
column chromatographic fractionation. According to these methods, 
monoglycerides, diglycerides, hydroxy fatty acids and epoxy fatty acids 
included in the crude fat can be removed. The fractionation refining is 
preferably performed following the step of removing water after the hot 
water washing step which in turn follows the deacidifying step, although 
it may be performed at any time in the refining process as described 
hereinbefore. The winterizing fractionation is performed by settling the 
harder fractions of the fat in a settling tank maintained at a suitable 
temperature. The fractionation using a surface active agent, which means a 
modified winterizing fractionation, is performed by crystallizing harder 
fractions in the fat admixed with a surface active agent. The solvent 
fractionation is performed by passing a mixture of fats and a solvent 
through cooling cylinders equipped with slowly moving internal scraper 
blades and then the crystallized fraction is removed by filtration. The 
column chromatographic fractionation is performed by passing a mixture of 
the fats and a non polar solvent through a column containing supports such 
as silica gel which can adsorb polar compounds such as hydroxy compounds 
and epoxy compounds, whereby the content of hydroxy compounds and epoxy 
compounds in the eluate can be minimized. 
The solid fat index which characterizes the refined sal fat of the present 
invention can be measured by conventional methods except for the tempering 
procedure, by which a sample fat in a usual tube for measurement of the 
solid fat index is tempered at 20.degree. C. for 2 hours and then at 
32.degree. C. for 1 hour alternately and such alternation is repeated 6 
times. The cooling curve is prepared by measurement while cooling the 
sample fat in the apparatus as shown in FIG. 1. The apparatus comprises an 
inner wall 1 and an outer wall 2, the walls being joined together at 5. 
The chamber 7 as defined between the walls 1 and 2 is maintained at a 
reduced pressure of about 10 mmHg. The lengths (unit:mm) of all parts of 
the apparatus are shown in FIG. 1. Twenty grams of melted fat 6 maintained 
at 80.degree. C. is introduced into the inner tube 1 into which a 
thermometer 4 equipped with rubber stopper 3 has been inserted right in 
the center of the inner tube. The apparatus is set vertically in a water 
bath maintained at 12.degree. C., so that the mark M of the glass tube may 
be positioned at the level of the water. The fat is then cooled gradually 
by the water bath maintained at 12.degree. C. and measurement of 
temperature (.theta.; .degree.C.) of the fat with the passing of time (t; 
min) is started at the time when the temperature reaches 40.degree. C. The 
outline of a cooling curve of the sal fat is shown in FIG. 2. As the sal 
fat tends to be supercooled, the heat of crystallization of the fat causes 
the temperature of the fat to rise during the cooling procedure. Therefore 
the cooling curve will always have a minimum point and a maximum point 
which are defined respectively as points P (t.sub.MIN, .theta..sub.MIN) 
and Q (t.sub.MAX, .theta..sub.MAX) shown in FIG.-2. 
Blends of the sal fat of this invention and one or more of oils and fats 
such as palm oil, palm olein, a middle melting fraction of palm oil, 
mowrah fat (seed fat of Madhuca longifolia) and its fractions, shea fat 
(see fat of Butyrospermum parkii) and its fractions, kokum butter (seed 
fat of Garcinia indica) and its fractions, mango kernel (seed fat of 
Mangifera indica) and its fractions are suitable for use as cocoa butter 
substitutes of better quality. The above-mentioned middle melting fraction 
of palm oil is the fraction which is obtained by removing lower and higher 
melting fractions from palm oil by a method of fractionating oils and 
fats. The above-mentioned palm olein is the fraction which is obtained by 
removing a higher melting fraction from palm oil by a method of 
fractionating oils and fats. As above-mentioned, a cocoa butter substitute 
composition of better quality having improved characteristic properties of 
the refined sal fat can be obtained by mixing the above-mentioned oils and 
fats with the refined sal fat. Specifically, a cocoa butter substitute 
composition comprising 80-95% by weight of the refined sal fat and 5-20% 
by weight of refined palm oil having an iodine value of 47-54 has a very 
good quality and improved characteristic properties as a cocoa butter 
substitute. A cocoa butter substitute composition can be obtained by 
mixing the above-mentioned oils and fats with the refined sal fat and also 
by refining a mixture of crude sal fat and crude oils and fats such as 
crude palm oil, crude mowrah fat, crude shea fat, crude kokum fat, crude 
mango kernel oil, and crude illipe fat under the condition of changing 
crude sal fat into refined sal fat according to the present invention. 
The following examples will illustrate this invention. However this 
invention is not limited to the following examples. 
EXAMPLE 1 
One thousand grams of crude sal fat (AV(acid value) 11.2, IV(iodine value) 
38.0) were subjected to an acid treatment by adding 4.0 g of phosphoric 
acid (75% purity) and stirring it for 10 minutes at 60.degree. C., and 
then it was allowed to stand still for 15 minutes. It was then filtered 
for removing aggregated gummy materials. 900 g of the filtrate or degummed 
fat were then subjected to deacidification by adding 170 g of 17 W/W % 
aqueous NaOH and stirring it for 10 minutes. After standing for several 
minutes, it was then filtered for removing the foots that were formed. Hot 
water was then added to the filtrate and it was stirred vigorously. After 
it was allowed to stand still for several minutes, the water layer was 
removed. Furthermore, the hot water washing was repeated two more times. 
The moisture entrained in the fat was removed by stirring under reduced 
pressure. It was then subjected to bleaching by adding activated clay in 
an amount of 7 weight % based on the weight of the fat and stirring at 
110.degree. C. for 5 minutes under reduced pressure. It was then filtered 
for removing the activated clay. The filtrate, or bleached fat, was then 
subjected to steam distillation at 230.degree. C. for 3 hours for 
effecting deodorization. The acid value of the refined fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 12.8 
Solid fat index at 30.degree. C. 
50.2 
t.sub.MAX 105 minutes 
.theta..sub.MAX 19.0.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as a cocoa butter 
substitute according to the following procedure. 
Table 1 
______________________________________ 
Formulation of chocolate 
______________________________________ 
Cocoa butter substitutes 
25 parts by weight 
(refined sal fat) 
Powdered sugar 50 parts by weight 
Chocolate liquor 5 parts by weight 
Cocoa powder 10 parts by weight 
Full milk powder 5 parts by weight 
Skimmed milk powder 5 parts by weight 
Lecithin 0.4 parts by weight 
Vanillin 0.02 parts by weight 
______________________________________ 
The ingredients were mixed according to the formulation of chocolate shown 
in the Table 1 except for a portion of the cocoa butter substitute and 
after the mixture was refined on a five-roller mill the additional cocoa 
butter substitute was added so as to satisfy the formulation. Then the 
mixture was subjected to conching in a rotary conche at a temperature of 
50.degree. C. for about 8 hours and then decreasing the temperature to 
35.degree. C. in the rotary conche. And after the mixture, namely, the 
chocolate paste, was subjected to tempering at a temperature of 27.degree. 
C. for 5 minutes, it was warmed up to 38.degree. C. in the tempering 
device. It was then filled into a mould and the mold was cooled by pasing 
it through a cooling tunnel. The solidified chocolate was then removed 
from the mould and was wrapped. It was then aged at a temperature of 
20.degree. C. for 2 weeks. 
It was checked whether the solidifying velocity of chocolate paste was 
reasonable or not during the cooling step following the tempering step, 
and it was also checked whether the solidified chocolate was easily 
removed from the mould in the removing step in the manufacturing process 
of chocolate. The quality of the finished product was examined from the 
viewpoints of the state of the surface of the chocolate, the solidity and 
heat resistance, the mouth-melting property, and the fat bloom resistance. 
The fat blooming resistance was checked by setting the chocolates in a box 
maintained at 20.degree. C. for 12 hours and then at 30.degree. C. for 12 
hours alternately. The alternation was repeated until the fat bloom 
appeared on the surface of chocolates. As a result, the chocolate paste 
obtained from the above-mentioned sal fat was solidified with good 
solidifying velocity and the solidified chocolate was easily removed from 
the mould. The qualities of the finished product were excellent. 
EXAMPLE 2 
One thousand grams of crude sal fat (AV 15.3, IV 38.7) were subjected to 
the acid treatment by adding 4.0 g of phosphoric acid (75% purity) and 
stirring it for 10 minutes at 60.degree. C. and then it was allowed to 
stand still for 15 minutes. It was then filtered for removing aggregated 
gummy materials. 900 g of the filtrate were then subjected to a first 
deacidification by adding 58 g of 17 W/W % aqueous NaOH. It was then 
filtered for removing the foots that were formed. 500 g of the filtrate 
were then subjected to a second deacidification by adding 16 g of 17 W/W % 
aqueous NaOH. It was then filtered for removing the foots that were 
formed. And it was then subjected to hot water washing, bleaching, and 
steam distillation under the same conditions as in Example 1. The acid 
value of the refined fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 15.9 
Solid fat index at 30.degree. C. 
49.2 
T.sub.MAX 110 minutes 
.theta..sub.MAX 17.6.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 1. The 
chocolate paste was solidified with a reasonable solidifying velocity and 
the solidified chocolate was easily removed from the mould. The qualities 
of the finished product were excellent. 
EXAMPLE 3 
Crude sal fat (AV 24.4, IV 39.5) was subjected to phosphoric acid 
treatment, first and second deacidification, and hot water washing. It was 
then subjected to column chromatographic fractionation by passing a 
mixture of 200 g of the sal fat and 300 g of n-hexane through a column 
(.phi.=3.5 cm) containing 200 g of silica gel and then passing 3000 g of 
n-hexane. The n-hexane was removed from the eluted solution by 
distillation. 150 g of the sal fat (hydroxy value 1.5) was obtained as an 
eluted fraction. The fat was then subjected to bleaching by using 5 W/W % 
of activated clay. It was then subjected to steam distillation for 
deodorization. The acid value of the refined fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows: 
______________________________________ 
Hydroxy value 1.4 
Solid fat index at 30.degree. C. 
51.5 
t.sub.MAX 80 minutes 
.theta..sub.MAX 24.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 1. The 
chocolate paste was solidified with reasonable solidifying velocity and 
the solidified chocolate was easily removed from the mould. The qualities 
of the finishing product were excellent. 
EXAMPLE 4 
Crude sal fat (AV 17.0, IV 39.0) was refined by the same procedure and 
under the same refining conditions as in Example 3. The acid value of the 
refined sal fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 1.0 
solid fat index at 30.degree. C. 
52.0 
t.sub.MAX 70 minutes 
.theta..sub.MAX 26.0.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 1. The 
chocolate paste was solidified with reasonable solidifying velocity and 
the solidified chocolate was easily removed from the mould. The qualities 
of the finished product were very excellent. 
EXAMPLE 5 
Crude sal fat (AV 24.4, IV 39.5) was subjected to column chromatographic 
fractionation by passing a mixture of 200 g of crude sal fat and 200 g of 
chloroform through a column (.phi.=3.5 cm) containing 200 g of Florisil 
(Trademark) and then passing 1500 g of chloroform. The chloroform was 
removed from the eluted solution by distillation. 156 g of the sal fat 
(hydroxy value 4.8) was obtained as an eluted fraction. The fat was then 
subjected to deacidification, bleaching, and deodorization by the same 
procedure and under the same conditions as in Example 1. The acid value of 
the refined sal fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 4.8 
Solid fat index at 30.degree. C. 
51.3 
t.sub.MAX 85 minutes 
.theta..sub.MAX 22.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 1. The 
chocolate paste was solidified with reasonable solidifying velocity and 
the solidified chocolate was easily removed from the mould. The qualities 
of the finished product were excellent. 
EXAMPLE 6 
Crude sal fat (AV 17.0, IV 39.0) was subjected to phosphoric acid 
treatment, deacidification, and hot water washing by the same procedure 
and under the same conditions as in Example 2. 400 g of the sal fat was 
mixed with 2000 g of n-hexane and the mixture was then cooled to 
-5.degree. C. and held at that temperature for 30 minutes. 275 g of a cake 
fat (hydroxy value 8.1) were obtained by filtration of the mixture. The 
cake fat was then subjected to bleaching and deodorization by the same 
procedure as in Example 2. The acid value of the refined sal fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 8.0 
Solid fat index at 30.degree. C. 
52.0 
t.sub.MAX 90 minutes 
.theta..sub.MAX 20.0.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 1. The 
chocolate paste was solidified with reasonable solidifying velocity and 
the solidified chocolate was easily removed from the mould. The qualities 
of the finished product were excellent. 
EXAMPLE 7 
Crude sal fat (AV 24.4, IV 39.5) was subjected to phosphoric acid 
treatment, deacidification, and hot water washing by the same procedure 
and under the same conditions as in Example 2. 400 g of the sal fat were 
mixed with 2400 g of acetone and the mixture was then cooled to 5.degree. 
C. and held at that temperature for 30 minutes. 280 g of a cake fat 
(hydroxy value 8.2) were obtained by filtration of the mixture. The cake 
fat was then subjected to bleaching and deodorization by the same 
procedure as in Example 3. The acid value of the refined sal fat was 0.05. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 8.0 
Solid fat index at 30.degree. C. 
50.7 
t.sub.MAX 95 minutes 
.theta..sub.MAX 18.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 1. The 
chocolate paste was solidified with reasonable solidifying velocity and 
the solidified chocolate was easily removed from the mould. The qualities 
of the finished product were excellent. 
COMATIVE EXAMPLE 1 
One thousand grams crude sal fat (AV 11.2, IV 38.0) was subjected to 
deacidification by adding 61 g of 17 W/W % aqueous NaOH and stirring it 
for 10 minutes. After standing for several minutes, it was then filtered 
for removing the foots that were formed. It was then subjected to 
bleaching by adding the activated clay in an amount of 3 weight %, based 
on the weight of the fat, and stirring at 110.degree. C. for 5 minutes 
under reduced pressure. It was then filtered for removing the activated 
clay. The filtrate was then subjected to steam distillation at 250.degree. 
C. for 2 hours for the deodorization. The acid value of the refined fat 
was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 12.7 
Solid fat index at 30.degree. C. 
48.0 
t.sub.MAX 130 minutes 
.theta..sub.MAX 16.5.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described hereinbefore. The 
chocolate paste was not solidified with reasonable solidifying velocity 
and the solidified chocolate was not easily removed from the mould. The 
qualities of the finished product were undesirable. 
COMATIVE EXAMPLE 2 
Crude sal fat (AV 17.0, IV 39.0) was refined by the same procedure as in 
Example 2. The acid value of the refined fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 17.6 
solid fat index at 30.degree. C. 
49.5 
t.sub.MAX 145 minutes 
.theta..sub.MAX 16.2.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described hereinbefore. The 
chocolate paste was not solidified with reasonable solidifying velocity 
and the solidified chocolate was not easily removed from the mould. The 
qualities of the finished product were undesirable. 
COMATIVE EXAMPLE 3 
Crude sal fat (AV 24.4, IV 39.5) was refined by the same procedure as in 
Example 2. The acid value of the refined fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 25.8 
Solid fat index at 30.degree. C. 
45.0 
t.sub.MAX 
maximum point did not appear. 
.theta..sub.MAX 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described hereinbefore. The 
chocolate paste was not solidifed with reasonable solidifying velocity and 
the solidified chocolate was not easily removed from the mould. The 
qualities of the finished product were undesirable. 
EXAMPLE 8 
One thounsand grams of crude sal fat (AV 5.3, IV 40.1) having 0.1 weight % 
of hydroxy and epoxy fatty acids based on the total fatty acids 
composition were subjected to the acid treatment by adding 2.0 g of 
phosphoric acid (75% purity) and stirring it for 10 minutes at 60.degree. 
C. It was then filtered for removing aggregated gummy materials. 900 g of 
the filtrate or degummed fat were then subjected to deacidification by 
adding 80 g of 20 W/W % aqueous NaOH and stirring for 10 minutes. After it 
was allowed to stand still for several minutes, it was then filtered for 
removing the foots that were formed. Hot water was then added to the 
filtrate and was stirred vigorously. After standing for several minutes, 
the water layer was removed. Furthermore, the hot water washing was 
repeated two more times. The moisture entrained in the fat was removed by 
stirring under reduced pressure. The fat was then subjected to bleaching 
by adding activated clay in an amount of 15 weight % based on the weight 
of the fat and stirring at 110.degree. C. for 5 minutes under reduced 
pressure. It was then filtered for removing the activated clay. The 
filtrate was then subjected to steam distillation at 250.degree. C. for 
one hour for effecting deodorization. The acid value of refined sal fat 
was 0.04. 
The hydroxy and epoxy fatty acids content, hydroxy value, solid fat index 
at 30.degree. C., t.sub.MAX and .theta..sub.MAX of the refined sal fat 
were as follows. 
______________________________________ 
Hydroxy & epoxy fatty acids content 
0.1 % 
Hydroxy value 5.9 
Solid fat index at 30.degree. C. 
60.5 
t.sub.MAX 50 minutes 
.theta..sub.MAX 22.5.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as a cocoa butter 
substitute according to the following procedure. 
Table 2 
______________________________________ 
Formulation of chocolate 
______________________________________ 
Cocoa butter substitute 
10.0 (parts by weight) 
(refined sal fat) -Powdered sugar 
45.0 (parts by weight) 
Cocoa butter 10.0 (parts by weight) 
Chocolate liquor 20.0 (parts by weight) 
Full milk powder 15.0 (parts by weight) 
Lecithin 0.30 (parts by weight) 
Vanillin 0.02 (parts by weight) 
______________________________________ 
The ingredients were mixed according to the formulation of chocolate shown 
in the Table 2 except for a portion of the cocoa butter substitute and 
cocoa butter and after the mixture was refined on a five-roller mill, the 
remaining cocoa butter substitute and cocoa butter was added so as to 
satisfy the formulation. Then the mixture was subjected to conching in a 
rotary conche at a temperature of 50.degree. C. for about 10 hours and 
then decreasing the temperature to 35.degree. C. in the rotary conche. And 
after the mixture, namely, the chocolate paste, was subjected to tempering 
at a temperature of 27.degree. C. for 5 minutes, it was warmed up to 
38.degree. C. in the tempering device. It was then filled into a mould and 
was cooled by passing it through a cooling tunnel. The solidified 
chocolate was then removed from the mould and was wrapped. It was then 
aged at a temperature of 20.degree. C. for 2 weeks. 
It was checked whether the solidifying velocity of chocolate paste was 
reasonable or not in the course of the cooling step following the 
tempering step, and it was also checked whether the solidified chocolate 
was easily removed from the mould in the removing step in the 
manufacturing process of chocolate. The quality of the finished product 
was examined from the viewpoints of the surface state, the solidity and 
heat resistance, the mouth-melting property, and the fat bloom resistance. 
The results are shown in Table 3. 
The fat blooming resistance was checked by setting the chocolates in a box 
maintained at 20.degree. C. for 12 hours and then at 30.degree. C. for 12 
hours alternately. The alternation was repeated until the fat bloom 
appeared on the surfaces of the chocolates. The result is shown in Table 
4. 
EXAMPLE 9 
Crude sal fat (AV 14.0, IV 39.0) having 1.1 weight % of hydroxy and epoxy 
fatty acids based on the total fatty acid composition was refined by the 
same procedure as in Example 8. 
The hydroxy and epoxy fatty acids content, hydroxy value, solid fat index 
at 30.degree. C., t.sub.MAX and .theta..sub.MAX of the refined sal fat 
were as follows. 
______________________________________ 
Hydroxy and epoxy fatty acids content 
1.1 % 
Hydroxy value 14.2 
Solid fat index at 30.degree. C. 
51.3 
t.sub.MAX 60 minutes 
.theta..sub.MAX 20.5.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described in Example 8. The result 
is shown in Tables 3 and 4. 
EXAMPLE 10 
Four hundred grams of crude sal fat (AV 5.6, IV 38.0) having 5.1 weight % 
of hydroxy and epoxy fatty acids based on the total fatty acid composition 
were mixed with 1600 g of n-hexane. The mixture was cooled to 15.degree. 
C. and kept at that temperature for 60 minutes with stirring. 370 g of 
filtrate was obtained by filtration of the mixture. The filtrate fat was 
refined by the same procedure as in Example 8. The acid value of the 
refined fat was 0.04. 
The hydroxy and epoxy fatty acids content, hydroxy value, solid fat index 
at 30.degree. C., t.sub.MAX and .theta..sub.MAX of the refined fat were as 
follows. 
______________________________________ 
Hydroxy and epoxy fatty acids content 
0.9 
Hydroxy value 5.0 
Solid fat index at 30.degree. C. 
58.4 
t.sub.MAX 55 minutes 
.theta..sub.MAX 20.5.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined fat as cocoa butter 
substitute according to the procedure described in Example 8. The results 
are shown in Tables 3 and 4. 
EXAMPLE 11 
Crude sal fat (AV 6.9, IV 39.1) having 3.2% of hydroxy and epoxy fatty 
acids based on the total fatty acids composition was subjected to the acid 
treatment, deacidification, and bleaching by the same procedure as in 
Example 8. 1000 g of the bleached fat were kept at 38.degree. C. for 48 
hours. Thereafter, 200 g of aqueous solution containing sodium lauryl 
sulfate (0.5 W/W %) and magnesium sulfate (2.0 W/W %) was added to the 
fat. It was then stirred vigorously and then crystallized fat was removed 
by centrifugation. It was then subjected to hot water washing. After 
removing the entrained water, it was subjected to the steam distillation 
at 250.degree. C. for one hour. The acid value of the refined fat was 
0.04. 
The hydroxy and epoxy fatty acids content, hydroxy value, solid fat index 
at 30.degree. C., t.sub.MAX and .theta..sub.MAX of the refined fat were as 
follows. 
______________________________________ 
Hydroxy and epoxy fatty acids content 
1.0 % 
Hydroxy value 7.3 
Solid fat index at 30.degree. C. 
52.3 
t.sub.MAX 75 minutes 
.theta..sub.MAX 19.0.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined fat as cocoa butter 
substitute according to the procedure described in Example 8. The results 
are shown in Tables 3 and 4. 
COMATIVE EXAMPLE 4 
Crude sal fat (AV 5.6, IV 38.0) having 5.1 weight % of hydroxy and epoxy 
fatty acids based on the total fatty acids composition was refined by the 
same procedure as in Example 8. The acid value of the refined sal fat was 
0.04. 
The hydroxy and epoxy fatty acids content, hydroxy value, solid fat index 
at 30.degree. C., t.sub.MAX and .theta..sub.MAX of the refined fat were as 
follows. 
______________________________________ 
Hydroxy and epoxy fatty acids content 
5.1% 
Hydroxy value 29.8 
Solid fat index at 30.degree. C. 
56.9 
t.sub.MAX 80 minutes 
.theta..sub.MAX 20.5.degree. C. 
______________________________________ 
Chocolate was manufactured by using the refined sal fat as cocoa butter 
substitute according to the procedure described hereinbefore. The 
chocolate paste was not solidified with reasonable solidifying velocity 
and the solidified chocolate was not easily removed from the mould. The 
qualities of the finished product were undesirable. 
Table-3 
______________________________________ 
The result of the chocolate preparing test 
the qualities of the prepared chocolate 
The result of The qualities 
the chocolate of the prepared 
preparing test 
chocolate 
Sample Mouth- 
(refined Solidifying 
Mould melting 
sal fat) velocity release property 
Flavour 
______________________________________ 
of example 8 
very very good good 
good good 
of example 9 
good good good good 
of example 10 
good good good good 
of example 11 
good good good good 
of comparative 
good bad bad bad 
example 4 
______________________________________ 
Table-4 
__________________________________________________________________________ 
The result of fat blooming test 
(one cycle: 20.degree. C. for 12 hours/30.degree. C. for 12 hours) 
Sample 0 5 10 
15 
20 
25 30 35 50 75 80 85 90 
__________________________________________________________________________ 
Chocolate 
of example 8 
- - - - - - - - - .+-. 
+ ++ ++ 
of example 9 
- - - - - - - - .+-. 
.+-. 
+ ++ ++ 
of example 10 
- - - - - - - - .+-. 
.+-. 
+ ++ ++ 
of example 11 
- - - - - - - .+-. 
.+-. 
+ + ++ ++ 
of comparative 
- - .+-. 
.+-. 
+ ++ ++ ++ ++ ++ ++ ++ ++ 
example 4 
__________________________________________________________________________ 
-State of the surface having luster 
.+-.State of the surface having slight fat bloom 
+State of the surface having apparent fat bloom 
++State of the surface having larger amount of fat bloom 
EXAMPLE 12 
10 Kg of crude sal fat (AV 8.5, IV 39.2) was refined by the same procedure 
as in Example 1. The acid value of the refined sal fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 9.2 
Solid fat index at 30.degree. C. 
51.6 
t.sub.MAX 95 minutes 
.theta..sub.MAX 19.8.degree. C. 
______________________________________ 
The refined sal fat was blended with refined palm oil (AV 0.04, IV 53.0) of 
which the proportions were 0 (Sample No. 1), 3 (Sample No. 2), 5 (Sample 
No. 3), 10 (Sample No. 4) 20 (Sample No. 5) and 30 (Sample No. 6) weight % 
based on the weight of blended fats. The solid fat index and the 
parameters of the cooling curve of the refined sal fat and blended fats 
are shown in Table 5. 
Chocolates were manufactured by using the refined sal fat and the blended 
fat as cocoa butter substitute according to the procedure described in 
Example 8. The results of the manufacturing process and the qualities of 
the finished products are shown in Table 6. The fat blooming resistance of 
these chocolates was checked by the procedure described hereinbefore, and 
the results are shown in Table 7. The qualities of the chocolates of 
Sample No. 3, 4 and 5 were very excellent as shown in Table 6 and Table 7. 
Table-5 
__________________________________________________________________________ 
Solid fat index and parameters of cooling curve 
of blended fat of sal fat and palm oil 
Cocoa butter 
substitute 
Sal Palm 
Sam- 
fat oil 
ple 
weight 
weight 
Solid fat index Cooling curve 
No. 
% % 20.degree. C. 
30.degree. C. 
35.degree. C. 
40.degree. C. 
(t.sub.MIN, .theta..sub.MIN) 
(t.sub.MAX, .theta..sub.MAX) 
__________________________________________________________________________ 
1 100 0 58.2 
51.6 
7.0 0 (60, 16.5) 
(95, 19.8) 
2 97 3 57.3 
49.8 
6.4 0 (58, 16.8) 
(92, 19.6) 
3 95 5 57.2 
45.7 
5.8 0 (52, 17.0) 
(80, 19.5) 
4 90 10 56.4 
40.9 
4.0 0 (50, 16.5) 
(75, 19.5) 
5 80 20 52.6 
38.3 
3.1 0 (55, 16.9) 
(85, 19.5) 
6 70 30 49.1 
30.6 
2.2 0 (80, 17.8) 
(110, 18.1) 
__________________________________________________________________________ 
Table-6 
______________________________________ 
Manufacturing test and qualities of chocolates 
Manufacturing test Qualities of chocolates 
Sample Solidifying Mould Mouth-melting 
No. velocity release property Flavour 
______________________________________ 
1 reasonable good good good 
2 reasonable good good good 
3 very reasonable 
good good good 
4 very reasonable 
very good very 
good good 
5 reasonable good good good 
6 un- bad good bad 
reasonable 
______________________________________ 
Table-7 
__________________________________________________________________________ 
Fat blooming test 
one cycle = 20.degree. C. for 12 hours/30.degree. C. for 12 hours 
Cycle 
No 
Sample 
No. 0 5 10 
15 
20 
25 30 35 50 75 80 85 90 
__________________________________________________________________________ 
1 - - - - - - - - .+-. 
+ ++ ++ ++ 
2 - - - - - - - - .+-. 
.+-. 
+ + ++ 
3 - - - - - - - - - - - .+-. 
.+-. 
4 - - - - - - - - - - - .+-. 
.+-. 
5 - - - - - - - - - - .+-. 
.+-. 
.+-. 
6 - - - - - .+-. 
+ + ++ ++ ++ ++ ++ 
__________________________________________________________________________ 
Symbol- 
- State of the surface having luster 
.+-. State of the surface having slight fat 
+ State of the surface having apparent fat bloom 
++ State of the surface having larger amount of fat bloom 
EXAMPLE 13 
10 Kg of crude sal fat (AV 14.0, IV 38.5) were refined by the same 
procedure as in Example 1. The acid value of the refined sal fat was 0.04. 
The hydroxy value, solid fat index at 30.degree. C., t.sub.MAX and 
.theta..sub.MAX of the refined sal fat were as follows. 
______________________________________ 
Hydroxy value 14.8 
Solid fat index at 30.degree. C. 
50.3 
t.sub.MAX 110 minutes 
.theta..sub.MAX 17.6.degree. C. 
______________________________________ 
The refined sal fat was blended with refined palm oil (AV 0.04, IV 48.9) of 
which the proportions were 0 (Sample No. 1), 3 (Sample No. 2), 5 (Sample 
No. 3), 10 (Sample No. 4), 15 (Sample No. 5), and 25 (Sample No. 6) weight 
% based on the weight of blended fats. The solid fat index and the 
parameters of the cooling curve of the refined sal fat and blended fats 
are shown in Table 8. 
Chocolate were manufactured by using the refined sal fat and the blended 
fat as cocoa butter substitute according to the procedure described in 
Example 8. The results of the manufacturing process and the qualities of 
the product are shown in Table 9. The fat blooming resistance of these 
chocolates was checked by the procedure described hereinbefore, and the 
results are shown in Table 10. The qualities of the chocolates of Sample 
No. 3, 4, and 5 were very excellent as shown in Table 9 and Table 10. 
Table-8 
__________________________________________________________________________ 
Solid fat index and parameters of cooling 
curve of blended fat of sal fat and palm oil 
Cocoa butter 
substitute 
Sal Palm 
Sam- 
fat oil 
ple 
weight 
weight 
Solid fat index Cooling curve 
No. 
% % 20.degree. C. 
30.degree. C. 
35.degree. C. 
40.degree. C. 
(t.sub.MIN' .theta..sub.MIN) 
(t.sub.MAX, .theta..sub.MAX) 
__________________________________________________________________________ 
1 100 0 59.3 
50.3 
6.5 0 (80, 15.2) 
(110, 17.6) 
2 97 3 58.9 
49.0 
6.0 0 (75, 15.5) 
(105, 18.0) 
3 95 5 57.2 
45.2 
5.5 0 (70, 15.7) 
(100, 18.2) 
4 90 10 55.7 
40.3 
4.2 0 (70, 16.0) 
(95, 18.2) 
5 85 15 52.6 
38.0 
3.2 0 (75, 15.9) 
(105, 17.5) 
6 75 25 48.3 
30.1 
2.0 0 (--)* (--)* 
__________________________________________________________________________ 
*Maximum point did not appear. 
Table-9 
______________________________________ 
Manufacturing test and qualities of chocolates 
Manufacturing test 
Qualities of chocolates 
Sample Solidifying 
Mould mouth-melting 
No. velocity release property flavour 
______________________________________ 
1 reasonable 
good good good 
2 reasonable 
good good good 
3 reasonable 
good good good 
4 reasonable 
good good good 
5 reasonable 
good good good 
6 un- bad good bad 
reasonable 
______________________________________ 
Table-10 
__________________________________________________________________________ 
Fat blooming test 
Cycle No. 
Sample 
No. 0 5 10 
15 
20 
25 
30 
35 
37 
40 
50 75 80 85 90 
__________________________________________________________________________ 
1 - - - - - - - - - .+-. 
.+-. 
+ + ++ ++ 
2 - - - - - - - - - - .+-. 
.+-. 
+ + ++ 
3 - - - - - - - - - - - - - .+-. 
.+-. 
4 - - - - - - - - - - - - - .+-. 
.+-. 
5 - - - - - - - - - - - - .+-. 
.+-. 
.+-. 
6 - - - - - .+-. 
.+-. 
.+-. 
+ + ++ ++ ++ ++ ++ 
__________________________________________________________________________ 
Symbol 
-State of the surface having luster 
.+-.State of the surface having slight fat bloom 
+State of the surface having apparent fat bloom 
++State of the surface having larger amount of fat bloom