HARD BUTTER COMPOSITION

Abstract: A hard butter composition suitable for a cocoa butter substitute which comprises as a main ingredient a β-­ unsaturated-α,α′-disaturated triglyceride, constituent satura­ ted fatty acids of which contain at least 4% by weight of one or plurality of fatty acids selected from the group consisting of behenic acid, lignoceric aid, cerotic acid and arachidic acid, provided that the amount of arachidic acid is less than 4% by weight based on the total weight of the constituent saturated fatty acids.

Description: The present invention relates to a hard butter composition. More particularly, the hard butter composition of the present invention is useful in fatty confectionery, for example chocolate may be produced by using the composition instead of a part or all of the cocoa butter. U.K. Patent 827172 (1960) teaches that a mixture (hard butter) obtained by mixing a palm mid-fraction, and Borneo tallow or a Borneo tallow type fat such as Shorea robusta , etc. in a ratio of from 25 : 75 to 75 : 25 is good as a cocoa butter substitute. According to the specification of this U.K. Patent, Borneo tallow or the Borneo tallow type fat used contains not less than 50 %, preferably not less than 60 %, of triglycerides composed of one unsaturated fatty acid residue (U) substantially derived from oleic acid (0) and two saturated fatty acid residues (S) rich in those derived from palmitic acid (P) and stearic acid (St). Almost all the remaining triglycerides are those composed of two unsaturated fatty acid residues (U) and one saturated fatty acid residue (S). Further, according to the specification, it is desirable to minimize the amount of triglycerides composed of three saturated fatty acid residues (SSS) and/or three unsaturated fatty acid residues (UUU). An analogous technique is disclosed in Japanese Patent Publication No 115863/1978. This publication teaches a hard butter containing triglycerides composed of saturated fatty acid residues substantially derived from fatty acids selected from P, St and arachic acid and unsaturated fatty acid residues substantially derived from fatty acids selected from 0 and linoleic acid, wherein the amount of the residue derived from arachidic acid is 4 to 15 % based on the total of S, and the amount of the residue derived from linoleic acid is not more than 20 % based on the total of U. The constituent triglycerides of this hard butter contain 50 to 80 %, preferably 55 to 75 %, of SUS ( β -unsaturated-α,α' -disaturated triglyceride); 15 to 50 %, preferably 25 to 45 % of SUU ( α or α' -saturated diunsaturated triglyceride); 1 to 5 %, preferably, 1 to 3 % of SSS; not more than 5 %, preferably not more than 3 %, of USU ( α or α' -diunsaturated triglyceride); and not more than 6 %, preferably not moe than 4 %, of UUU. The constituent triglycerides of Shorea robusta disclosed in the above U.K. Patent Specification contain a relatively large amount of arachic acid residue in addition to the residues derived from P and St. However, they scarcely contain fatty acid residues derived from fatty acids having more longer carbon chains. Further, although the amount of arachic acid is defined in the above Japanese Patent Laid Open Publication, it does not teach the effect of fatty acids having more longer carbon chains as constituent fatty acids of triglycerides. On the other hand, Japanese Patent Publication No 27497/1985 discloses a process for producing a trans-acid type bard butter having a specific fatty acid composition consisting of elaidic acid, palmitic acid, behenic acid and other fatty acids, wherein the fatty acid residues are randomly distributed. However, such a trans-acid type hard butter has inferior miscibility with cocoa butter (i.e., difficulty of obtaining uniform crystallization during tempering step) and, therefore, has drawbacks, for example, poor taste of fatty confectionery such as chocolate produced by using the hard butter due to a significant limitation of the amount of cocoa-liquor. FR-A-2 435 206 describes a cocoa butter substitute consisting essentially of a mixture of triglycerides of saturated and unsaturated fatty acids of which 50 to 80 mol. % are a triglyceride of the SUS type. The saturated acids employed in the mixture consist essentially of palmitic acid, stearic acid and arachidic acid with the provision that the arachidic acid is present in an amount of 4 to 15 mol. % of the total amount of saturated acids. Recently, the preference has tended to be for food to be soft. On the other hand, in this field, it has been requested to develop a hard butter which maintains a certain degree of hardness even at a high temperature, and does not produce or at least resists "fat blooming". However, both of these requested properties are quite inconsistent with each other and it is very difficult to impart both properties to a hard butter, simultaneously. In addition, a hard butter to be used as a cocoa butter substitute should melt rapidly and sharply at about the body temperature. Further, workability during tempering thereof is also an important factor. In this regard, even if the difference in compositions of hard butters is only a very little, the above property and factor are significantly varied, and it is very difficult to discover relationships between properties and compositions of hard butters even for those skilled in the art. For example, although a fat or oil containing a large amount of diglycerides and/or dihydroxy fatty acid glycerides advantageously effects an improvement of anti-blooming property, tempering is inhibited because formation of crystal nuclei and crystal growth in tempering are slow and, in general, excess cooling is required, which results in inconveniences during working such as slow solidification rate, difficulty in release from a mold in a molding step, etc. It would be desirable to obtain a hard butter which has a soft mouth feel (is soft biting) and also has a certain degree of hardness at a high temperature with a good anti-blooming property as well as good workability during production such as in tempering and, in addition, can rapidly and sharply melt at about the body temperature. It has been found that certain triglycerides containing saturated fatty acids having carbon chains which are longer than or the same as that of arachic acid as the constituent saturated fatty acids at the α and/or α' positions make it possible to obtain a hard butter having both an improved anti-blooming property and good miscibility with cocoa butter without diglycerides or dihydroxy fatty acid glycerides which inhibit tempering, and to produce fatty confectionery such as chocolate having softer mouth feel. The present invention provides a hard butter composition which comprises as a main ingredient a triglyceride SUS, constituent saturated fatty acids of which contain at least 4 % by weight of one or more of behenic acid, lignoceric acid, cerotic acid and arachidic acid, provided that the amount of arachidic acid is less than 4 % by weight based on the total weight of the constituent saturated fatty acids. The main ingredient of the composition of the present invention is the triglyceride SUS. The constituent saturated fatty acids thereof contain at least 4 % by weight of one or more of fatty acids selected from the group consisting of behenic acid, lignoceric acid, cerotic acid and arachidic acid, provided that the amount of arachidic acid, if any, is always less than 4 % by weight based on the total weight of all constituent saturated fatty acids of the glyceride. When the amount of these saturated fatty acids is lower than 4 % by weight, the desired improvement cannot be obtained. On the other hand, when the total amount of behenic acid, lignoceric acid, cerotic acid and arachidic acid in a fatty confectionery is too great, difficulty arises in tempering and the melting point is depressed. Accordingly, the total amount of behenic acid, lignoceric acid, cerotic acid and arachidic acid is preferably not more than 30 % by weight based on the total amount of all the constituent saturated fatty acids of the glyceride. The constituent saturated fatty acids of the glyceride other than behenic acid, lignoceric acid, cerotic acid and arachidic acid are substantially composed of fatty acids having carbon atoms of not less than 16, e.g., P and St. The composition of the present invention contains the triglyceride SUS in an amount of, preferably, 50 % by weight or more, more preferably, 65 % by weight or more based on the total amount of triglycerides in the composition. The composition can contain other triglycerides such as SUU, SSS, SSU, USU and UUU, provided that U should be substantially free from elaidic acid, that is, the content of elaidic acid is usually not more than 3 % by weight based on the total amount of fatty acids of triglycerides. The amounts of SSS, SSU, USU and UUU are preferably not more than 6 % by weight, more preferably, not more than 3 % by weight based on the total amount of triglycerides in the composition, respectively. When the contents of SSS, SSU, and USU are too high, viscosity is abnormally increased in the tempering step. When the content of UUU is too high, high-temperature resistance of products becomes inferior. The composition may contain a relatively higher amount of SUU. The total triglyceride content of the composition is preferably not less than 90 % by weight, more preferably not less than 97 % by weight based on the weight of the composition. The hard butter composition of the present invention is a fat having the above desired triglyceride composition or a mixture of such a fat and other fat ingredients suitable for a cocoa butter substitute such as palm mid-fraction. Fats having the desired triglyceride composition can be produced by processing of natural fats and oils or synthesis of glycerides. For example, the fat can be produced by using natural fats and oils such as Niam Fat (kernel oil of Lophira alata , Lophira ochnaceae , Lophira proceral ) and the like as starting materials, or by using processed fats and oils obtained by introducing fatty acids having desired longer carbon chains derived from botanical wax components and the like into fats and oils as starting materials. Introduction of suitable fatty acids into fats and oils may be carried out according to a conventional method, for example, as follows. Fats and oils containing unsaturated fatty acids having not less than 20 carbon atoms, for example rapeseed oil, black mustard oil, white mustard oil, radish seed oil, fish oils such as herring oil and sardine oil, whale oil, liver oil such as that from shark, or plant wax such as rice bran wax, for example, can be used as souces for fatty acids to be introduced into fats and oils by subjecting them to suitable known means such as hydrogenation or hydrolysis, for example. The fat having a desired triglyceride composition can be produced by selectively introducing the fatty acids from one of the above sources or fatty esters obtained by conventional esterification of the fatty acids with monovalent alcohol into the α and α' positions of a fat or oil rich in unsaturated fatty acids residues at the β position thereof, for example, oleic safflower oil, camelia oil, palm oil, rapeseed oil, shea fat, sal fat, mango fat, kokum butter, Borneo tallow, malabar fat or a fractionated oil thereof according to a known selective transesterification and, if necessary, fractionating and removing high melting point and/or low melting point fractions of the resulting fat or oil (i.e., fractionation of the mid-fraction rich in SUS). Such selective transesterification and fractionation of the mid-fraction are disclosed by, for example, Japanese Patent Laid Open Publication No 127094/1981 (corresponding to U.S. Patent No 4,416,991). Optionally, the fat thus obtained may be mixed with other fat, particularly SUS rich fat such as palm-mid fraction to give the hard butter composition of the present invention. Or the fat thus obtained can be directly mixed with cocoa butter during production of fat confectionery. The following examples, reference examples and experiment further illustrate the present invention in detail but are not to be construed to limit the scope thereof. All "parts" and "%'s" are by weight unless otherwise stated. Example 1 High erucic acid rapeseed oil (10 parts) and low erucic acid rapeseed oil (90 parts) were mixed, hydrogenated (iodine value:<1 ), hydrolyzed and esterified to obtain fatty acid ethyl esters. The ethyl esters (70 parts) were mixed with high oleic acid sunflower oil (30 parts) and the mixture was subjected to transesterification by using an enzyme preparation having selectivity to the α and α' positions to obtain an oil (iodine value: 44.2). The resulting oil was further fractionated by using a solvent to obtain a mid-fraction (iodine value: 40.0, fractionation yield: 84.1 %). The oil was mixed with palm mid-fraction in a ratio of 9 : 1 and the mixture was refined according to a conventional method to obtain a hard butter composition (hard butter A). The ingredients and solid fat index (SFI) of the hard butter A are shown in Table 1. Example 2 A hard butter composition (hard butter B) was obtained in the same manner as in Example 1 except that 25 parts of high erucic acid rapeseed oil and 75 parts of low erucic acid rapeseed oil were used. The ingredients and SFI of the hard butter B are shown in Table 1. Reference Example 1 A hard butter composition (hard butter C) was obtained in the same manner as in Example 1 except that 100 parts of low erucin rapeseed oil was used without using high erucin rapeseed oil. The ingredients and SFI of the hard butter C are shown in Table 1. Reference Example 2 A hard butter composition (hard butter D) was obtained in the same manner as in Example 1 except that oil foots of sal fat were decomposed with sulfuric acid and subjected to fractional distillation to obtain a fatty acid fraction and the fatty acid fraction was extremely hydrogenated, esterified to the ethyl ester and used as a source for fatty acid to be introduced into high oleic sunflower oil. The ingredients and SFI of hard butter D are shown in Table 1. Experiment Hard butter A, B, C or D or Cocoa butter E (19.8 parts), cacao mass (15.7 parts), powdered whole milk (20 parts), powdered sugar (44.5 parts) and lecithin (0.5 part) were mixed and worked in a conche. Then, the mixture was subjected to tempering treatment wherein the mixture at 45 to 50°C was cooled to 26.5 to 27.0°C with stirring in a water bath and then the temperature of the water bath was raised (during this period,an increase in viscosity was measured). When the mixture reached 28 o C, it was cast in a mold and cooled at 5°C for 30 minutes. After aging at 18 to 20°C for 7 days, a portion of the product was stored at 30, 31 or 32°C for 2 hours and then its hardness was determined. Another portion of the product was further aged at 18 to 20°C for 20 days and then it was subjected to a storage test to determine anti-blooming property wherein storage at 20°C for 12 hours and then at 32°C for 12 hours was repeated and the number of repetitions necessary for producing bloom was recorded. The results of the experiment are shown in Table 2. As seen from hardness in Table 2, all hard butters A to D are more resistant to a high temperature than cocoa butter E. However, hard butter C which contains less behenic acid, lignoceric acid, cerotic acid and arachic acid has inferior mouth feel because melt property in the mouth thereof is poor and it lacks soft chewing property. Further, although the amount of arachic acid of hard butter D is substantially the same as that of behenic acid of hard butter B, the latter is superior to the former with respect to mouth feel and anti-blooming property. Hard butter A shows similar effect to hard butter B. This shows that the effect of behenic acid is superior to that of arachic acid. Reference Example 3 In the same manner as in Example 1, a fatty fraction was recovered by using the same starting materials except that transesterification was carried out by using sodium methylate (i.e., non-selective random transesterification). The composition of this fraction is shown in Table 3. As seen from Table 3, this fatty fraction contained only 14.4 % of SUS. Even if solvent fractionation was carried out, the ratio of SUS/SSU in the mid-fraction was hardly changed in comparison with that before fractionation. Then, this fatty fraction had poor miscibility with cocoa butter (i.e., difficulty in uniform crystallization in a tempering step) and inferior melt property in the mouth. Example 3 Ethyl esters of fatty acids obtained by hydrogenating to a high degree a mixture of high erucin rapeseed and low erucin rapeseed (10.5 : 59.5) and hydrolyzed and esterified (70 parts) were mixed with high oleic sunflower oil (30 parts) and the mixture was transesterified by using an enzyme preparation having selectivity to α and α' positions. The transesterified oil was subjected to solvent fractionation to obtain a mid-fraction. The composition of this fraction is shown in Table 3. This fraction has good soft mouth feel at a low temperature and improved anti-blooming property and the fraction itself can be used as the hard butter composition of the present invention. Example 4 Fatty acid ethyl esters obtained by hydrolyzing hardened rice bran wax and esterifying the resulting fatty acids (6 parts), other fatty acid ethyl esters obtained by subjecting hardened low erucin rapeseed oil to ethanolysis (79 parts) and high oleic sunflower oil (15 parts) were mixed and the mixture was transesterifed by using lipase having selectivity to the α and α' positions. The resulting oil was subjected to distillation to remove unreacted fatty acid ethyl esters. The oil was subjected to solution fractionation to remove high melting point fraction (4.2 %, iodine value: 8.6). The composition of the fraction obtained is shown in Table 3. It will be seen from the foregoing that we have provided hard butter compositions with good miscibility with cocoa butter and good soft mouth feel at a low temperature. Further, they have improved high-temperature resistance and improved anti-blooming property. Particularly, hard butter composition containing saturated fatty acid residues derived from behenic acid, lignoceric acid and cerotic acid, especially behenic acid and lignoceric acid, have better melt property in the mouth, soft biting property and anti-blooming property than hard butter composition containing saturated fatty acid residue derived from arachidic acid. The above triglycerides make it possible to obtain a hard butter composition having soft mouth feel at a low temperature as well as improved rapid melting at a temperature slightly lower than body temperature and improved anti-blooming property. Further, it is possible to obtain a hard butter composition having desired softness with a low content of diglycerides such as not more than 3 % to eliminate inhibition of tempering (a phenomenon requiring excess cooling) due to the diglycerides. Although no mechanism for the advantageous effects attained by the above triglycerides has yet become completely apparent, it is considered that soft mouth feel can be imparted because the difference in the number of carbon atoms between the glyceride SUS having saturated fatty acid residues derived from behenic acid, lignoceric acid, cerotic acid and arachidic acid, particularly, from the former three acids, and the glyceride SUS having the saturated fatty acid residues derived from only saturated fatty acids having 16 to 18 carbon atoms, which is a main ingredient of cocoa butter, is quite great and packing of respective crystalline units is relatively loose. Further, it is also considered that fat-blooming can be substantially prevented because, between SUS type glycerides having great differences in their carbon chain length, a transfer rate of crystals from a certain crystalline form to a most stable one is lowered and growth of fat crystals which form coarse crystals during storage is prevented. In addition, it is also considered that tempering can be carried out smoothly because the glyceride having saturated fatty acid residues derived from behenic acid, lignoceric acid and cerotic acid is an SUS type having a high melting point and, thereby, it can become good crystal nucleus during tempering. In this connection, it can be used as crystal seeds in a tempering step.

Claims: A hard butter composition which comprises as a main ingredient a triglyceride SUS, constituent saturated fatty acids of which contain at least 4 % by weight of one or more of behenic acid, lignoceric acid, cerotic acid and arachidic acid, provided that the amount of arachidic acid is less than 4 % by weight based on the total weight of the constituent saturated fatty acids. A hard butter composition according to claim 1, wherein the amount of behenic acid, lignoceric acid, cerotic acid and arachidic acid is from 4 to 30 % by weight based on the total weight of the constituent saturated fatty acids. A hard butter composition according to claim 1 or claim 2, wherein the constituent saturated fatty acids are behenic acid or lignoceric acid. A hard butter composition according to any one of the preceding claims, wherein the composition contains at least 50 % by weight of the triglyceride SUS based on the total weight of triglycerides in the composition. A process for preparing a hard butter composition as defined in any one of the preceding claims which comprises selectively introducing one or more of behenic acid, lignoceric acid, cerotic acid and arachidic acid into the α and α' positions of a fat or oil rich in oleic acid at the β position thereof. A process as claimed in claim 5, which further comprises collecting the mid-fraction of the resultant fat or oil. A process as claimed in claim 5 or claim 6, which further comprises mixing the fat or oil obtained by the process with a fat or oil rich in SUS. A food product or food product ingredient comprising a hard butter composition as claimed in any one of claims 1 to 4. A food product or food product ingredient as claimed in claim 8 which comprises chocolate or other fatty confectionery. The use of a process as claimed in any one of claims 5 to 7 in the preparation of a food product or food product ingredient.

Inventors: IZUMI, TSUGIO, KIDA, HARUYASU, MAEDA, HIROKAZU, SAGI, NOBUO
Applicants: FUJI OIL COMPANY, LIMITED
Application year: 1986
Main classification: A23D9
IPC codes: A23D9, A23G1