WO2000024850A1 - Fat compositions and process for producing the same - Google Patents

Fat compositions and process for producing the same Download PDF

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Publication number
WO2000024850A1
WO2000024850A1 PCT/JP1999/005808 JP9905808W WO0024850A1 WO 2000024850 A1 WO2000024850 A1 WO 2000024850A1 JP 9905808 W JP9905808 W JP 9905808W WO 0024850 A1 WO0024850 A1 WO 0024850A1
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WIPO (PCT)
Prior art keywords
oil
weight
fat
saturated fatty
fatty acids
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PCT/JP1999/005808
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French (fr)
Japanese (ja)
Inventor
Toshiji Horisawa
Kazuhito Okada
Toshiyuki Teranishi
Shinzo Kobayashi
Takahiko Shoyama
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Kaneka Corporation
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Publication of WO2000024850A1 publication Critical patent/WO2000024850A1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23DEDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/001Spread compositions
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23DEDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00Other edible oils or fats, e.g. shortenings, cooking oils
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10Ester interchange

Definitions

  • the present invention relates to edible processed fats and oils. More specifically, the present invention relates to a hardened fish oil substitute fat composition. Background art
  • Hardened fish oils have long been widely used as edible oils and fats, and they are especially important as raw materials for commercial margarines and shortenings. This is because hydrogenated fish oils are more plastic and less expensive than other animal or vegetable fats or their processed fats and oils.
  • the catch of small fish for example, sardines and mackerel
  • a plastic fat composition is produced using other animal or vegetable fats and oils.
  • the plastic range is wide, and the texture, gloss, nobby or whipping property is remarkable. Only inferior things were obtained.
  • trans isomer which is a constituent fatty acid of fats and oils
  • development of fats and oils having a low trans isomer content is desired.
  • a proposal has been made to hydrogenate oils and fats in the presence of a noble metal such as palladium and platinum and sodium methoxide as a transesterification catalyst (Japanese Patent Laid-Open No. 7-118688). No.
  • the present inventors analyzed the composition of the hardened fish oil, and assuming that the constituent fatty acids were randomly arranged, the distribution of triglyceride / total carbon in the hardened fish oil, and the total amount of fish oil. We found that the distribution of glyceride / toluene carbonate was extremely good, and based on this finding, if a triglyceride composition close to hardened fish oil could be obtained, it would be as good as or better than hardened fish oil. Characteristics As a result of intensive studies considering the possibility of expression, the oil and fat composition of the present invention and the method for producing the same have been completed.
  • the oil / fat composition of the present invention is a fat / oil mixture in which the total content of saturated fatty acids, the content of saturated fatty acids having 12 or less carbon atoms, and the content of saturated fatty acids having 20 or more carbon atoms are adjusted to predetermined ranges, respectively.
  • the first aspect of the oil / fat composition of the present invention is that the saturated fatty acid has a total content of 48% to 52% by weight, and a saturated fatty acid having 12 or less carbon atoms is 12.5% to 16% by weight.
  • a random transesterified fat containing 4 to 14% by weight of a saturated fatty acid having 20 or more carbon atoms and having a rising melting point of 29.0 ⁇ 1.5 ° C.
  • the oil and fat composition has a penetration value of 110 ⁇ 22.
  • the second aspect of the oil / fat composition of the present invention is that the saturated fatty acid has a total content of 68% to 75% by weight, and a saturated fatty acid having 12 or less carbon atoms is 11% to 16% by weight and a saturated fatty acid having 12 or less carbon atoms.
  • the third aspect of the oil / fat composition of the present invention is that the saturated fatty acid has a total content of 79% to 82% by weight, and a saturated fatty acid having 12 or less carbon atoms is 12% to 17% by weight and a carbon number is 12% to 17%.
  • the oil composition had a value of 25 ⁇ 7.
  • the content of trans isomer as a constituent fatty acid is 3% by weight or less.
  • a fourth aspect of the oil and fat composition of the present invention is an oil and fat composition obtained by blending at least two kinds selected from the group consisting of the above oil and fat compositions.
  • the rising melting point, fatty acid composition, and trans isomer content in the present invention are based on the standard fats and oils analysis test method (edited by the Japan Oil Chemists' Society, 1989). More specifically, the rising melting point is a value measured by the above-mentioned analytical test method 2.2.2. 4 Melting point (rising melting point), and the fatty acid composition is the above-mentioned analytical test method 2.4.2.2 Fatty acid composition (FID heated gas chromatography) ) Measurements, The trans isomer content is a value measured by the above-mentioned analytical test method 2.4.1.4.1 Isolated trans isomer (differential infrared spectroscopy).
  • the rising melting point here means that oil and fat are collected in a capillary tube, solidified under predetermined conditions, immersed in a water tank, and the water tank temperature is increased at a predetermined speed under a pressure difference of 30 mm from the lower part of the capillary tube to oil and fat. Is the temperature at which it gradually melts and finally begins to slip and rise ⁇ This temperature is the temperature at which it begins to rise, which has a close relationship with the melting of fats and oils in the mouth.
  • the rising melting point of fats and oils products has a lot to do with the texture in the mouth when eating it as a food, especially the mouthfeel. For example, if there is too much solid at a temperature near body temperature that seems to bite a candle, it is not suitable for edible use.
  • the penetration value in the present invention is based on the consistency test method of JIS K 220-199.
  • the mass of the cone (so-called cone) is 102.5 g and the mass of the plunger is 47.5 g, and the bene can is made of tin and has an inner diameter of 57 mm and a depth of 25 mm.
  • Use digital auto-onenet one-night (Mitamura Riken Kogyo).
  • the preparation of the sample for the measurement of the penetration is performed as follows.
  • the penetration value is the degree of penetration represented by the penetration as described above.
  • the hardness of an oil or fat product has a significant effect on workability when kneading or painting on bread, for example. Since the hardness of oil and fat products changes with temperature, the temperature differs depending on the season and the region, and the desired hardness often differs depending on the application, usage method, and usage environment. Has been seen.
  • hardened fish oil is an important raw material fat, but hardened fish oil alone is not sufficient. It is rare that they can be added, and those having various characteristics are desired and used.
  • the first hardened fish oil (hardened fish oil A) has a rising melting point of 29.0 ⁇ 1.5.
  • the penetration value at 20 ° C. has a characteristic of 110 ⁇ 22.
  • the second hardened fish oil (hereafter referred to as hardened fish oil B) has a rising melting point of 38.0 ⁇ 1.5 ° C and a characteristic value of 20 ⁇ 25 at 20.
  • the third hardened fish oil (hereinafter, hardened fish oil C) has a rising melting point of 43.0 ⁇ 1.5 ° C and a penetration value of 30 ° C of 25 ⁇ 7
  • These hardened fish oil A, hardened fish oil B and hardened fish oil C can be used alone or in combination of two or three, depending on the required characteristics of the product using them. Further, at least one of these hardened fish oils can be blended with other animal or vegetable fats or processed animal or vegetable fats and oils.
  • the oil / fat composition of the present invention can be used as a substitute oil / fat for the hardened fish oils A to C.
  • the first oil / fat composition of the present invention (hereinafter referred to as AA oil / fat composition) has characteristics equivalent to the above-mentioned hardened fish oil A, and has a total saturated fatty acid content of 48% by weight or less.
  • a random mixture of fats and oils containing 12.5% by weight to 16% by weight of saturated fatty acids having 12 or less carbon atoms and 4% by weight to 14% by weight of saturated fatty acids having 20 or more carbon atoms at 52% by weight. It is obtained by transesterification, has a rising melting point of 29.0 ⁇ 1.5, and has a characteristic of a penetration value of 110 ⁇ 22 at 20 ° C. It can be used as an alternative to fish oil A.
  • the second oil / fat composition of the present invention (hereinafter referred to as BB oil / fat composition) has characteristics equivalent to the above-mentioned hardened fish oil B, and has a total saturated fatty acid content of 68% by weight to 75% by weight. 11% to 16% by weight of saturated fatty acids having 12 or less carbon atoms
  • the oil / fat composition of the present invention (hereinafter, referred to as CC oil / fat composition) has characteristics equivalent to the hardened fish oil spoon, and has a total saturated fatty acid content of 79% by weight to 82% by weight.
  • the oil and fat mixture containing 12 to 17% by weight of a saturated fatty acid having 12 or less carbon atoms and 8 to 24% by weight of a saturated fatty acid having 20 or more carbon atoms is obtained by random ester exchange. It has a rising melting point of 43.0 ⁇ 1.5, a penetration value at 30 ° C of 25 ⁇ 7, and is an alternative to hardened fish oil C. Can be used as
  • the relationship between the fatty acid composition and the properties of random transesterified fats and oils is particularly affected by the total content of saturated fatty acids. If the total content of saturated fatty acids is too low, the rising melting point of the random transesterified fat will be too low, and the penetration value will be too large (that is, the penetration will be large and soft), and the total content of saturated fatty acids will be too high. If it is too large, the rising melting point of the random transesterified fat will be too high, and the penetration value will be too small (low penetration and hard).
  • the content of saturated fatty acids having 12 or less carbon atoms also affects the elevated melting point and the penetration value, but does not have as great an effect as the total content of saturated fatty acids.
  • the content of saturated fatty acids with 20 or more carbon atoms has a small effect on the melting point and the penetration value.
  • margarine using a random oil containing almost no saturated fatty acids having 20 or more carbon atoms lacks commerciality.
  • the total content of saturated fatty acids is 48% to 52% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 12.5% to 16% by weight.
  • the characteristic value of the hardened fish oil A that is, the rising melting point is 29.0 ⁇ 1.5, 20 °
  • the Veneto of C may fall out of the range of 110 ⁇ 22), so if you use it as a substitute for hardened fish oil A as a raw material for margarine and shortening, you must correct the blending ratio. It is not preferable because it causes inconveniences such as not to be performed.
  • the total content of saturated fatty acids is 68% to 75% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 11% to 16% by weight and the number of carbon atoms is 12% or less.
  • the characteristic value of the hardened fish oil ie, the melting point is 38.0 ⁇ 1.5 :, 20 ° C
  • the blending ratio must be modified. Disadvantageously occurs.
  • Those using a random oil containing less than 5% by weight of a saturated fatty acid having 20 or more carbon atoms do not show satisfactory margarine properties. Further, even if the content of the saturated fatty acid having 20 or more carbon atoms is 20% by weight or more, the effect does not increase. Therefore, the content of the saturated fatty acid having 20 or more carbon atoms needs to be 5% by weight to 20% by weight.
  • the total content of saturated fatty acids is 79% to 82% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 12% to 17% by weight and the number of carbon atoms is 2%.
  • the characteristic value of the hardened fish oil C that is, the rising melting point is 43.0 ⁇ 1.5 ° C, 30 ° C
  • the net penetration value may fall outside the range of 25 ⁇ 7), and when used as a substitute for hardened fish oil C as a raw material for margarine and shortening, the blending ratio must be modified. Inconvenience occurs, which is not preferable.
  • the oil / fat composition of the present invention having properties equivalent to hydrogenated fish oil A and having a trans isomer content of 3% by weight or less as a constituent fatty acid (hereinafter referred to as AT oil / fat composition) has a total content of saturated fatty acids.
  • Saturated fat with a ratio of 48% to 52% by weight and a carbon number of 12 or less Contains 12.5% to 16% by weight of fatty acid and 4% to 14% by weight of saturated fatty acid having 20 or more carbon atoms, and reduces the trans isomer content as a constituent fatty acid to 3% by weight or less.
  • oil / fat composition of the present invention (hereinafter, referred to as BT oil / fat composition) having properties equivalent to hydrogenated fish oil B and having a trans isomer content of 3% by weight or less as a constituent fatty acid is a saturated fatty acid.
  • the oil / fat composition of the present invention (hereinafter referred to as CT oil / fat composition) having properties equivalent to hydrogenated fish oil C and having a trans isomer content as a constituent fatty acid of 3% by weight or less is a saturated fatty acid. It has a total content of 79% to 82% by weight, contains 12% to 17% by weight of a saturated fatty acid having 12 or less carbon atoms, and 8% to 24% by weight of a saturated fatty acid having 20 or more carbon atoms.
  • the asphalt melting point obtained by random transesterification of an oil / fat mixture having a trans isomer content of 3% by weight or less as a constituent fatty acid is 43.0 ⁇ 1.5 t, It has a characteristic value of 25 ⁇ 7 and can be used as an alternative fat for the hardened fish oil C or CC fat composition.
  • AA fat composition BB fat composition, CC fat composition, AT fat composition, BT fat composition, and CT fat composition use the same as hardened fish oil A, hardened fish oil B and hardened fish oil C.
  • it may be used alone, or may be used in combination of two or more kinds.Furthermore, at least one kind selected from the group consisting of these oil and fat compositions and other animal and vegetable oils and fats Or blended with animal and vegetable processed fats and oils Can be used.
  • the raw material fat used for obtaining the A A fat composition, the BB fat composition and the C C fat composition of the present invention may be any one satisfying the following requirements.
  • a The raw material fat used for obtaining the A fat composition has a saturated fatty acid content of 48% by weight to 52% by weight and a saturated fatty acid having 12 or less carbon atoms of 12.5% by weight to 12.5% by weight.
  • Fats and oils containing 6% by weight and 4 to 14% by weight of a saturated fatty acid having 20 or more carbon atoms need to be selected from fats and oils that provide a mixture of fats and oils.
  • the raw fat used for obtaining the BB fat composition has a total saturated fatty acid content of 68% by weight to 75% by weight and a saturated fatty acid having 12 or less carbon atoms of 11% by weight to 16% by weight. It is necessary that the fat or oil is selected from fats and oils that provide a fat and oil mixture containing 5% to 14% by weight of a saturated fatty acid having 20% or more carbon atoms by weight.
  • the raw fat used for obtaining the CC fat composition has a total saturated fatty acid content of 9% to 82% by weight and a saturated fatty acid having 12 or less carbon atoms of 12% to 17%. It is necessary that the fat or oil be selected from fats and oils that provide a fat and oil mixture containing 8% to 24% by weight of a saturated fatty acid having 20 or more carbon atoms by weight.
  • the BB fat composition and the CC fat composition all of the fats containing saturated fatty acids having 12 or less carbon atoms and the fats containing saturated fatty acids having 20 or more carbon atoms are required. is necessary. In order to adjust the fatty acid composition to a desired range, fats and oils composed of other fatty acids can be used.
  • a raw material fat or oil containing a saturated fatty acid having 12 or less carbon atoms for example, coconut oil, palm kernel oil, babassu oil, milk fat and the like can be used alone or in combination.
  • Hydrogenated fats and oils of these fats alone or in combination, fractionated fats and oils, hydrogenated fats and fats of fractionated fats, fractionated fats and oils of hydrogenated fats and transesterified fats and oils can also be used.
  • Fats and oils containing fatty acids having 20 or more carbon atoms include, for example, Heyersinna evening oil, white mustard oil, monkey fat, fish oil, and the like. Transesterified fats and oils can be used.
  • fats and oils include, for example, soybean oil, rapeseed oil, corn oil, rice oil, cottonseed oil , Palm oil, tallow, lard, etc. can be used alone or in combination.
  • hydrogenated fats and oils of these fats alone or as a mixed oil, fractionated fats and oils, hydrogenated fats and oils of fractionated fats and oils, and separated fats and transesterified fats and oils of hydrogenated fats and oils can be used.
  • the raw fat used for obtaining the AT fat composition, the BT fat composition and the CT fat composition of the present invention is the raw fat used for obtaining the AA fat composition, the BB fat composition and the CC fat composition described above.
  • the fat must be selected from fats and oils in which the trans isomer content as a constituent fatty acid of the fat or oil mixture is 3% by weight or less. If the trans isomer content as a constituent fatty acid exceeds 3% by weight, it is inconvenient in that it is far from the trans isomer content of natural fats and oils and tends to depart from market needs. Natural fats and oils contain almost no trans isomer, but may be present, for example, in the hydrogenated fats in an amount of 30 to 50% by weight. Therefore, when a hydrogenated oil or fat is used as a feed oil, it is necessary to limit the trans isomer content.
  • the trans isomer content of the hydrogenated oil and fat is required to be 10.0% by weight or less.
  • the trans isomer content of the hydrogenated oil and fat is required to be 15.0% by weight or less.
  • the main fatty acid composition of each of the above-mentioned various random ester exchanged oils and fats is set within a required range, and the raw oil and fat satisfying the required conditions is used. It can be prepared by selecting more than one species and determining the mixing ratio of each raw material fat.
  • the method for obtaining the above-mentioned various random transesterified fats and oils may be a method using an alkaline catalyst such as sodium methylate or a method using an enzyme such as lipase. The method is not particularly limited and may be obtained by a known non-selective transesterification method.
  • Can be Random transesterified fats and oils are deodorized and used like ordinary fats and oils.
  • the total content of saturated fatty acids is 48% to 52% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 12.5% to 16% by weight and the content is 20% or more.
  • a random transesterification reaction is carried out using an oil or fat mixture having a saturated fatty acid content of 4% by weight to 14% by weight and a trans isomer exceeding 3% by weight or less than 3% by weight. Random reaction oils (7 types of AA oil and fat composition and 7 types of AT oil and fat composition, a total of 14 types) were prepared.
  • the mixed oil was charged into a random reaction vessel, heated with stirring under reduced pressure, and dehydrated at 120 to 30 Hg. Next, 0.3% by weight of sodium methylate was added, and the mixture was reacted for 40 minutes in a nitrogen stream with stirring. After the reaction solution was cooled to 90 ° C, a 10% aqueous solution of citric acid was added to adjust the pH to 11 or less. After stirring was stopped and the mixture was allowed to stand, an oil layer and an aqueous layer were separated. New warm water at 90 ° C was added to the oil layer and stirred, and then the system was allowed to stand still to perform so-called hot water washing to separate the oil layer and the aqueous layer.
  • the fatty acid composition of the random reaction oil produced in this manner was almost the same as that of the raw material mixed oil used.
  • the triglyceride / total carbon distribution of the raw material mixed oil and the random reaction oil was measured by gas chromatography, and the unreacted rate was determined. Data for which the unreacted rate exceeded 3 mol% was not used as data.
  • the unreacted ratio is based on the fatty acid composition of the raw mixed oil, the triglyceride composition of the raw mixed oil and the random reactive oil, and the composition of the mixture of the random reactive oil. Approximate solutions were calculated by the least-squares method, assuming that they consisted of reserides, equilibrium diglycerides, and unreacted triglycerides.
  • Table 1 shows the blending of the raw fats and oils (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oil.
  • Random transesterification reaction as in Example 1 using a fat / oil mixture in which the trans isomer is more than 3% by weight or less than 3% by weight in the range of Table 2 shows the blending of the raw fats and oils (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oils for which 7 types and 7 types of BT fats and oils compositions were prepared.
  • Palm oil 57.2 39.4 39.6 47.4 49.7 Oiling Hardened rapeseed oil (IV 74) 29.6 29.8 19.6 19.8 25.6 25.4 25.4
  • Random reaction oil (CC oil and fat composition) by random transesterification as in Example 1 using an oil or fat mixture having a trans isomer content of more than 3% by weight or less than 3% by weight.
  • Table 3 shows the blending of the raw fats and oils (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oils, which prepared 7 types and 7 types of CT fats and oils compositions (total of 14 types).
  • a random transesterification reaction was carried out in the same manner as in Example 1 to obtain a random reaction oil (four kinds of AAA fat compositions, four kinds of BBB fat compositions and four kinds of CCC fat compositions). 4 kinds of products, a total of 1 2 kinds). Table 4 shows the blending of the base oil (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oil.
  • a fat / oil mixture having a saturated fatty acid content and a saturated fatty acid content of 12 or less carbon atoms falling within the range of the present invention was prepared in the same manner as in Example 1 using fats and oils containing almost no fatty acids having 20 or more carbon atoms. Then, a random transesterification reaction was performed to prepare a random reaction oil (one kind of AAA oil composition, one kind of BBB oil composition, and one kind of CCC oil composition). The results are shown in Table 4.
  • Comparative Examples 13 and 14 Comparative Examples 14 and 15, even when a fat / oil mixture containing almost no fatty acid having 20 or more carbon atoms was used, the hardened fish oil A, the hardened fish oil B, or the hardened fish oil was used. It was found that a reaction oil having properties equivalent to C was obtained.
  • Margarine was prepared using the oil-and-fat composition having properties corresponding to the hardened fish oil A, hardened fish oil B, or hardened fish oil C obtained as described above, and the properties thereof were evaluated. ⁇ Production method and conditions of margarine>
  • mixture oil oils and fats mixed with raw materials (hereinafter referred to as “mixed oil”) 8 0.9 4 parts by weight, emulsifier MS (manufactured by RIKEN Vitamin) 0.1 part by weight, soybean lecithin 0.1 Parts by weight, 10 parts by weight of carotene as coloring agent, 0.01 parts by weight of annatto dye, 5 parts per million of flavor and 5 ppm of milk flavor and 70 ppm of milk flavor at 60 ° C Kept.
  • mixed oil oils and fats mixed with raw materials
  • emulsifier MS manufactured by RIKEN Vitamin
  • Pre-emulsification and quenching plasticization Mix the oil phase and the aqueous phase prepared in 1) and 2) above, maintain at 60 ° C and continuously emulsify and homogenize through an emulsification tank. It was quenched and plasticized by a combinator type model machine consisting of a ring cylinder. In quenching plasticization, the temperature at the second stage outlet is 20 ° C ⁇ 2 ° C lower than the rising melting point of the compounded oil. So that the outlet temperature of the third stage is 13 higher than the rising melting point of the blended oil. The refrigerant flow rate was adjusted so that the temperature was lower by C ⁇ 2 ° C, and the outlet temperature of the first stage was close to the average value of the outlet temperature of the second stage and the inlet temperature of the first stage.
  • the number of rotations of the cooling cylinder was 500 rpm for the first, second, and third stages, and the flow rate was approximately 50 KgZHr.
  • Tempering The product filled in the dampole was stored and aged for 36 hours at a temperature 5 ° C and a temperature 1 ° C lower than the rising melting point of the compounded oil.
  • Penetration value A sample was taken in a state in which both sides of a double-sided can (57 mm in diameter and 40 mm in length) were completely inserted into the margarine filled in the cardboard box and pushed up at both ends. ⁇ Both ends of the can were cut with a knives and immersed in a constant temperature water bath at the measurement temperature. Two hours later, measurement was performed overnight at Venetome.
  • the measurement was carried out in a constant temperature room using a Hobart mixer (manufactured by Kant-I-Mixer Co., Ltd.) type N50 (for 5 coats) and set at the measurement temperature. The test was performed twice, at the end of tempering and four weeks later.
  • the evaluation criteria are the same as those described in the section on the evaluation items and methods and conditions for gugu margarine products.
  • Comparative Examples 16 to 18 were obtained in Comparative Example 13, Comparative Example 14, or Comparative Example 15 with one or more selected from hydrogenated fish oil A, hydrogenated fish oil B, and hydrogenated fish oil C.
  • An oil / fat composition was used.
  • Examples 43 to 57 one or two kinds selected from hardened fish oil A, hardened fish oil B, and hardened fish oil C, and the oil and fat compositions obtained in Examples 1 to 42 were used.
  • the properties of the hardened fish oil used here were as follows.
  • Hardened fish oil A rising melting point 29.8 t :, 20 Torr value 10 5
  • Hardened fish oil B with rising melting point 38.4, 20 training value 24
  • Hardened fish oil C rising melting point 4 3.5 ° C , 30 ⁇ toration value 27
  • Table 5-7 shows the blending of the base oil of the blended oil (the blending ratio is% by weight) and the rising melting point of the blended oil. Show 'Table 5
  • Tables 8 to 10 show the results of daily changes in the properties of margarine products.
  • the daily change in consistency (hardness) of the product even when using a mixed oil of hardened fish oil A, hardened fish oil B, or hardened fish oil C, contains almost all fatty acids having 20 or more carbon atoms. Even if a mixed oil of a random oil of fat and oil and hardened fish oil A, hardened fish oil B or hardened fish oil C is used, the oil and fat composition of the present invention and hardened fish oil A, hardened fish oil B or hardened fish oil C can also be used. It was found that there was almost no difference even when using the blended oil.
  • Example 46 Example 47
  • Example 48 Example 49
  • Whib ⁇ (Shino 22.1 22.0 22.2 22.1 22.1 22.3 22 Initial temperature (° c) 21.5 21.7 21.8 21.5 21.7 21.4 21.6 Final temperature (° C) 22.2 22.3 22.5 22.5 22.7 22.8 22.4 Whib time
  • the oil / fat composition according to the present invention can be used as a raw material for margarine or shortening, whether mixed with hardened fish oil or not, even if not mixed with hardened fish oil. It is possible to provide a product whose texture and gloss are equivalent. In addition, those having a trans isomer content of 3% by weight or less can provide margarine or shortening having properties equivalent to those of products using hydrogenated fish oil.

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Abstract

Fat compositions usable as substitutes for hardened fish oil. With the recent rapid decrease in catch of fishes serving fish oil materials, substitutes for fish oil have been required. Compositions for hardened fish oil which are comparable in product properties to fish oil can be obtained through a random ester interchange reaction of a fat mixture wherein the total saturated fatty acid content, the content of saturated fatty acids having 12 or less carbon atoms and the content of saturated fatty acids having 20 or more carbon atoms have been regulated each within a specific range. The thus obtained compositions are usable as materials in producing margarine and shortening.

Description

明細書  Specification
発明の名称 Title of invention
油脂組成物及びその製造方法 技術分野  Oil and fat composition and method for producing the same
本発明は食用加工油脂に関する。 更に詳しくは硬化魚油代替油脂組成物に関す る。 背景技術  The present invention relates to edible processed fats and oils. More specifically, the present invention relates to a hardened fish oil substitute fat composition. Background art
硬化魚油は食用加工油脂として従来から広く用いられており、 とりわけ業務用 マーガリン類ならびにショートニングの原料として重要な位置を占めている。 そ の背景には、 硬化魚油が他の動植物油脂あるいはそれらの加工油脂に較べ可塑性 に優れ、 また安価であったことがある。 ところが、 魚油の原料となる小魚 (例え ば、 いわし類やさば類) の漁獲量が、 日本近海だけでなく世界的に減少し続け、 価格も高騰し、 入手することさえ困難になりつつある。 かかる情況の中にあって 、 他の動植物油脂を用いて可塑性油脂組成物が製造されているが、 硬化魚油と比 較すれば、 可塑性範囲の広さや、 キメ、 ツヤ、 ノビあるいはホイップ性は著しく 劣る物しか得られていなかった。  Hardened fish oils have long been widely used as edible oils and fats, and they are especially important as raw materials for commercial margarines and shortenings. This is because hydrogenated fish oils are more plastic and less expensive than other animal or vegetable fats or their processed fats and oils. However, the catch of small fish (for example, sardines and mackerel), which is the raw material for fish oil, continues to decrease not only in the waters around Japan but also worldwide, and the prices are rising, making it difficult to obtain them. . Under such circumstances, a plastic fat composition is produced using other animal or vegetable fats and oils. However, compared to hardened fish oil, the plastic range is wide, and the texture, gloss, nobby or whipping property is remarkable. Only inferior things were obtained.
それらの欠点を改良するため、 パーム系油脂とラウリン系油脂および液体油の 配合油をエステル交換した油脂で良好なクリームを得ることが提案され (特開昭 5 2— 7 8 2 0 3号) 、 また同様に硬化魚油との相溶性のある特性を持つ可塑性 油脂組成物を得ることが提案されている (特開平 8— 2 4 2 7 6 5号) 。 また、 同様のエステル交換により、 液体油のシミだしがなく、 グレーニングの発生が抑 制される可塑性油脂組成物の製造法の提案もされている (特開平 9 - 24 1 6 7 2号) 。 また、 ランダムエステル交換反応において、 炭素数 2 0以上の脂肪酸を 含有する油脂を用いて焼き菓子用油脂等を改善する提案がある (例えば、 特開昭 5 8— 94 3 4 5号、 特開平 4一 6 6 04 5号、 特開平 4一 7 1 44 1号、 特開 平 9一 2 24 5 7 1号) 。 更に、 炭素数 2 0以上の脂肪酸を含有する油脂、 ラウ リン系油脂及びパーム系油脂等の配合油をエステル交換反応させることによって 、 油脂組成物の可塑性等を改善する提案もある (例えば、 特開昭 5 0— 2 6 8 0 4号、 特開昭 5 4— 3 1 4 0 7号、 特開昭 5 4 — 3 4 0 0 2号、 特開平 9 一 1 6 5 5 9 5号) 。 In order to improve those drawbacks, it has been proposed to obtain a good cream by transesterifying a blended oil of palm-based fat, lauric-based fat and liquid oil (Japanese Patent Application Laid-Open No. 52-72803). Also, it has been proposed to obtain a plastic fat composition having properties compatible with hardened fish oil (Japanese Patent Application Laid-Open No. H8-224765). In addition, a method for producing a plastic fat composition in which liquid oil is not stained by the same transesterification and the occurrence of graining is suppressed has been proposed (Japanese Patent Application Laid-Open No. Hei 9-2416772). . Further, in a random transesterification reaction, there is a proposal to improve fats and oils for baked confectionery by using fats and oils containing fatty acids having 20 or more carbon atoms (for example, Japanese Patent Application Laid-Open Nos. 58-94345, JP-A-6-66045, JP-A-4-17441, JP-A-9-1224571). Furthermore, by transesterifying a blended oil such as a fat or oil containing a fatty acid having 20 or more carbon atoms, a lauric fat or a palm fat, etc. There are also proposals for improving the plasticity and the like of fats and oils compositions (for example, Japanese Patent Application Laid-Open Nos. Sho 50-26804, Sho 54-31407, Sho 54-34). No. 02, Japanese Unexamined Patent Publication No. Hei 9 (1995) -65555).
しかしながら、 これらの提案は、 従来の動植物油脂の可塑性の改善あるいは、 硬化魚油との相溶性の改善を追究したものであって、 それらの効果があっても、 可塑性範囲の広さや、 キメ、 ツヤ、 ノビあるいはホイップ性においては硬化魚油 に勝るものではなく、 硬化魚油と混合することによって商品価値を有する可塑性 油脂組成物を提供するにすぎなかった。  However, these proposals seek to improve the plasticity of conventional animal and vegetable fats and oils or the compatibility with hardened fish oil, and even with these effects, the broad plasticity range, texture, and gloss On the other hand, it does not surpass hardened fish oil in the nobby or whipping properties, but merely provides a plastic oil / fat composition having commercial value by mixing with hardened fish oil.
また、 近年、 栄養学的観点から、 油脂の構成脂肪酸であるトランス異性体につ いての論議が展開され、 トランス異性体含量の少ない油脂の開発が望まれている 。 トランス酸含有率の低い可塑性油脂の開発例として、 パラジウム、 白金等の貴 金属とエステル交換触媒であるナトリウムメ トキシドを共存させて油脂を水素添 加する提案 (特開平 7— 1 1 8 6 8 8号) があり、 また、 トランス酸を含まない 油脂の開発例として、 パ一ム油と菜種油あるいはパーム核油とパ一ム極度硬化油 を 1, 3—位置特異性リパーゼを用いてエステル交換させる提案がある (特開平 4— 6 5 4 9 3号) 。  In recent years, from the nutritional point of view, discussion has been made on trans isomer which is a constituent fatty acid of fats and oils, and development of fats and oils having a low trans isomer content is desired. As an example of the development of plastic oils and fats with a low trans acid content, a proposal has been made to hydrogenate oils and fats in the presence of a noble metal such as palladium and platinum and sodium methoxide as a transesterification catalyst (Japanese Patent Laid-Open No. 7-118688). No. 8), and as trans-acid-free fats and oils, transesterification of palm oil and rapeseed oil or palm kernel oil and extremely hardened palm oil using 1,3-regiospecific lipase There is a proposal (Japanese Patent Application Laid-Open No. 4-658493).
しかしながら、 いずれの提案の場合も、 可塑性は改善されていると報告されて いるものの、 硬化魚油に代替できる程の特長は報告されていないし、 特性評価も なされていない。  However, although the plasticity of both proposals was reported to be improved, no features were reported that could replace hardened fish oil, and no characterization was performed.
以上のように、 これまでの技術では、 硬化魚油と同等の特性を有し、 硬化魚油 に代替できる油脂組成物は知られておらず、 かかる油脂組成物が求められている 。 また卜ランス酸含有率の少ない油脂も求められている。 発明の開示  As described above, in the conventional techniques, there is no known fat / oil composition which has properties equivalent to that of hardened fish oil and can be substituted for hardened fish oil, and such fat / oil composition is required. There is also a need for oils and fats having a low transonic acid content. Disclosure of the invention
かかる情況の中にあって、 本発明者等は硬化魚油の組成を解析し、 構成脂肪酸 がランダムに配列していると仮定した場合の硬化魚油のトリグリセライ ド · トー タルカーボン分布と、 魚油の卜リグリセライ ド · トー夕ルカ一ボン分布が、 極め て良く一致することを知見し、 この知見に基づいて、 硬化魚油に近いトリグリセ ライ ド組成物を得ることができれば、 硬化魚油と同等あるいはそれ以上の特性を 発現する可能性があると考え、 鋭意研究した結果、 本発明の油脂組成物及びその 製造方法を完成するに至った。 Under these circumstances, the present inventors analyzed the composition of the hardened fish oil, and assuming that the constituent fatty acids were randomly arranged, the distribution of triglyceride / total carbon in the hardened fish oil, and the total amount of fish oil. We found that the distribution of glyceride / toluene carbonate was extremely good, and based on this finding, if a triglyceride composition close to hardened fish oil could be obtained, it would be as good as or better than hardened fish oil. Characteristics As a result of intensive studies considering the possibility of expression, the oil and fat composition of the present invention and the method for producing the same have been completed.
即ち、 本発明の油脂組成物は、 飽和脂肪酸の総含有率、 炭素数 1 2以下の飽和 脂肪酸の含有率及び炭素数 2 0以上の飽和脂肪酸の含有率をそれぞれ所定の範囲 に調整した油脂混合物のランダムエステル交換油脂であって、 硬化魚脂と同等の 上昇融点及びベネトレ一ション値を有する硬化魚油代替油脂組成物である。 そして、 本発明の油脂組成物の第 1は、 飽和脂肪酸の総含有率が 4 8重量%〜 5 2重量%で、 炭素数 1 2以下の飽和脂肪酸を 1 2 . 5重量%〜 1 6重量%及び 炭素数 2 0以上の飽和脂肪酸を 4重量%〜 1 4重量%含有する油脂混合物のラン ダムエステル交換油脂であって、 上昇融点が 2 9 . 0 ± 1 . 5 °Cで、 2 0でのべ ネトレーション値が 1 1 0 ± 2 2の油脂組成物である。  That is, the oil / fat composition of the present invention is a fat / oil mixture in which the total content of saturated fatty acids, the content of saturated fatty acids having 12 or less carbon atoms, and the content of saturated fatty acids having 20 or more carbon atoms are adjusted to predetermined ranges, respectively. , A hardened fish oil substitute oil / fat composition having the same elevated melting point and penetration value as hardened fish fat. The first aspect of the oil / fat composition of the present invention is that the saturated fatty acid has a total content of 48% to 52% by weight, and a saturated fatty acid having 12 or less carbon atoms is 12.5% to 16% by weight. %, And a random transesterified fat containing 4 to 14% by weight of a saturated fatty acid having 20 or more carbon atoms and having a rising melting point of 29.0 ± 1.5 ° C. The oil and fat composition has a penetration value of 110 ± 22.
本発明の油脂組成物の第 2は、 飽和脂肪酸の総含有率が 6 8重量%〜 7 5重量 %で、 炭素数 1 2以下の飽和脂肪酸を 1 1重量%〜 1 6重量%及び炭素数 2 0以 上の飽和脂肪酸を 5重量%〜 2 0重量%含有する油脂混合物のランダムエステル 交換油脂であって、 上昇融点が 3 8 . 0 ± 1 . 5 T:で、 2 0 °Cのベネトレ一ショ ン値が 2 5 ± 5の油脂組成物である。  The second aspect of the oil / fat composition of the present invention is that the saturated fatty acid has a total content of 68% to 75% by weight, and a saturated fatty acid having 12 or less carbon atoms is 11% to 16% by weight and a saturated fatty acid having 12 or less carbon atoms. A random transesterified fat or oil of a fat or oil mixture containing 5% to 20% by weight of a saturated fatty acid of 20 or more, having a rising melting point of 38.0 ± 1.5 T: It is an oil / fat composition having an option value of 25 ± 5.
本発明の油脂組成物の第 3は、 飽和脂肪酸の総含有率が 7 9重量%〜8 2重量 %で、 炭素数 1 2以下の飽和脂肪酸を 1 2重量%〜 1 7重量%及び炭素数 2 0以 上の飽和脂肪酸を 8重量%〜 2 4重量%含有する油脂混合物のランダムエステル 交換油脂であって、 上昇融点が 4 3 . 0 ± 1 . 5 で、 3 0 °Cのべネトレーショ ン値が 2 5 ± 7の油脂組成物である。  The third aspect of the oil / fat composition of the present invention is that the saturated fatty acid has a total content of 79% to 82% by weight, and a saturated fatty acid having 12 or less carbon atoms is 12% to 17% by weight and a carbon number is 12% to 17%. A random transesterified fat of a fat mixture containing 8 to 24% by weight of saturated fatty acids of 20 or more, with a melting point of 43.0 ± 1.5 and a penetration of 30 ° C. The oil composition had a value of 25 ± 7.
上記本発明の油脂組成物の第 1〜第 3の好ましい実施態様としては、 構成脂肪 酸としてのトランス異性体含有率が 3重量%以下である。  In the first to third preferred embodiments of the oil and fat composition of the present invention, the content of trans isomer as a constituent fatty acid is 3% by weight or less.
また、 本発明の油脂組成物の第 4は、 上記のような油脂組成物からなる群より 選択される少なくとも 2種を配合して得られる油脂組成物である。  A fourth aspect of the oil and fat composition of the present invention is an oil and fat composition obtained by blending at least two kinds selected from the group consisting of the above oil and fat compositions.
本発明における上昇融点、 脂肪酸組成及びトランス異性体含有率は、 基準油脂 分析試験法 (日本油化学会編一 1 9 9 6 ) に基づく。 更に詳しくは、 上昇融点は 前記分析試験法 2. 2. 4. 2 融点 (上昇融点) による測定値、 脂肪酸組成は前記分析 試験法 2. 4. 2. 2 脂肪酸組成 (F I D昇温ガスクロマトグラフ法) による測定値、 また、 トランス異性体含有率は前記分析試験法 2. 4. 4. 1 孤立トランス異性体 (差 赤外スペク トル法) による測定値を表す。 The rising melting point, fatty acid composition, and trans isomer content in the present invention are based on the standard fats and oils analysis test method (edited by the Japan Oil Chemists' Society, 1989). More specifically, the rising melting point is a value measured by the above-mentioned analytical test method 2.2.2. 4 Melting point (rising melting point), and the fatty acid composition is the above-mentioned analytical test method 2.4.2.2 Fatty acid composition (FID heated gas chromatography) ) Measurements, The trans isomer content is a value measured by the above-mentioned analytical test method 2.4.1.4.1 Isolated trans isomer (differential infrared spectroscopy).
ここでいう上昇融点とは、 油脂を毛細管に採取し所定条件下で固化させた後、 水槽に浸潰し毛細管下部から水柱 3 0 mmの差圧下、 水槽温度を所定速度で上げ ていくと、 油脂は徐々に溶融していき、 遂にはスリップして上昇し始める力^ こ の上昇し始める温度のことであり、 油脂製品の口溶けと密接な関係がある。 油脂製品の上昇融点は、 食品として食する時、 口での食感、 とりわけ口どけと 大いに関係する。 例えば、 体温近くの温度で固体が多すぎてローソクをかじって いるようであっては食用には不向きである。  The rising melting point here means that oil and fat are collected in a capillary tube, solidified under predetermined conditions, immersed in a water tank, and the water tank temperature is increased at a predetermined speed under a pressure difference of 30 mm from the lower part of the capillary tube to oil and fat. Is the temperature at which it gradually melts and finally begins to slip and rise ^ This temperature is the temperature at which it begins to rise, which has a close relationship with the melting of fats and oils in the mouth. The rising melting point of fats and oils products has a lot to do with the texture in the mouth when eating it as a food, especially the mouthfeel. For example, if there is too much solid at a temperature near body temperature that seems to bite a candle, it is not suitable for edible use.
また本発明におけるベネトレ一シヨン値は、 J I S K 2 2 2 0 — 1 9 9 3の ちょう度試験法に基づく。 但し、 円すい (いわゆるコーン) の質量は 1 0 2 . 5 g、 プランジャー質量は 4 7 . 5 gの物を、 またベネ缶はブリキ製で内径 5 7 m m、 深さ 2 5 mmの物を使用し、 ぺネトロメ一夕一はデジタル式オート · ぺネト ロメ一夕 (三田村理研工業製) を用いる。  Further, the penetration value in the present invention is based on the consistency test method of JIS K 220-199. However, the mass of the cone (so-called cone) is 102.5 g and the mass of the plunger is 47.5 g, and the bene can is made of tin and has an inner diameter of 57 mm and a depth of 25 mm. Use digital auto-onenet one-night (Mitamura Riken Kogyo).
ベネ卜レ一ション測定用サンプルの調製は次のようにする。  The preparation of the sample for the measurement of the penetration is performed as follows.
測定する油脂を 6 0 〜 6 5 °Cに加熱して、 厚さ 5 c m以上の氷を水平に置き 、 その上においたベネ缶に溢れ出す程度まで注ぐ。 そのまま氷上で 1 . 5時間固 化静置した後、 所望測定温度の恒温水槽に浸漬しておき、 2時間後にベネトロメ 一夕一で測定する。  Heat the oil or fat to be measured to 60-65 ° C, place ice 5cm or more in thickness horizontally and pour it to the extent that it overflows into the cans placed on it. After leaving it to set on ice for 1.5 hours, immerse it in a thermostatic water bath at the desired measurement temperature, and measure it overnight with Venetome after 2 hours.
ベネトレ一シヨン値は、 上記のようにちよう度を針入度で表したものであって The penetration value is the degree of penetration represented by the penetration as described above.
、 測定温度における硬度を表す指標である。 It is an index representing the hardness at the measurement temperature.
また、 油脂製品の硬さは、 例えばパンに練り込むとかパンに塗るとかする際の 作業性に大きな影響を与える。 油脂製品の硬さは温度によって変化するので、 季 節によって、 また地域によって気温が異なり、 また使用する用途、 使用方法、 使 用する環境によって所望の硬さが異なることが多く、 上昇融点とともに重要視さ れている。  In addition, the hardness of an oil or fat product has a significant effect on workability when kneading or painting on bread, for example. Since the hardness of oil and fat products changes with temperature, the temperature differs depending on the season and the region, and the desired hardness often differs depending on the application, usage method, and usage environment. Has been seen.
それらの要望に応えるには単独の油脂では満足することが困難であり、 種々の 油脂を加工し、 それらを混合して特長ある多くの製品が上市されている。  It is difficult to satisfy these demands with a single fat and oil, and various fats and oils are processed and mixed to produce many distinctive products on the market.
硬化魚油が重要な原料油脂であることは先にも触れたが、 硬化魚油も単独で満 足できることは希であり種々の特性を持つものが望まれ使用されている。 It was mentioned earlier that hardened fish oil is an important raw material fat, but hardened fish oil alone is not sufficient. It is rare that they can be added, and those having various characteristics are desired and used.
以下、 本発明に関わる硬化魚油代替油脂組成物について説明する。  Hereinafter, the hardened fish oil alternative fat composition according to the present invention will be described.
先ず、 硬化魚油の中でも代表的な次の 3品種を対象に、 その特性値を明示する 第一の硬化魚油 (以下、 硬化魚油 Aという。 ) は、 上昇融点が 2 9. 0 ± 1. 5 であって、 2 0°Cのベネトレ一ション値が 1 1 0 ± 2 2の特性を持つもので ある。  First, the characteristics of the first three hardened fish oils, which are representative of the following three varieties, are specified. The first hardened fish oil (hardened fish oil A) has a rising melting point of 29.0 ± 1.5. Wherein the penetration value at 20 ° C. has a characteristic of 110 ± 22.
第二の硬化魚油 (以下、 硬化魚油 Bという。 ) は、 上昇融点が 3 8. 0 ± 1. 5°Cであって、 2 0でのベネトレーシヨン値が 2 5 ± 5の特性を持つものである 第三の硬化魚油 (以下、 硬化魚油 Cという。 ) は、 上昇融点が 4 3. 0 ± 1. 5°Cであって、 3 0°Cのベネトレーション値が 2 5 ± 7の特性を持つものである これら硬化魚油 A、 硬化魚油 B及び硬化魚油 Cは、 これらを使用する製品の所 要特性に応じて、 単独でも用いられるし、 2種又は 3種を配合して用いることが できるし、 更に、 これらの硬化魚油の少なくとも 1種と他の動植物油脂あるいは 動植物加工油脂とを配合して用いることもできる。  The second hardened fish oil (hereafter referred to as hardened fish oil B) has a rising melting point of 38.0 ± 1.5 ° C and a characteristic value of 20 ± 25 at 20. The third hardened fish oil (hereinafter, hardened fish oil C) has a rising melting point of 43.0 ± 1.5 ° C and a penetration value of 30 ° C of 25 ± 7 These hardened fish oil A, hardened fish oil B and hardened fish oil C can be used alone or in combination of two or three, depending on the required characteristics of the product using them. Further, at least one of these hardened fish oils can be blended with other animal or vegetable fats or processed animal or vegetable fats and oils.
本発明の油脂組成物は、 上記硬化魚油 A〜Cの代替油脂として用いることがで きるものである。  The oil / fat composition of the present invention can be used as a substitute oil / fat for the hardened fish oils A to C.
先ず、 本発明の第一の油脂組成物 (以下、 AA油脂組成物という。 ) は、 前記 硬化魚油 Aに相当する特性を有するものであり、 飽和脂肪酸の総含有率が 4 8重 量%〜 5 2重量%で、 炭素数 1 2以下の飽和脂肪酸を 1 2. 5重量%〜 1 6重量 %及び炭素数 2 0以上の飽和脂肪酸を 4重量%〜 1 4重量%含有する油脂混合物 をランダムエステル交換することによって得られるものであり、 上昇融点が 2 9 . 0 ± 1. 5 であって、 2 0 °Cのぺネトレーシヨン値が 1 1 0 ± 2 2の特性を 持つものであり、 硬化魚油 Aの代替油脂として用いることができる。  First, the first oil / fat composition of the present invention (hereinafter referred to as AA oil / fat composition) has characteristics equivalent to the above-mentioned hardened fish oil A, and has a total saturated fatty acid content of 48% by weight or less. A random mixture of fats and oils containing 12.5% by weight to 16% by weight of saturated fatty acids having 12 or less carbon atoms and 4% by weight to 14% by weight of saturated fatty acids having 20 or more carbon atoms at 52% by weight. It is obtained by transesterification, has a rising melting point of 29.0 ± 1.5, and has a characteristic of a penetration value of 110 ± 22 at 20 ° C. It can be used as an alternative to fish oil A.
本発明の第 2の油脂組成物 (以下、 B B油脂組成物という。 ) は、 前記硬化魚 油 Bに相当する特性を有するものであり、 飽和脂肪酸の総含有率が 6 8重量%〜 7 5重量%で、 炭素数 1 2以下の飽和脂肪酸を 1 1重量%〜 1 6重量%及び炭素 数 2 0以上の飽和脂肪酸を 5重量%〜 2 0重量%含有する油脂混合物: エステル交換することによって得られるものであり、 上昇融点が 3 8 . 0土 1 . 5 °Cであって、 2 0 °Cのぺネ卜レ一ション値が 2 5 ± 5の特性を持つものであり 、 硬化魚油 Bの代替油脂として用いることができる。 The second oil / fat composition of the present invention (hereinafter referred to as BB oil / fat composition) has characteristics equivalent to the above-mentioned hardened fish oil B, and has a total saturated fatty acid content of 68% by weight to 75% by weight. 11% to 16% by weight of saturated fatty acids having 12 or less carbon atoms An oil or fat mixture containing 5% to 20% by weight of a saturated fatty acid having a number of 20 or more: Obtained by transesterification, and has a rising melting point of 38.0 soil 1.5 ° C; It has a characteristic that the penetration value at 0 ° C. is 25 ± 5, and can be used as an alternative to hardened fish oil B.
本発明の油脂組成物 (以下、 C C油脂組成物という。 ) は、 前記硬化魚油じに 相当する特性を有するものであり、 飽和脂肪酸の総含有率が 7 9重量%〜8 2重 量%で、 炭素数 1 2以下の飽和脂肪酸を 1 2重量%〜 1 7重量%及び炭素数 2 0 以上の飽和脂肪酸を 8重量%〜 2 4重量%含有する油脂混合物をランダムエステ ル交換することによって得られるものであり、 上昇融点が 4 3 . 0 ± 1 . 5でで あって、 3 0 °Cのぺネトレ一シヨン値が 2 5 ± 7の特性を持つものであり、 硬化 魚油 Cの代替油脂として用いることができる。  The oil / fat composition of the present invention (hereinafter, referred to as CC oil / fat composition) has characteristics equivalent to the hardened fish oil spoon, and has a total saturated fatty acid content of 79% by weight to 82% by weight. The oil and fat mixture containing 12 to 17% by weight of a saturated fatty acid having 12 or less carbon atoms and 8 to 24% by weight of a saturated fatty acid having 20 or more carbon atoms is obtained by random ester exchange. It has a rising melting point of 43.0 ± 1.5, a penetration value at 30 ° C of 25 ± 7, and is an alternative to hardened fish oil C. Can be used as
脂肪酸組成とランダムエステル交換油脂の特性との関係については、 特に飽和 脂肪酸の総含有率が大きく影響する。 飽和脂肪酸の総含有率が少なすぎるとラン ダムエステル交換油脂の上昇融点が低くなりベネトレ一ション値が大きく (つま り、 針入度が大きく、 軟らかく) なりすぎ、 また飽和脂肪酸の総含有率が多すぎ るとランダムエステル交換油脂の上昇融点が高くなりすぎベネトレ一ション値は 小さく (針入度が小さく、 硬く) なりすぎる。 炭素数 1 2以下の飽和脂肪酸の含 有率も上昇融点及びベネトレーション値に影響を与えるが、 飽和脂肪酸の総含有 率程には大きな影響はない。 飽和脂肪酸の総含有率及び炭素数 1 2以下の飽和脂 肪酸の含有率が同じ条件であれば、 炭素数 2 0以上の飽和脂肪酸の含有率は上昇 融点及びべネトレーシヨン値に与える影響は小さい。 但し、 炭素数 2 0以上の飽 和脂肪酸をほとんど含まないランダム油を用いたマーガリンは商品性に欠ける。  The relationship between the fatty acid composition and the properties of random transesterified fats and oils is particularly affected by the total content of saturated fatty acids. If the total content of saturated fatty acids is too low, the rising melting point of the random transesterified fat will be too low, and the penetration value will be too large (that is, the penetration will be large and soft), and the total content of saturated fatty acids will be too high. If it is too large, the rising melting point of the random transesterified fat will be too high, and the penetration value will be too small (low penetration and hard). The content of saturated fatty acids having 12 or less carbon atoms also affects the elevated melting point and the penetration value, but does not have as great an effect as the total content of saturated fatty acids. Provided that the total content of saturated fatty acids and the content of saturated fatty acids with 12 or less carbon atoms are the same, the content of saturated fatty acids with 20 or more carbon atoms has a small effect on the melting point and the penetration value. . However, margarine using a random oil containing almost no saturated fatty acids having 20 or more carbon atoms lacks commerciality.
A A油脂組成物においては、 飽和脂肪酸の総含有率が 4 8重量%〜 5 2重量% で、 炭素数 1 2以下の飽和脂肪酸の含有率が 1 2 . 5重量%〜 1 6重量%及び炭 素数 2 0以上の飽和脂肪酸の含有率が 4重量%〜 1 4重量%の範囲を外れると、 硬化魚油 Aの特性値 (即ち、 上昇融点が 2 9 . 0 ± 1 . 5で、 2 0 °Cのベネトレ —シヨン値が 1 1 0 ± 2 2 ) の範囲を外れてしまうことがあり、 硬化魚油 Aの代 替油としてマ一ガリンゃショートニング原料として用いる際には配合割合を修正 しなければならないなどの不都合が生じ好ましくない。 炭素数 2 0以上の飽和脂 肪酸を 4重量%未満含有するランダム油を用いたものは満足できるマ一ガリン特 性を示さない。 また、 炭素数 2 0以上の飽和脂肪酸の含有率を 1 4重量%以上に してもその効果が増大することはない。 よって、 炭素数 2 0以上の飽和脂肪酸含 有率は 4重量%〜 1 4重量%である必要がある。 In the AA fat composition, the total content of saturated fatty acids is 48% to 52% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 12.5% to 16% by weight. When the content of the saturated fatty acid having a prime number of 20 or more is out of the range of 4% by weight to 14% by weight, the characteristic value of the hardened fish oil A (that is, the rising melting point is 29.0 ± 1.5, 20 ° The Veneto of C may fall out of the range of 110 ± 22), so if you use it as a substitute for hardened fish oil A as a raw material for margarine and shortening, you must correct the blending ratio. It is not preferable because it causes inconveniences such as not to be performed. Saturated fat with 20 or more carbon atoms Those using random oil containing less than 4% by weight of fatty acid do not show satisfactory margarine characteristics. Even if the content of the saturated fatty acid having 20 or more carbon atoms is 14% by weight or more, the effect does not increase. Therefore, the content of the saturated fatty acid having 20 or more carbon atoms needs to be 4% by weight to 14% by weight.
Β Β油脂組成物においては、 飽和脂肪酸の総含有率が 6 8重量%〜 7 5重量% で、 炭素数 1 2以下の飽和脂肪酸の含有率が 1 1重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸の含有率が 5重量%〜 2 0重量%の範囲を外れると、 硬化 魚油 Βの特性値 (即ち、 上昇融点が 3 8 . 0 ± 1 . 5 :、 2 0 °Cのベネトレ一シ ヨン値が 2 5 ± 5 ) の範囲を外れてしまうことがあり、 硬化魚油 Bの代替油とし てマ一ガリンゃショートニング原料として用いる際には配合割合を修正しなけれ ばならないなどの不都合が生じ好ましくない。 炭素数 2 0以上の飽和脂肪酸を 5 重量%未満含有するランダム油を用いたものは満足できるマーガリン特性を示さ ない。 また、 炭素数 2 0以上の飽和脂肪酸の含有率を 2 0重量%以上にしてもそ の効果が増大することはない。 よって、 炭素数 2 0以上の飽和脂肪酸の含有率は 5重量%〜 2 0重量%である必要がある。  Β In the fat and oil composition, the total content of saturated fatty acids is 68% to 75% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 11% to 16% by weight and the number of carbon atoms is 12% or less. When the content of saturated fatty acids of 20 or more is out of the range of 5% by weight to 20% by weight, the characteristic value of the hardened fish oil (ie, the melting point is 38.0 ± 1.5 :, 20 ° C) May be out of the range of 25 ± 5), and when used as a substitute for hardened fish oil B as a raw material for margarine and shortening, the blending ratio must be modified. Disadvantageously occurs. Those using a random oil containing less than 5% by weight of a saturated fatty acid having 20 or more carbon atoms do not show satisfactory margarine properties. Further, even if the content of the saturated fatty acid having 20 or more carbon atoms is 20% by weight or more, the effect does not increase. Therefore, the content of the saturated fatty acid having 20 or more carbon atoms needs to be 5% by weight to 20% by weight.
C C油脂組成物においては、 飽和脂肪酸の総含有率が 7 9重量%〜8 2重量% で、 炭素数 1 2以下の飽和脂肪酸の含有率が 1 2重量%〜 1 7重量%及び炭素数 2 0以上の飽和脂肪酸の含有率が 8重量%〜 2 4重量%の範囲を外れると、 硬化 魚油 Cの特性値 (即ち、 上昇融点が 4 3 . 0 ± 1 . 5 °C、 3 0 °Cのべネトレーシ ヨン値が 2 5 ± 7 ) の範囲を外れてしまうことがあり、 硬化魚油 Cの代替油とし てマ一ガリンゃショートニング原料として用いる際には配合割合を修正しなけれ ばならないなどの不都合が生じ好ましくない。 炭素数 2 0以上の飽和脂肪酸を 8 重量%未満含有するランダム油を用いたものは満足できるマーガリン特性を示さ ない。 また、 炭素数 2 0以上の飽和脂肪酸の含有率を 2 4重量%以上にしてもそ の効果が増大することはない。 よって、 炭素数 2 0以上の飽和脂肪酸の含有率は 8重量%〜2 4重量%である必要がある。  In the CC fat composition, the total content of saturated fatty acids is 79% to 82% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 12% to 17% by weight and the number of carbon atoms is 2%. When the content of the saturated fatty acid of 0 or more is out of the range of 8% by weight to 24% by weight, the characteristic value of the hardened fish oil C (that is, the rising melting point is 43.0 ± 1.5 ° C, 30 ° C) The net penetration value may fall outside the range of 25 ± 7), and when used as a substitute for hardened fish oil C as a raw material for margarine and shortening, the blending ratio must be modified. Inconvenience occurs, which is not preferable. Those using a random oil containing less than 8% by weight of a saturated fatty acid having 20 or more carbon atoms do not show satisfactory margarine properties. Further, even if the content of the saturated fatty acid having 20 or more carbon atoms is 24% by weight or more, the effect does not increase. Therefore, the content of the saturated fatty acid having 20 or more carbon atoms needs to be 8% by weight to 24% by weight.
硬化魚油 Aに相当する特性を有し、 構成脂肪酸としてのトランス異性体含有率 が 3重量%以下である本発明の油脂組成物 (以下、 A T油脂組成物という。 ) は 、 飽和脂肪酸の総含有率が 4 8重量%〜 5 2重量%で、 炭素数 1 2以下の飽和脂 肪酸を 1 2. 5重量%〜 1 6重量%及び炭素数 20以上の飽和脂肪酸を 4重量% 〜 1 4重量%含有し、 構成脂肪酸としての卜ランス異性体含有率が 3重量%以下 になる油脂混合物をランダムエステル交換することによって得られる、 上昇融点 が 2 9. 0 ± 1. 5°Cであって、 20°Cのぺネトレ一シヨン値が 1 1 0 ± 22の 特性を持つものであり、 硬化魚油 Α又は ΑΑ油脂組成物の代替油脂として用いる ことができる。 The oil / fat composition of the present invention having properties equivalent to hydrogenated fish oil A and having a trans isomer content of 3% by weight or less as a constituent fatty acid (hereinafter referred to as AT oil / fat composition) has a total content of saturated fatty acids. Saturated fat with a ratio of 48% to 52% by weight and a carbon number of 12 or less Contains 12.5% to 16% by weight of fatty acid and 4% to 14% by weight of saturated fatty acid having 20 or more carbon atoms, and reduces the trans isomer content as a constituent fatty acid to 3% by weight or less. Obtained by random transesterification of a mixture of fats and oils, having an ascending melting point of 29.0 ± 1.5 ° C and a penetration value at 20 ° C of 110 ± 22 It can be used as a substitute for fats and oils of hardened fish oils or fats and oils compositions.
また、 硬化魚油 Bに相当する特性を有し、 構成脂肪酸としてのトランス異性体 含有率が 3重量%以下である本発明の油脂組成物 (以下、 BT油脂組成物という 。 ) は、 飽和脂肪酸の総含有率が 68重量%〜 7 5重量%で、 炭素数 1 2以下の 飽和脂肪酸を 1 1重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸を 5重量 %〜2 0重量%含有し、 構成脂肪酸としてのトランス異性体含有率が 3重量%以 下になる油脂混合物をランダムエステル交換することによって得られる、 上昇融 点が 38. 0 ± 1. 5 であって、 2 0 X:のべネトレーシヨン値が 2 5 ± 5の特 性を持つものであり、 硬化魚油 B又は B B油脂組成物の代替油脂として用いるこ とができる。  Further, the oil / fat composition of the present invention (hereinafter, referred to as BT oil / fat composition) having properties equivalent to hydrogenated fish oil B and having a trans isomer content of 3% by weight or less as a constituent fatty acid is a saturated fatty acid. Total content of 68% to 75% by weight, 11% to 16% by weight of saturated fatty acids having 12 or less carbon atoms and 5% to 20% by weight of saturated fatty acids having 20 or more carbon atoms Containing a trans-isomer as a constituent fatty acid having a trans-isomer content of 3% by weight or less, obtained by random transesterification, has an ascending melting point of 38.0 ± 1.5, and 20 X : It has a characteristic of a net penetration value of 25 ± 5, and can be used as an alternative fat for the hardened fish oil B or BB fat composition.
更に、 硬化魚油 Cに相当する特性を有し、 構成脂肪酸としてのトランス異性体 含有率が 3重量%以下である本発明の油脂組成物 (以下、 CT油脂組成物という 。 ) は、 飽和脂肪酸の総含有率が 7 9重量%〜 82重量%で、 炭素数 1 2以下の 飽和脂肪酸を 1 2重量%〜 1 7重量%及び炭素数 20以上の飽和脂肪酸を 8重量 %〜 24重量%含有し、 構成脂肪酸としてのトランス異性体含有率が 3重量%以 下になる油脂混合物をランダムエステル交換することによって得られる、 上昇融 点が 43. 0 ± 1. 5 tであって、 30でのベネトレ一シヨン値が 2 5 ± 7の特 性を持つものであり、 硬化魚油 C又は C C油脂組成物の代替油脂として用いるこ とができる。  Further, the oil / fat composition of the present invention (hereinafter referred to as CT oil / fat composition) having properties equivalent to hydrogenated fish oil C and having a trans isomer content as a constituent fatty acid of 3% by weight or less is a saturated fatty acid. It has a total content of 79% to 82% by weight, contains 12% to 17% by weight of a saturated fatty acid having 12 or less carbon atoms, and 8% to 24% by weight of a saturated fatty acid having 20 or more carbon atoms. The asphalt melting point obtained by random transesterification of an oil / fat mixture having a trans isomer content of 3% by weight or less as a constituent fatty acid is 43.0 ± 1.5 t, It has a characteristic value of 25 ± 7 and can be used as an alternative fat for the hardened fish oil C or CC fat composition.
これら AA油脂組成物、 B B油脂組成、 C C油脂組成物、 AT油脂組成物、 B T油脂組成物、 及び CT油脂組成物は、 硬化魚油 A、 硬化魚油 B及び硬化魚油 C と同様に、 これらを使用する製品の所要特性に応じて、 単独でも用いられるし、 2種以上を配合して用いることができるし、 更に、 これらの油脂組成物からなる 群から選ばれた少なくとも 1種と他の動植物油脂あるいは動植物加工油脂と配合 して用いることができる。 These AA fat composition, BB fat composition, CC fat composition, AT fat composition, BT fat composition, and CT fat composition use the same as hardened fish oil A, hardened fish oil B and hardened fish oil C. Depending on the required characteristics of the product to be used, it may be used alone, or may be used in combination of two or more kinds.Furthermore, at least one kind selected from the group consisting of these oil and fat compositions and other animal and vegetable oils and fats Or blended with animal and vegetable processed fats and oils Can be used.
本発明の A A油脂組成物、 B B油脂組成物及び C C油脂組成物を得るために用 いる原料油脂は、 次の必要条件を満足するものであればよい。  The raw material fat used for obtaining the A A fat composition, the BB fat composition and the C C fat composition of the present invention may be any one satisfying the following requirements.
1 ) A A油脂組成物を得るために用いられる原料油脂は、 飽和脂肪酸の含有率が 4 8重量%〜 5 2重量%で、 炭素数 1 2以下の飽和脂肪酸を 1 2 . 5重量%〜 1 1) A The raw material fat used for obtaining the A fat composition has a saturated fatty acid content of 48% by weight to 52% by weight and a saturated fatty acid having 12 or less carbon atoms of 12.5% by weight to 12.5% by weight.
6重量%及び炭素数 2 0以上の飽和脂肪酸を 4重量%〜 1 4重量%含有する油脂 混合物を提供する油脂から選ばれた油脂であることが必要である。 Fats and oils containing 6% by weight and 4 to 14% by weight of a saturated fatty acid having 20 or more carbon atoms need to be selected from fats and oils that provide a mixture of fats and oils.
2 ) B B油脂組成物を得るために用いられる原料油脂は、 飽和脂肪酸の総含有率 が 6 8重量%〜 7 5重量%で、 炭素数 1 2以下の飽和脂肪酸を 1 1重量%〜 1 6 重量%及び炭素数 2 0以上の飽和脂肪酸を 5重量%〜 1 4重量%含有する油脂混 合物を提供する油脂から選ばれた油脂であることが必要である。  2) The raw fat used for obtaining the BB fat composition has a total saturated fatty acid content of 68% by weight to 75% by weight and a saturated fatty acid having 12 or less carbon atoms of 11% by weight to 16% by weight. It is necessary that the fat or oil is selected from fats and oils that provide a fat and oil mixture containing 5% to 14% by weight of a saturated fatty acid having 20% or more carbon atoms by weight.
3 ) C C油脂組成物を得るために用いられる原料油脂は、 飽和脂肪酸の総含有率 が Ί 9重量%〜 8 2重量%で、 炭素数 1 2以下の飽和脂肪酸を 1 2重量%〜 1 7 重量%及び炭素数 2 0以上の飽和脂肪酸を 8重量%〜 2 4重量%含有する油脂混 合物を提供する油脂から選ばれた油脂であることが必要である。  3) The raw fat used for obtaining the CC fat composition has a total saturated fatty acid content of 9% to 82% by weight and a saturated fatty acid having 12 or less carbon atoms of 12% to 17%. It is necessary that the fat or oil be selected from fats and oils that provide a fat and oil mixture containing 8% to 24% by weight of a saturated fatty acid having 20 or more carbon atoms by weight.
従って、 A A油脂組成物、 B B油脂組成物及び C C油脂組成物を得るためには 、 いずれについても、 炭素数 1 2以下の飽和脂肪酸を含む油脂及び炭素数 2 0以 上の飽和脂肪酸を含む油脂が必要である。 脂肪酸組成を所望の範囲にするために 、 その他の脂肪酸からなる油脂を用いることもできる。  Therefore, in order to obtain the AA fat composition, the BB fat composition and the CC fat composition, all of the fats containing saturated fatty acids having 12 or less carbon atoms and the fats containing saturated fatty acids having 20 or more carbon atoms are required. is necessary. In order to adjust the fatty acid composition to a desired range, fats and oils composed of other fatty acids can be used.
炭素数 1 2以下の飽和脂肪酸を含む原料油脂としては、 例えば、 ヤシ油、 パー ム核油、 ババス油、 乳脂等をそれぞれ単独若しくは混合して用いることができる 。 また、 これらの油脂の単独若しくは混合油の水素添加油脂、 分別油脂、 分別油 脂の水素添加油脂、 水素添加油脂の分別油脂、 及びエステル交換油脂を用いるこ ともできる。  As a raw material fat or oil containing a saturated fatty acid having 12 or less carbon atoms, for example, coconut oil, palm kernel oil, babassu oil, milk fat and the like can be used alone or in combination. Hydrogenated fats and oils of these fats alone or in combination, fractionated fats and oils, hydrogenated fats and fats of fractionated fats, fractionated fats and oils of hydrogenated fats and transesterified fats and oils can also be used.
炭素数 2 0以上の脂肪酸を含む油脂としては、 例えば、 ハイエルシンナ夕ネ油 、 シロカラシナ油、 サル脂、 魚油等があり、 これら油脂の単独若しくは混合油の 水素添加油脂、 水素添加油脂の分別油脂及びエステル交換油脂を用いることがで きる。  Fats and oils containing fatty acids having 20 or more carbon atoms include, for example, Heyersinna evening oil, white mustard oil, monkey fat, fish oil, and the like. Transesterified fats and oils can be used.
その他の油脂としては、 例えば、 大豆油、 なたね油、 コーン油、 米油、 綿実油 、 パーム油、 牛脂、 豚脂等を単独若しくは混合して用いることができる。 また、 これら油脂の単独若しくは混合油の水素添加油脂、 分別油脂、 分別油脂の水素添 加油脂、 水素添加油脂の分別油脂及びエステル交換油脂を用いることもできる。 本発明の A T油脂組成物、 B T油脂組成物、 及び C T油脂組成物を得るために 用いる原料油脂は、 前記した A A油脂組成物、 B B油脂組成物及び C C油脂組成 物を得るために用いる原料油脂と類似であるが、 油脂混合物の構成脂肪酸として のトランス異性体含有率が 3重量%以下になる油脂から選ばれた油脂である必要 がある。 構成脂肪酸としてのトランス異性体含有率が 3重量%を越えると、 天然 の油脂のトランス異性体含有率からかけ離れ、 市場のニーズからも離れがちにな る点で不都合である。 天然の油脂はトランス異性体をほとんど含んでいないが、 水素添加油脂中には例えば 3 0〜 5 0重量%存在することがある。 従って、 原料 油として水素添加油脂を用いる場合には、 トランス異性体含有率を限定する必要 がある。 例えば、 ランダムエステル交換する油脂混合物中に水素添加油脂を 3 0 重量%使用する場合には、 水素添加油脂のトランス異性体含有率は 1 0 . 0重量 %以下であることが要求される。 同様に水素添加油脂を 2 0重量%使用する場合 には、 水素添加油脂の卜ランス異性体含有率は 1 5 . 0重量%以下であることが 要求される。 これらの要求は、 水素添加油脂を作製する際の反応条件、 例えば触 媒種、 触媒添加量、 温度、 圧力等が通常の条件であれば、 トランス異性体含有率 は用いる原料油脂によってそれぞれ再現され、 水素添加終了時点の沃素価を規定 すれば容易に満足させることができる。 Other fats and oils include, for example, soybean oil, rapeseed oil, corn oil, rice oil, cottonseed oil , Palm oil, tallow, lard, etc. can be used alone or in combination. Also, hydrogenated fats and oils of these fats alone or as a mixed oil, fractionated fats and oils, hydrogenated fats and oils of fractionated fats and oils, and separated fats and transesterified fats and oils of hydrogenated fats and oils can be used. The raw fat used for obtaining the AT fat composition, the BT fat composition and the CT fat composition of the present invention is the raw fat used for obtaining the AA fat composition, the BB fat composition and the CC fat composition described above. It is similar to that described above, but the fat must be selected from fats and oils in which the trans isomer content as a constituent fatty acid of the fat or oil mixture is 3% by weight or less. If the trans isomer content as a constituent fatty acid exceeds 3% by weight, it is inconvenient in that it is far from the trans isomer content of natural fats and oils and tends to depart from market needs. Natural fats and oils contain almost no trans isomer, but may be present, for example, in the hydrogenated fats in an amount of 30 to 50% by weight. Therefore, when a hydrogenated oil or fat is used as a feed oil, it is necessary to limit the trans isomer content. For example, when 30% by weight of a hydrogenated oil and fat is used in a fat and oil mixture to be subjected to random transesterification, the trans isomer content of the hydrogenated oil and fat is required to be 10.0% by weight or less. Similarly, when 20% by weight of hydrogenated oil is used, the trans isomer content of the hydrogenated oil and fat is required to be 15.0% by weight or less. These requirements are met by the reaction conditions for producing hydrogenated oils and fats, such as catalyst species, catalyst addition amount, temperature, pressure, etc., under normal conditions. If the iodine value at the end of hydrogenation is specified, it can be easily satisfied.
次に、 本発明の油脂組成物の製造方法について説明する。 本発明の製造方法に おいてランダムエステル交換する前の油脂混合物は、 上記の各種ランダムエステ ル交換油脂の主要脂肪酸組成をそれぞれ所要の範囲において設定し、 それらの所 要条件を満足する原料油脂 3種以上の選定及び各原料油脂の混合率を求めて調製 することができる。 上記の各種ランダムエステル交換油脂を得る方法は、 ナトリ ゥムメチラート等のアル力リ触媒による方法でもリパーゼ等の酵素による方法で もよく、 特に制限されるものではなく公知の非選択的エステル交換法によって得 ることができる。 ランダムエステル交換油脂は通常の油脂製品と同様に、 脱臭し て使用される。 発明を実施するための最良の形態 Next, a method for producing the oil / fat composition of the present invention will be described. In the oil and fat mixture before random transesterification in the production method of the present invention, the main fatty acid composition of each of the above-mentioned various random ester exchanged oils and fats is set within a required range, and the raw oil and fat satisfying the required conditions is used. It can be prepared by selecting more than one species and determining the mixing ratio of each raw material fat. The method for obtaining the above-mentioned various random transesterified fats and oils may be a method using an alkaline catalyst such as sodium methylate or a method using an enzyme such as lipase.The method is not particularly limited and may be obtained by a known non-selective transesterification method. Can be Random transesterified fats and oils are deodorized and used like ordinary fats and oils. BEST MODE FOR CARRYING OUT THE INVENTION
以下に実施例と比較例を挙げて更に本発明を説明するが、 本発明はこれらの実 施例に限定されるものではない。  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
(実施例 1 〜 1 4 )  (Examples 1 to 14)
飽和脂肪酸の総含有率が 4 8重量%〜 5 2重量%で、 炭素数 1 2以下の飽和脂 肪酸の含有率が 1 2 . 5重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸の 含有率が 4重量%〜 1 4重量%の範囲にあって、 卜ランス異性体が 3重量%を超 えるかもしくは 3重量%以下の油脂混合物を用いて、 ランダムエステル交換反応 してランダム反応油 (A A油脂組成物 7種及び A T油脂組成物 7種の計 1 4種) を作成した。  The total content of saturated fatty acids is 48% to 52% by weight, and the content of saturated fatty acids having 12 or less carbon atoms is 12.5% to 16% by weight and the content is 20% or more. A random transesterification reaction is carried out using an oil or fat mixture having a saturated fatty acid content of 4% by weight to 14% by weight and a trans isomer exceeding 3% by weight or less than 3% by weight. Random reaction oils (7 types of AA oil and fat composition and 7 types of AT oil and fat composition, a total of 14 types) were prepared.
ランダムエステル交換反応の方法及び条件を以下に示す。  The method and conditions of the random transesterification are shown below.
<ランダムエステル交換反応の方法及び条件 > <Method and conditions of random transesterification reaction>
ランダム反応容器に原料混合油を仕込み、 減圧下撹拌しつつ加熱し 1 2 0で、 3 0 誦 Hgに達するまで脱水した。 次いで、 ナトリウムメチラ一トを 0 . 3重量% 加え、 撹拌下窒素気流中で 4 0分反応させた。 反応液を 9 0 °Cまで冷却した後、 1 0 %クェン酸水溶液を加えて p H 1 1以下にし、 撹拌を止め静置した後、 油層 と水層を分離した。 油層に新たに 9 0 °Cの温水を加え撹拌した後、 静置して油層 と水層を分離するいわゆる温水洗浄を行った。 分離した水層の P Hが 8以下にな るまで温水洗浄を繰り返した後、 減圧下撹拌しつつ加熱し 1 0 0 °C、 3 0 匪 Hgに 達するまで脱水した。 次いで、 活性白土 3重量%を加え、 減圧下撹拌して 1 0 0 t:、 3 O mmHgに達してから 3 0分後に全量濾過した。  The mixed oil was charged into a random reaction vessel, heated with stirring under reduced pressure, and dehydrated at 120 to 30 Hg. Next, 0.3% by weight of sodium methylate was added, and the mixture was reacted for 40 minutes in a nitrogen stream with stirring. After the reaction solution was cooled to 90 ° C, a 10% aqueous solution of citric acid was added to adjust the pH to 11 or less. After stirring was stopped and the mixture was allowed to stand, an oil layer and an aqueous layer were separated. New warm water at 90 ° C was added to the oil layer and stirred, and then the system was allowed to stand still to perform so-called hot water washing to separate the oil layer and the aqueous layer. Washing with warm water was repeated until the pH of the separated aqueous layer became 8 or less, followed by heating while stirring under reduced pressure and dehydration until the temperature reached 100 ° C. and 30 Hg. Next, 3% by weight of activated clay was added, and the mixture was stirred under reduced pressure to reach 100 t: and 30 mm after reaching 30 mmHg.
このようにして製造したランダム反応油の脂肪酸組成は、 用いた原料混合油 とほとんど差がなかった。  The fatty acid composition of the random reaction oil produced in this manner was almost the same as that of the raw material mixed oil used.
原料混合油及びランダム反応油のトリグリセライ ド · トータルカーボン分布 をガスクロマトグラフによって測定し、 未反応率を求め、 未反応率が 3モル% を越えたものはデータとしなかった。  The triglyceride / total carbon distribution of the raw material mixed oil and the random reaction oil was measured by gas chromatography, and the unreacted rate was determined. Data for which the unreacted rate exceeded 3 mol% was not used as data.
未反応率は原料混合油の脂肪酸組成、 原料混合油及びランダム反応油のトリ グリセライ ド · 卜一夕ルカ一ボン組成に基づき、 ランダム反応油が平衡卜リグ リセライ ド、 平衡ジグリセライ ド及び未反応卜リグリセライ ドからなるものと して、 最小二乗法によって近似解を算出した。 The unreacted ratio is based on the fatty acid composition of the raw mixed oil, the triglyceride composition of the raw mixed oil and the random reactive oil, and the composition of the mixture of the random reactive oil. Approximate solutions were calculated by the least-squares method, assuming that they consisted of reserides, equilibrium diglycerides, and unreacted triglycerides.
原料油脂の配合 (配合率は重量%である) 、 ランダム反応油の脂肪酸組成及び 特性を表 1に示す。 Table 1 shows the blending of the raw fats and oils (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oil.
表 1 室 例 4 ς 7 Q Q 10 ■ i ' 14 リダ ]^ 、:由の名称 *τ AA-1 ΑΑ-3 ΑΑ-5 A A- 6 A A- 7 AT-2 AT - 3 AT-4 AT- 5 AT - 6 AT - 7Table 1 Room Example 4 ς 7 QQ 10 ■ i '14 Lida] ^,: Name * τ AA-1 ΑΑ-3 ΑΑ-5 A A- 6 A A- 7 AT-2 AT-3 AT-4 AT -5 AT-6 AT-7
! 、 7 OR n 7 7 ! , 7 OR n 7 7
料配 な ね油 28.0 35.2 1 6.7 25.4 44.9 1 3.3 26.0 37.3 41.5 28.8 33.8 46.0 27.9 35.1 油合 / \―ム油 26.2 1 7.7 33.8 23.6 3.2 40.8 25.8 脂率 硬化 油(IV = 65) 38.3 25.8 49.5 34.5 4.6 59.7 37 Filling oil 88.0 35.2 1 6.7 25.4 44.9 1 3.3 26.0 37.3 41.5 28.8 33.8 46.0 27.9 35.1 Oil / ¥ -oil 26.2 1 7.7 33.8 23.6 3.2 40.8 25.8 Fat ratio Hardened oil (IV = 65) 38.3 25.8 49.5 34.5 4.6 59.7 37
% 硬化ハイエルシンなたね油 IV = 1 0) 12.0 1 3.0 1 1 .3 12.4 26.2 2.7 12.1 14.9 14.9 1 5.0 14.9 26.6 7.2 14.9 脂 飽和脂肪酸含有率 48.0 48.0 52.0 52.0 50.0 50.0 50.0 48.0 48.0 52.0 52.0 50.0 50.0 50.0 肪組 炭素数 1 2以下の飽和酸含有率 12.5 15.0 1 3.0 1 6.0 14.0 14.0 14.0 1 2.5 15.0 1 3.0 16.0 14.0 14.0 14.0 酸成 炭素数 20以上の飽和酸含有率 8.0 8.0 8.0 8.0 14.0 4.0 8.0 8.0 8.0 8.0 8.0 14.0 4.0 8.0 % Hardened Hyersin rapeseed oil IV = 1 0) 12.0 1 3.0 1 1.3 12.4 26.2 2.7 12.1 14.9 14.9 1 5.0 14.9 26.6 7.2 14.9 Fats Saturated fatty acid content 48.0 48.0 52.0 52.0 50.0 50.0 50.0 48.0 48.0 52.0 52.0 50.0 50.0 50.0 Fatty carbon 12.5 15.0 13.0 16.0 14.0 14.0 14.0 12.5 15.0 13.0 16.0 14.0 14.0 14.0 Acidification Saturated acid content with 20 or more carbons 8.0 8.0 8.0 8.0 14.0 4.0 8.0 8.0 8.0 8.0 8.0 14.0 4.0 8.0
% トランス異性体含有率 1 7.0 1 1.9 21.7 1 5.5 4.0 25.3 1 6.8 1 .2 1.2 1.2 1.2 2.1 0.6 1 .2 反 上昇融点 (°c) 29.5 27.6 30.3 29.9 28.9 29.3 29.1 29.7 27.8 30.4 29.1 28.7 29.5 28.8 応特 ベネトレーシヨン測定温度 (°C) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 油性 ベネトレ一シヨン値 127 1 12 93 90 105 100 98 130 1 10 90.0 92 103 102 100 % Trans isomer content 1 7.0 1 1.9 21.7 1 5.5 4.0 25.3 1 6.8 1.2 1.2 1.2 1.2 2.1 0.6 1.2 Anti rising temperature (° c) 29.5 27.6 30.3 29.9 28.9 29.3 29.1 29.7 27.8 30.4 29.1 28.7 29.5 28.8 Special measurement temperature (° C) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Oiliness Venetization value 127 1 12 93 90 105 100 98 130 1 10 90.0 92 103 102 100
表 1より、 いずれの実施例においても硬化魚油 Aと同等の特性を持つ反応油が 得られることがわかった。 From Table 1, it was found that a reaction oil having properties equivalent to that of the hardened fish oil A was obtained in all the examples.
(実施例 1 5〜 2 8 ) (Examples 15 to 28)
飽和脂肪酸含有率が 6 8重量%〜 7 5重量%で、 炭素数 1 2以下の飽和脂肪酸 1 1重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸 5重量%〜 2 0重量% の範囲にあって、 トランス異性体が 3重量%を超えるか、 もしくは 3重量%以下 の油脂混合物を用いて、 実施例 1 と同様にランダムエステル交換反応してランダ ム反応油 (B B油脂組成物 7種及び B T油脂組成物 7種の計 1 4種) を作成した 原料油脂の配合 (配合率は重量%である) 、 ランダム反応油の脂肪酸組成及び 特性を表 2に示す。 Saturated fatty acid content of 68% to 75% by weight, saturated fatty acid having 12 or less carbon atoms 11% to 16% by weight and saturated fatty acid having 20 or more carbon atoms 5% to 20% by weight Random transesterification reaction as in Example 1 using a fat / oil mixture in which the trans isomer is more than 3% by weight or less than 3% by weight in the range of Table 2 shows the blending of the raw fats and oils (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oils for which 7 types and 7 types of BT fats and oils compositions were prepared.
表 2 実施例 NO. 15 16 17 18 19 20 21 22 23 24 25 26 27 28 ランダム反応油の名称 BB-1 BB-2 BB-3 BB-4 BB-5 BB-6 BB-7 BT-1 BT-2 BT-3 BT-4 BT-5 BT-6 BT-7 やし油 19.0 24.2 22.4 27.6 24.2 24.1 24.2 18.8 24.1 22.3 27.6 24.2 24.0 24.1 原 なたね油 27.5 26.1 Table 2 Example No.15 16 17 18 19 20 21 22 23 24 25 26 27 28 Name of random reaction oil BB-1 BB-2 BB-3 BB-4 BB-5 BB-6 BB-7 BT-1 BT -2 BT-3 BT-4 BT-5 BT-6 BT-7 Palm oil 19.0 24.2 22.4 27.6 24.2 24.1 24.2 18.8 24.1 22.3 27.6 24.2 24.0 24.1 Raw rapeseed oil 27.5 26.1
料配 パー厶油 57.2 39.4 39.6 47.4 49.7 油合 硬化なたね油(IV = 74) 29.6 29.8 19.6 19.8 25.6 25.4 25.4 Distribution Palm oil 57.2 39.4 39.6 47.4 49.7 Oiling Hardened rapeseed oil (IV = 74) 29.6 29.8 19.6 19.8 25.6 25.4 25.4
脂率 硬化パ一ム油(IV = 10) 32.6 27.2 39.1 33.7 11.8 41.4 31.5 6.9 31.5 21.2 15J 15.3 20.3 9.1Fat ratio Hardened palm oil (IV = 10) 32.6 27.2 39.1 33.7 11.8 41.4 31.5 6.9 31.5 21.2 15J 15.3 20.3 9.1
% 硬化ハイエルシンなたね油(IV = 10) 18.8 18.8 18.9 18.9 38.4 9.1 18.9 % Hardened Hyersin rapeseed oil (IV = 10) 18.8 18.8 18.9 18.9 38.4 9.1 18.9
硬化ハイエルシンなたね油(IV= 1) 17.1 16.9 17.1 17.1 34.4 8.3 17.1 脂 飽和脂肪酸含有率 68.0 68.0 75.0 75.0 71.0 71.0 71.0 68.0 68.0 75.0 75.0 71.0 71.0 71.0 肪組 炭素数 12以下の飽和酸含有率 11.0 14.0 13.0 16.0 14.0 14.0 14.0 11.0 14.0 13.0 16.0 14.0 14.0 14.0 酸成 炭素数 20以上の飽和酸含有率 10.0 10.0 10.0 10.0 20.0 5.0 10.0 10.0 10.0 10.0 10.0 20.0 5.0 10.0 Hardened Hyersin rapeseed oil (IV = 1) 17.1 16.9 17.1 17.1 34.4 8.3 17.1 Fat Saturated fatty acid content 68.0 68.0 75.0 75.0 71.0 71.0 71.0 68.0 68.0 75.0 75.0 71.0 71.0 71.0 Fat group Saturated acid content with 12 or less carbon atoms 11.0 14.0 13.0 16.0 14.0 14.0 14.0 11.0 14.0 13.0 16.0 14.0 14.0 14.0 Acid content of saturated acid with 20 or more carbon atoms 10.0 10.0 10.0 10.0 20.0 5.0 10.0 10.0 10.0 10.0 10.0 20.0 5.0 10.0
% 卜ランス異性体含有率 16.2 15.9 12.7 12.3 14.5 14.5 14.4 0.7 2.7 1.9 1.4 1.6 1.7 0.9 反 上昇融点 (°c) 37.7 38.4 39.4 38.8 38.0 38.5 38.3 37.8 38.6 39.3 38.7 38.5 38.7 38.4 応特 ベネトレ一シヨン測定温度 (°c) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 油性 ベネトレ一シヨン値 28 28 22 20 25 23 23 29 26 21 23 24 25 27 % Trans isomer content 16.2 15.9 12.7 12.3 14.5 14.5 14.4 0.7 2.7 1.9 1.4 1.6 1.7 0.9 Anti rising melting point (° c) 37.7 38.4 39.4 38.8 38.0 38.5 38.3 37.8 38.6 39.3 38.7 38.5 38.7 38.4 ° c) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Oiliness Venetization value 28 28 22 20 25 23 23 29 26 21 23 24 25 27
j 6 表 2より、 いずれの実施例においても硬化魚油 Bと同等の特性を持つ反応油が 得られることがわかった。 from j 6 Table 2, reactions oils having the same characteristics and cured fish oil B in any of the embodiments could be obtained.
(実施例 2 9〜 4 2 ) (Examples 29 to 42)
飽和脂肪酸含有率が 7 9重量%〜 8 2重量%で、 炭素数 1 2以下の飽和脂肪酸 1 2重量%〜 1 7重量%及び炭素数 2 0以上の飽和脂肪酸 8重量%〜 2 4重量% の範囲にあって、 トランス異性体が 3重量%を超えるか、 もしくは 3重量%以下 の油脂混合物を用いて、 実施例 1 と同様にランダムエステル交換反応してランダ ム反応油 (C C油脂組成物 7種及び C T油脂組成物 7種の計 1 4種) を作成した 原料油脂の配合 (配合率は重量%である) 、 ランダム反応油の脂肪酸組成及び 特性を表 3に示す。 Saturated fatty acid content of 79% to 82% by weight, saturated fatty acids having 12 or less carbon atoms 12% to 17% by weight and saturated fatty acids having 20 or more carbon atoms 8% to 24% by weight Random reaction oil (CC oil and fat composition) by random transesterification as in Example 1 using an oil or fat mixture having a trans isomer content of more than 3% by weight or less than 3% by weight. Table 3 shows the blending of the raw fats and oils (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oils, which prepared 7 types and 7 types of CT fats and oils compositions (total of 14 types).
表 3 実施例 NO. 29 30 31 32 33 34 35 36 37 38 39 40 41 42 ランダム反応油の名称 CC-1 CC-2 CC-3 CC-4 CC-5 CC-6 CC-7 CT-1 CT-2 CT-3 CT-4 CT-5 CT-6 CT-7 原 やし油 20.6 25.8 24.1 29.3 25.9 25.8 25.8 20.6 25.8 24.1 29.3 25.9 25.8 25.8 料配パ一ム油 24.6 24.8 17.0 17.3 21.2 20.9 20.9 30.0 30.2 22.4 22.7 32.1 24.5 26.4 油合硬化パー厶油(IV = 10) 31.9 26.4 35.9 30.4 6.4 38.1 30.3 28.9 23.4 33.0 27.5 0.4 36.1 27.3 脂率硬化ハイエルシンなたね油(IV = 10) 22.9 23.0 23.0 23.0 46.5 15.2 23.0 Table 3 Example NO.29 30 31 32 33 34 35 36 37 38 39 40 41 42 Name of random reaction oil CC-1 CC-2 CC-3 CC-4 CC-5 CC-6 CC-7 CT-1 CT -2 CT-3 CT-4 CT-5 CT-6 CT-7 Raw palm oil 20.6 25.8 24.1 29.3 25.9 25.8 25.8 20.6 25.8 24.1 29.3 25.9 25.8 25.8 Delivery oil 24.6 24.8 17.0 17.3 21.2 20.9 20.9 30.0 30.2 22.4 22.7 32.1 24.5 26.4 Oil-hardened palm oil (IV = 10) 31.9 26.4 35.9 30.4 6.4 38.1 30.3 28.9 23.4 33.0 27.5 0.4 36.1 27.3 Oil-hardened hyersin rapeseed oil (IV = 10) 22.9 23.0 23.0 23.0 46.5 15.2 23.0
%硬化ハイエルシンなたね油(IV= 1) 20.5 20.6 20.5 20.5 41.6 13.6 20.5 脂 飽和脂肪酸含有率 79.0 79.0 82.0 82.0 80.5 80.5 80.5 79.0 79.0 82.0 82.0 80.5 80.5 80.5 肪組炭素数 12以下の飽和酸含有率 12.0 15.0 14.0 17.0 15.0 15.0 15.0 12.0 15.0 14.0 17.0 15.0 15.0 15.0 酸成炭素数 20以上の飽和酸含有率 12.0 12.0 12.0 12.0 24.0 8.0 12.0 12.0 12.0 12.0 12.0 24.0 8.0 12.0 % Hardened Hyersin rapeseed oil (IV = 1) 20.5 20.6 20.5 20.5 41.6 13.6 20.5 Fat Saturated fatty acid content 79.0 79.0 82.0 82.0 80.5 80.5 80.5 79.0 79.0 82.0 82.0 80.5 80.5 80.5 Fatty acid content of fatty acid group with 12 or less 12.0 15.0 14.0 17.0 15.0 15.0 15.0 12.0 15.0 14.0 17.0 15.0 15.0 15.0 Saturated acid content with 20 or more acid carbons 12.0 12.0 12.0 12.0 24.0 8.0 12.0 12.0 12.0 12.0 12.0 24.0 8.0 12.0
% トランス異性体含有率 4.4 4.0 4.7 4.3 4.2 4.3 4.3 2.5 2.1 2.8 2.4 0.4 3.0 2.4 反 上昇融点 (°c) 42.5 42.0 44.2 43.5 42.2 42.5 42.3 43.2 41.8 44.3 43.0 42.5 42.9 43.0 応特ベネトレ一シヨン測定温度 (°c) 30 30 30 30 30 30 30 30 30 30 30 30 30 30 油性ぺネトレ一シヨン値 32 25 26 23 26 25 24 30 26 25 26 24 26 25 % Trans isomer content 4.4 4.0 4.7 4.3 4.2 4.3 4.3 2.5 2.1 2.8 2.4 0.4 3.0 2.4 Anti rising melting point (° c) 42.5 42.0 44.2 43.5 42.2 42.5 42.3 43.2 41.8 44.3 43.0 42.5 42.9 43.0 c) 30 30 30 30 30 30 30 30 30 30 30 30 30 30 Oily penetration value 32 25 26 23 26 25 24 30 26 25 26 24 26 25
1 1 .
1 o 表 3よりいずれの実施例においても硬化魚油 Cと同等の特性を持つ反応油が得 られることがわかった。  1 o From Table 3, it was found that a reactive oil having the same characteristics as the hardened fish oil C was obtained in all the examples.
(比較例 1〜 1 2 ) (Comparative Examples 1 to 12)
本発明の脂肪酸組成の範囲をわずかずつ超える油脂混合物を用いて、 実施例 1 と同様にランダムエステル交換反応してランダム反応油 (A A A油脂組成物 4種 、 B B B油脂組成物 4種及び C C C油脂組成物 4種の計 1 2種) を作成した。 原料油の配合 (配合率は重量%である) 、 ランダム反応油の脂肪酸組成及び特 性を表 4に示す。 Using a fat mixture slightly exceeding the range of the fatty acid composition of the present invention, a random transesterification reaction was carried out in the same manner as in Example 1 to obtain a random reaction oil (four kinds of AAA fat compositions, four kinds of BBB fat compositions and four kinds of CCC fat compositions). 4 kinds of products, a total of 1 2 kinds). Table 4 shows the blending of the base oil (the blending ratio is% by weight) and the fatty acid composition and characteristics of the random reaction oil.
表 4 Table 4
Figure imgf000021_0001
Figure imgf000021_0001
表 4より、 いずれの比較例とも本発明の油脂組成物と同等の特性を持つものは 得られないことがわかった。 From Table 4, it was found that none of the comparative examples had properties equivalent to those of the oil and fat composition of the present invention.
(比較例 1 3〜: L 5) (Comparative Example 13: L5)
炭素数 2 0以上の脂肪酸をほとんど含まない油脂を用いて、 実施例 1 と同様 に飽和脂肪酸含有率及び炭素数 1 2以下の飽和脂肪酸含有率は本発明の範囲にあ る油脂混合物を調製して、 ランダムエステル交換反応してランダム反応油 (AA A油脂組成物 1種、 B B B油脂組成物 1種及び C C C油脂組成物 1種の計 3種) を作成した。 その結果を表 4に示す。  A fat / oil mixture having a saturated fatty acid content and a saturated fatty acid content of 12 or less carbon atoms falling within the range of the present invention was prepared in the same manner as in Example 1 using fats and oils containing almost no fatty acids having 20 or more carbon atoms. Then, a random transesterification reaction was performed to prepare a random reaction oil (one kind of AAA oil composition, one kind of BBB oil composition, and one kind of CCC oil composition). The results are shown in Table 4.
表 4より、 比較例 1 3、 比較例 1 4及び比較例 1 5において、 炭素数 2 0以上 の脂肪酸をほとんど含まない油脂混合物を用いた場合でも、 硬化魚油 A、 硬化魚 油 B又は硬化魚油 Cに相当する特性を有する反応油が得られることがわかった。  From Table 4, it can be seen that in Comparative Examples 13 and 14, Comparative Examples 14 and 15, even when a fat / oil mixture containing almost no fatty acid having 20 or more carbon atoms was used, the hardened fish oil A, the hardened fish oil B, or the hardened fish oil was used. It was found that a reaction oil having properties equivalent to C was obtained.
(実施例 4 3〜 5 7、 比較例 1 6〜 1 8、 対照例 1〜 3 ) (Examples 43 to 57, Comparative Examples 16 to 18, Control Examples 1 to 3)
以上のようにして得た硬化魚油 A、 硬化魚油 B、 又は硬化魚油 Cに相当する特 性を有する油脂組成物等を用いてマーガリンを作製しその特性を評価した。 <マーガリンの作製方法及び条件 >  Margarine was prepared using the oil-and-fat composition having properties corresponding to the hardened fish oil A, hardened fish oil B, or hardened fish oil C obtained as described above, and the properties thereof were evaluated. <Production method and conditions of margarine>
1 ) 油相部の調製; 原料配合した油脂 (以下 「調合油」 という) 8 0. 9 4重 量部、 乳化剤としてエマルジー M S (理研ビタミン製) 0. 1重量部、 大豆レシ チン 0. 1重量部、 着色料としてカロチン 1 0 p pm、 アナトー色素 0. 0 1重 量部、 香料としてバタ一フレ一バ一 5 p pm、 ミルクフレ一バ一 7 0 p p mを混 合し 6 0°Cに保った。  1) Preparation of oil phase; oils and fats mixed with raw materials (hereinafter referred to as “mixed oil”) 8 0.9 4 parts by weight, emulsifier MS (manufactured by RIKEN Vitamin) 0.1 part by weight, soybean lecithin 0.1 Parts by weight, 10 parts by weight of carotene as coloring agent, 0.01 parts by weight of annatto dye, 5 parts per million of flavor and 5 ppm of milk flavor and 70 ppm of milk flavor at 60 ° C Kept.
2 ) 水相部の調製;脱脂乳 (乳固型分 8 %) 1 4. 4重量部、 食塩 1. 2重量 部を混合し水分が 1 6. 4重量部になるように水を追加し、 80°C以上で 3 0分 殺菌した。  2) Preparation of aqueous phase; skim milk (milk solids content: 8%) 14.4 parts by weight, 1.2 parts by weight of common salt were mixed, and water was added so that the water content was 16.4 parts by weight. Sterilized at 80 ° C or higher for 30 minutes.
3 ) 予備乳化及び急冷可塑化; 上記 1 ) および 2) で調製した油相部と水相部 を混合し、 6 0°Cに保ち以下連続的に乳化槽を通して乳化均質化し、 3段のクー リングシリンダーからなるコンビネータータイプのモデル機で急冷可塑化した。 急冷可塑化は、 2段目出口温度が調合油の上昇融点よりも 2 0°C± 2°C低い温 度になるように、 また 3段目の出口温度が調合油の上昇融点よりも 1 3。C ± 2 °C 低い温度となるように、 また 1段目の出口温度が 2段目出口温度と 1段目入口温 度の平均値に近くなるように冷媒流量を調節して行った。 3) Pre-emulsification and quenching plasticization: Mix the oil phase and the aqueous phase prepared in 1) and 2) above, maintain at 60 ° C and continuously emulsify and homogenize through an emulsification tank. It was quenched and plasticized by a combinator type model machine consisting of a ring cylinder. In quenching plasticization, the temperature at the second stage outlet is 20 ° C ± 2 ° C lower than the rising melting point of the compounded oil. So that the outlet temperature of the third stage is 13 higher than the rising melting point of the blended oil. The refrigerant flow rate was adjusted so that the temperature was lower by C ± 2 ° C, and the outlet temperature of the first stage was close to the average value of the outlet temperature of the second stage and the inlet temperature of the first stage.
ク一リングシリンダーの回転数は、 1段目、 2段目、 3段目とも 5 0 0 r p m で行い、 流量は概ね 5 0 K g Z H rであった。  The number of rotations of the cooling cylinder was 500 rpm for the first, second, and third stages, and the flow rate was approximately 50 KgZHr.
4 ) 充填 ;急冷可塑化した製品を 5 K gのダンボールに充填した。  4) Filling: The quenched plasticized product was filled into a 5 kg corrugated cardboard.
5 ) テンパリング; ダンポールに充填した製品を、 調合油の上昇融点より 5 °C 土 1 °C低い温度で 3 6時間保管して熟成した。  5) Tempering: The product filled in the dampole was stored and aged for 36 hours at a temperature 5 ° C and a temperature 1 ° C lower than the rising melting point of the compounded oil.
6 ) 保管条件; テンパリング終了後、 マーガリンを調合油の上昇融点より 1 5 :〜 2 0 °C低い温度で保管した。  6) Storage conditions; After tempering, margarine was stored at a temperature 15 to 20 ° C lower than the rising melting point of the compounded oil.
<マーガリン製品の評価項目とその方法及び条件 >  <Margarine product evaluation items, methods and conditions>
1 ) ぺネトレーシヨン値; ダンボールに充填してあるマ一ガリンに、 両切りべ ネ缶 (内径 5 7 mm、 長さ 4 0 mm) の片方から完全に突っ込み両端に盛り上げ た状態でサンプルを採取し、 ぺネ缶の両端をバタ一ナイフで面切りし、 測定温度 の恒温水糟に浸潰しておき 2時間後にベネトロメ一夕一で測定した。  1) Penetration value: A sample was taken in a state in which both sides of a double-sided can (57 mm in diameter and 40 mm in length) were completely inserted into the margarine filled in the cardboard box and pushed up at both ends.ぺ Both ends of the can were cut with a knives and immersed in a constant temperature water bath at the measurement temperature. Two hours later, measurement was performed overnight at Venetome.
2 ) キメ及びツヤ ; ダンポールに充填してあるマ一ガリンを、 バターナイフを 用いてその表面を平滑に削り取って、 マ一ガリンの表面状態を各々 5点法で評価 した。  2) Texture and gloss; The surface of the margarine filled in the damper was cut off smoothly using a butter knife, and the surface condition of the margarine was evaluated by a 5-point method.
3 ) キメの評価基準;  3) Texture evaluation criteria;
5点 =極めてなめらかで、 ザラザラ感が全くない。  5 points = extremely smooth, with no roughness.
4点 =なめらかで、 ザラザラ感が殆どない。  4 points = Smooth, with almost no roughness.
3点 =ややなめらかであるが、 ザラザラ感がある。  3 points = Smooth, but rough.
2点 =なめらかさが殆どなくザラザラ感がかなり強い。  2 points = There is almost no smoothness and the roughness is quite strong.
1点 =なめらかさが全くなく、 ザラザラしている。  1 point = There is no smoothness and it is rough.
4 ) ツヤの評価基準; 4) Gloss evaluation criteria;
5点 =極めて光沢がある。  5 points = extremely glossy.
4点 =かなり光沢がある。  4 points = quite shiny.
3点 =光沢がある。  3 points = glossy
2点 =光沢が殆どない。 1点 =光沢が全くない。 2 points = Little gloss. 1 point = no gloss.
<バタークリーム試験 > <Butter cream test>
ホバートミキサー (カント一ミキサー社製) タイプ N 5 0 ( 5コート用) を用 い測定温度に設定した恒温室で行った。 試験はテンパリング終了時点と 4週間後 の 2回行った。  The measurement was carried out in a constant temperature room using a Hobart mixer (manufactured by Kant-I-Mixer Co., Ltd.) type N50 (for 5 coats) and set at the measurement temperature. The test was performed twice, at the end of tempering and four weeks later.
測定温度に保持したマ一ガリン試料 3 0 0 gをボールに入れ、 ホバ一トミキサ 一にセッ トし撹拌スピード N〇. 1 (低速) で 2分間撹拌し試料をほぐした。 次 いで撹拌しながら、 比重 1 . 3 1に調整したシロップ 2 4 0 m 1 を 1分間で添加 し、 撹拌スピードを N O . 2 (中速) にし、 5分後撹拌を止めてボール内壁に付 着している試料をかき落とし更に撹拌した。 撹拌を止めてクリームを秤量缶に採 取して秤量し、 クリ一ミング価 (含気空気量 m 1ノ試料 g X 1 0 0 ) を求めた。 撹拌スピードを N O . 2 (中速) にしてからの実質撹拌時間が 1 0分と 1 5分 のクリーミング価を求めた。 この操作後のクリームについて、 次の項目について 評価した。  300 g of a margarine sample maintained at the measurement temperature was put in a bowl, set in a hover mixer, and stirred at a stirring speed N〇.1 (low speed) for 2 minutes to loosen the sample. Then, while stirring, add 240 ml of syrup adjusted to a specific gravity of 1.31 over 1 minute, set the stirring speed to NO.2 (medium speed), stop stirring after 5 minutes, and attach the ball The worn sample was scraped off and further stirred. The stirring was stopped, and the cream was collected in a weighing can and weighed to determine a creaming value (aerated air amount m 1 sample g X 100). The creaming values of the actual stirring time of 10 minutes and 15 minutes after the stirring speed was set to NO.2 (medium speed) were determined. The cream after this operation was evaluated for the following items.
ぐクリーム評価項目〉 Gu cream evaluation item>
1 ) シロップの分離; シロップ分離の程度を次の評価基準で評価した。  1) Syrup separation: The degree of syrup separation was evaluated according to the following evaluation criteria.
5点 =シロップの分離が認められず、 光沢が均一である。  5 points = No syrup separation, uniform gloss.
4点 =シロップの分離はないが、 光沢がやや不均一である。  4 points = no syrup separation, but slightly uneven gloss.
3点 =小粒のシロップ分離が認められる。  3 points = small syrup separated.
2点 =小粒のシ口ップ分離がかなり認められる  2 points = considerable separation of small grains
1点 =大粒のシロップ分離が認められる  1 point = large syrup separated
2 ) かたさ ;絞り性の評価; クリームを花形口金付絞り袋に詰め、 絞り出す時 のかたさを評価した。  2) Hardness; evaluation of squeezability; The cream was packed in a squeeze bag with a flower-shaped base and the hardness when squeezed out was evaluated.
5点 =かたさが適度であって、 絞りやすい。  5 points = Moderate hardness and easy to squeeze.
4点 =かたさにやや難点があるが、 絞りやすい。  4 points = Difficulty in hardness, but easy to squeeze.
3点 =ややかたい又はやや軟らかいが、 絞りやすい。  3 points = Slightly soft or slightly soft, but easy to squeeze.
2点 =ややかたく又はやや軟らかく、 やや絞りにくい。  2 points = Slightly hard or slightly soft, slightly difficult to draw.
1点 =かた過ぎて又は柔らか過ぎて、 絞りにくい。  1 point = too hard or too soft, difficult to squeeze.
3 ) キメ及びツヤ ;花形口金付絞り袋から絞り出したクリームの表面状態を評 価した。 3) Texture and gloss; Evaluation of the surface condition of the cream squeezed out of a squeeze bag with a flower-shaped base. Valued.
評価基準はぐマーガリン製品の評価項目とその方法及び条件 >に記したものと 同じである。  The evaluation criteria are the same as those described in the section on the evaluation items and methods and conditions for gugu margarine products.
4 ) のび;絞り出したクリ 'ムの表面状態を評価した。  4) Growth: The surface condition of the squeezed cream was evaluated.
5点=絞り目 (エツジ がシャープで、 目がきれいにたっている。  5 points = iris eye (edge is sharp, eyes are clean.
4点 =絞り目 (エツジ がシャープであるが、 わずかに乱れている。 3点 =絞り目 (エツジ が少し切れ、 ところどころアバ夕になる。  4 points = iris (edge is sharp but slightly disturbed. 3 points = iris (edge is cut a little, and some places are abalone.
2点 =絞り目 (エッジ がかなり切れ、 かなりアバ夕である。  2 points = iris (the edge is quite broken, it is quite ababa.
1点 =絞り目 (エッジ がデコボコで非常にもろい。  1 point = aperture (The edge is rough and very fragile.
55 )) ここしし ;;絞絞りり出出しした 2 55)) here;; squeezed out 2
たククリリームに振動を 3 与え、 振動前後の保型性を評価した。 5点 =形が振動前と変化していない。 非常に安定している。  The vibrator was subjected to three vibrations and the shape retention before and after the vibration was evaluated. 5 points = Shape has not changed from before vibration. Very stable.
4点 =形が極わずかに変化しているが安定している。  4 points = shape is very small but stable.
3点 =形が若干くずれ変形しかかっている。  3 points = The shape is slightly deformed.
2点 =形がくずれ変形している。  2 points = Shape is deformed.
1点 =形が大きく変形している。  1 point = Shape is greatly deformed.
ぐマ一ガリンの作製と評価〉 Preparation and evaluation of gumagallin>
上昇融点及び硬さの異なるマーガリンを作製し、 評価した。  Margarines with different rising melting points and hardness were prepared and evaluated.
対照例 1 〜 3は、 硬化魚油 A、 硬化魚油 B、 硬化魚油 Cから選ばれた油脂を主 体とする油脂を用いた。  In Comparative Examples 1 to 3, fats and oils selected from hardened fish oil A, hardened fish oil B, and hardened fish oil C were used.
比較例 1 6〜 1 8は、 硬化魚油 A、 硬化魚油 B、 硬化魚油 Cから選ばれた 1種 又は 2種以上と、 比較例 1 3、 比較例 1 4、 又は比較例 1 5で得た油脂組成物を 用いた。  Comparative Examples 16 to 18 were obtained in Comparative Example 13, Comparative Example 14, or Comparative Example 15 with one or more selected from hydrogenated fish oil A, hydrogenated fish oil B, and hydrogenated fish oil C. An oil / fat composition was used.
実施例 4 3〜 5 7は、 硬化魚油 A、 硬化魚油 B、 硬化魚油 Cから選ばれた 1種 又は 2種、 及び実施例 1 〜 4 2で得た油脂組成物を用いた。  In Examples 43 to 57, one or two kinds selected from hardened fish oil A, hardened fish oil B, and hardened fish oil C, and the oil and fat compositions obtained in Examples 1 to 42 were used.
なお、 ここで用いた硬化魚油の特性は以下の通りであった。  The properties of the hardened fish oil used here were as follows.
硬化魚油 A 上昇融点 2 9 . 8 t:、 2 0 トレーション値 1 0 5 硬化魚油 B 上昇融点 3 8 . 4で、 2 0 トレ一シヨン値 2 4 硬化魚油 C 上昇融点 4 3 . 5 °C、 3 0 ^トレーション値 2 7 調合油の原料油配合 (配合率は重量%である) と調合油の上昇融点を表 5〜 7 示す' 表 5
Figure imgf000026_0001
Hardened fish oil A, rising melting point 29.8 t :, 20 Torr value 10 5 Hardened fish oil B, with rising melting point 38.4, 20 training value 24 Hardened fish oil C, rising melting point 4 3.5 ° C , 30 ^ toration value 27 Table 5-7 shows the blending of the base oil of the blended oil (the blending ratio is% by weight) and the rising melting point of the blended oil. Show 'Table 5
Figure imgf000026_0001
表 6 Table 6
Figure imgf000027_0001
Figure imgf000027_0001
表 7 Table 7
Figure imgf000028_0001
Figure imgf000028_0001
マーガリン製品の特性の経日変化の結果を表 8〜 1 0に示す Tables 8 to 10 show the results of daily changes in the properties of margarine products.
表 8 Table 8
対照例 1 比較例 16 実施例 43 実施例 44 実施例 45 Control Example 1 Comparative Example 16 Example 43 Example 44 Example 45
1曰 130 131 136 133 1361 says 130 131 136 133 136
10°C 1週 135 133 127 136 128 ぺネ 2週 130 133 128 130 124 値 3週 128 125 125 128 12810 ° C 1 week 135 133 127 136 128 ぺ 2 weeks 130 133 128 130 124 Value 3 weeks 128 125 125 128 128
4週 129 123 120 130 1204 weeks 129 123 120 130 120
8週 125 120 120 128 1228 weeks 125 120 120 128 122
1曰 173 175 181 177 1751 Said 173 175 181 177 175
15°C 1週 175 170 183 177 172 ぺネ 2週 170 176 180 174 168 値 3週 170 168 182 170 17015 ° C 1 week 175 170 183 177 172 ぺ 2 weeks 170 176 180 174 168 Value 3 weeks 170 168 182 170 170
4週 175 165 178 173 1654 weeks 175 165 178 173 165
8週 168 165 175 171 168 キメ 1曰 5 5 5 5 58 weeks 168 165 175 171 168 Texture 1 5 5 5 5 5
1週 5 4 5 5 51 week 5 4 5 5 5
2週 5 3 5 5 52 weeks 5 3 5 5 5
3週 5 3 5 5 53 weeks 5 3 5 5 5
4週 5 3 5 5 54 weeks 5 3 5 5 5
8週 4 2 4 4 4 ツヤ 1曰 5 4 5 5 58 weeks 4 2 4 4 4 Glossy 1 says 5 4 5 5 5
1週 5 4 5 5 51 week 5 4 5 5 5
2週 5 3 5 5 52 weeks 5 3 5 5 5
3週 5 3 5 5 53 weeks 5 3 5 5 5
4週 5 3 5 5 54 weeks 5 3 5 5 5
8週 4 2 4 4 4 8 weeks 4 2 4 4 4
表 9 Table 9
Figure imgf000030_0001
Figure imgf000030_0001
表 1〇 Table 1〇
Figure imgf000031_0001
Figure imgf000031_0001
表 8〜 1 0より、 対照例、 比較例、 実施例のいずれにおいてもベネトレーショ ン値 (ベネ値) の経日変化の差異はほとんどないことがわかった。 From Tables 8 to 10, it was found that there was almost no difference in the daily change of the penetration value (bene value) in any of the control example, the comparative example, and the example.
即ち、 製品のちょう度 (硬さ) の経日変化については、 硬化魚油 A、 硬化魚油 B又は硬化魚油 Cの配合油を用いたものであっても、 炭素数 2 0以上の脂肪酸を ほとんど含まない油脂のランダム油と硬化魚油 A、 硬化魚油 B又は硬化魚油 Cの 配合油を用いたものであっても、 また、 本発明の油脂組成物と硬化魚油 A、 硬化 魚油 B又は硬化魚油 Cの配合油を用いたものであってもほとんど差がないことが わかった。  In other words, the daily change in consistency (hardness) of the product, even when using a mixed oil of hardened fish oil A, hardened fish oil B, or hardened fish oil C, contains almost all fatty acids having 20 or more carbon atoms. Even if a mixed oil of a random oil of fat and oil and hardened fish oil A, hardened fish oil B or hardened fish oil C is used, the oil and fat composition of the present invention and hardened fish oil A, hardened fish oil B or hardened fish oil C can also be used. It was found that there was almost no difference even when using the blended oil.
表 8〜 1 0より、 キメ及びツヤの経日変化については、 対照例 1〜 3のいずれ もが 8週間後でも良好な商品性を有するのに対して、 比較例 1 6〜 1 8は 2週間 後で既に商品性に欠けるものとなることがわかった。 また実施例 4 3〜 5 7のい ずれもが、 8週間後でも良好な商品性を有し対照例と同等であることがわかった クリーム評価結果を表 1 1〜 1 3に示す t From Tables 8 to 10, it can be seen from the comparison of the change in texture and gloss over time that Comparative Examples 1 to 3 have good commercial properties even after 8 weeks, while Comparative Examples 16 to 18 have 2 A week later, it turned out to be unproductive. The t showing Embodiment 4 3-5 7 noise deviation also is a cream evaluation results were found to be comparable to the Control Example had good marketability even after 8 weeks in Table 1 1-1 3
表 11 Table 11
対照例 1 比較例 16 実施例 43 実施例 44 実施例 45 ホイップ ;皿、 ソ 14.1 13.4 13.5 13.8 13.5 初温 (°C) 14.0 13.5 13.5 13.4 13.6 終温 (°c) 15.1 14.5 14.5 14.6 14.8 ホイップ 時間  Control Example 1 Comparative Example 16 Example 43 Example 44 Example 45 Whip; Dish, Saw 14.1 13.4 13.5 13.8 13.5 Initial temperature (° C) 14.0 13.5 13.5 13.4 13.6 Final temperature (° c) 15.1 14.5 14.5 14.6 14.8 Whip time
時間と 10分 190 150 182 185 190 ホイップ価 15分 200 183 210 198 205 クリーム 分 離 5 5 5 5 組織 の び 5 5 5 5 5 こ し 4 3 4 4 4 キ メ 4 3 4 4 4 ッ ャ 4 3 4 4 4 Time and 10 minutes 190 150 182 185 190 Whip value 15 minutes 200 183 210 198 205 Cream separation 5 5 5 5 Tissue growth 5 5 5 5 5 Strain 4 3 4 4 4 Texture 4 3 4 4 4 Char 4 3 4 4 4
表 12 Table 12
対照例 2 実施例 46 実施例 47 実施例 48 実施例 49 実施例 50 ホイッブ ϋ ( しノ 22.1 22.0 22.2 22.1 22.1 22.3 22 初温(°c) 21.5 21.7 21.8 21.5 21.7 21.4 21.6 終温 (°C) 22.2 22.3 22.5 22.5 22.7 22.8 22.4 ホイッブ 時間  Control Example 2 Example 46 Example 47 Example 48 Example 49 Example 50 Whib ϋ (Shino 22.1 22.0 22.2 22.1 22.1 22.3 22 Initial temperature (° c) 21.5 21.7 21.8 21.5 21.7 21.4 21.6 Final temperature (° C) 22.2 22.3 22.5 22.5 22.7 22.8 22.4 Whib time
時間と 10分 180 175 190 185 180 175 176 ホイップ価 15分 220 205 225 223 221 215 220 クリーム 分 離 5 5 5 5 5 5 5 組織 の び 4 4 4 4 4 4 4 こ し 5 4 5 5 5 5 5 キ メ 4 3 4 4 4 4 4 ッ ャ 4 3 4 4 4 4 4  Time and 10 minutes 180 175 190 185 180 175 176 Whip value 15 minutes 220 205 225 223 221 215 215 220 Cream separation 5 5 5 5 5 5 5 Tissue growth 4 4 4 4 4 4 4 Strain 5 4 5 5 5 5 5 Texture 4 3 4 4 4 4 4 Charger 4 3 4 4 4 4 4 4
Bird
表 13 Table 13
対照例 3 比較例 18 実施例 51 実施例 52 実施例 53 実施例 54 実施例 55 実施例 56 実施例 5フ ホイッフ 室温 (°C) 30.5 31.2 30.8 30.6 30.5 30J 30.4 30.4 30.6 初温 (°C) 30.2 31.0 30.5 30.6 30.2 30.3 30.6 30.2 30.8 終温 (°c) 31.0 31.5 31.8 31.5 31.5 31.9 31.3 31.0 31.8 ホイップ 時間  Control Example 3 Comparative Example 18 Example 51 Example 52 Example 53 Example 54 Example 55 Example 56 Example 5 F Whiff Room temperature (° C) 30.5 31.2 30.8 30.6 30.5 30J 30.4 30.4 30.6 Initial temperature (° C) 30.2 31.0 30.5 30.6 30.2 30.3 30.6 30.2 30.8 Final temperature (° c) 31.0 31.5 31.8 31.5 31.5 31.9 31.3 31.0 31.8 Whip time
時間と 10分 172 168 175 170 175 180 175 168 174 ホイップ価 15分 205 190 210 208 208 212 202 205 210 クリーム 分 離 5 5 5 5 5 5 5 5 5 組織 の び 4 3 4 4 4 4 4 4 4 こ し 5 4 5 5 5 5 5 5 5 キ メ 5 4 5 5 5 5 5 5 5 ッ ャ 4 3 4 4 4 4 4 4 4 Time and 10 minutes 172 168 175 170 175 180 175 168 174 Whip value 15 minutes 205 190 210 208 208 212 202 205 210 Cream separation 5 5 5 5 5 5 5 5 5 5 Tissue growth 4 3 4 4 4 4 4 4 4 5 4 5 5 5 5 5 5 5 Texture 5 4 5 5 5 5 5 5 5 Char 4 3 4 4 4 4 4 4 4
なお、 バタ一クリーム試験の結果は、 テンパリング終了時点と 4週間後でほと んど違いが認められなかったのでテンパリング終了時点の結果を示した。 The results of the butter cream test showed the results at the end of tempering since almost no difference was observed after 4 weeks from the end of tempering.
表 1 ;!〜 1 3より、 クリーム評価結果については、 ホイップ価、 シロップの分 離及びのびは対照例、 比較例、 及び実施例との差異はほとんどないことがわかつ た。 こし、 キメ及びツヤは対照例に対し比較例は劣るものであることがわかった 。 実施例はいずれも対照例に匹敵する商品性に優れたものであることがわかった  table 1 ;! From 13 to 13, it was found that the whipping value, the separation of syrup, and the spread of the cream evaluation were almost the same as those of the control, comparative, and examples. The texture and gloss were found to be inferior in the comparative example to the control example. All the examples were found to be excellent in commercial properties comparable to the control example.
産業上の利用可能性 Industrial applicability
本発明による油脂組成物は、 マーガリンあるいはショートニング原料として、 硬化魚油と混合使用してもまた、 硬化魚油と混合しなくとも、 硬化魚油を用いた 製品のキメ及びツヤの経日変化並びにホイップクリームのこし、 キメ及びツヤが 同等の特性を有する製品を提供することができる。 また、 トランス異性体含有率 が 3 %重量以下のものは、 硬化魚油を用いた製品と同等の特性を有するマ一ガリ ンあるいはショートニングを提供することができる。  The oil / fat composition according to the present invention can be used as a raw material for margarine or shortening, whether mixed with hardened fish oil or not, even if not mixed with hardened fish oil. It is possible to provide a product whose texture and gloss are equivalent. In addition, those having a trans isomer content of 3% by weight or less can provide margarine or shortening having properties equivalent to those of products using hydrogenated fish oil.

Claims

請求の範囲 The scope of the claims
1. 飽和脂肪酸の総含有率が 4 8重量%〜 5 2重量%で、 炭素数 1 2以下の飽 和脂肪酸を 1 2. 5重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸を 4重 量%〜 1 4重量%含有する油脂混合物のランダムエステル交換油脂であって、 上 昇融点が 2 9. 0 ± 1. 5°Cで、 2 0°Cのぺネトレ一シヨン値が 1 1 0土 2 2で ある油脂組成物。 1. Saturated fatty acids having a total content of saturated fatty acids of 48% to 52% by weight and having 12 or less carbon atoms 12.5% to 16% by weight and saturated fatty acids having 20 or more carbon atoms Is a random transesterified fat containing 4% by weight to 14% by weight of a fat and oil mixture having an upper melting point of 29.0 ± 1.5 ° C and a penetration value of 20 ° C. An oil / fat composition which is 110 soil 22.
2. 飽和脂肪酸の総含有率が 6 8重量%〜 7 5重量%で、 炭素数 1 2以下の飽 和脂肪酸を 1 1重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸を 5重量% 〜 2 0重量%含有する油脂混合物のランダムエステル交換油脂であって、 上昇融 点が 3 8. 0 ± 1. 5°Cで、 2 0 °Cのぺネトレ一シヨン値が 2 5 ± 5である油脂 組成物。  2. Saturated fatty acids having a total content of saturated fatty acids of 68% to 75% by weight, saturated fatty acids having 12 or less carbon atoms of 11% to 16% by weight, and saturated fatty acids having 20 or more carbon atoms of 5% or less. It is a random transesterified fat containing an oil / fat mixture containing 20% by weight to 20% by weight, having an ascending melting point of 38.0 ± 1.5 ° C and a penetration value at 20 ° C of 25 ± 5%. 5. The fat or oil composition which is 5.
3. 飽和脂肪酸の総含有率が 7 9重量%〜 8 2重量%で、 炭素数 1 2以下の飽 和脂肪酸を 1 2重量%〜 1 7重量%及び炭素数 2 0以上の飽和脂肪酸を 8重量% 〜 24重量%含有する油脂混合物のランダムエステル交換油脂であって、 上昇融 点が 4 3. 0土 1. 5°Cで、 3 0 °Cのぺネトレ一シヨン値が 2 5 ± 7である油脂 組成物。  3. The total saturated fatty acid content is 79% to 82% by weight, the saturated fatty acid having 12 or less carbon atoms is 12% to 17% by weight and the saturated fatty acid having 20 or more carbon atoms is 8%. It is a random transesterified fat containing a fat mixture containing 24 wt% to 24 wt%, with an ascending melting point of 43.0 soil 1.5 ° C, and a penetration value of 30 ° C of 25 ± 7. A fat or oil composition that is:
4. 構成脂肪酸としてのトランス異性体含有率が 3重量%以下である請求項 1 〜 3のいずれかに記載の油脂組成物。  4. The fat or oil composition according to any one of claims 1 to 3, wherein the content of trans isomer as a constituent fatty acid is 3% by weight or less.
5. 請求項 1〜 4記載の油脂組成物からなる群より選択される少なくとも 2種 を配合して得られる油脂組成物。 5. An oil / fat composition obtained by blending at least two types selected from the group consisting of the oil / fat compositions according to claim 1 to 4.
6. 請求項 1〜 4記載の油脂組成物からなる群より選択される少なくとも 1種 と、 他の動植物油脂及び動植物加工油脂の少なくとも 1種とを配合してなる油脂 組成物。  6. An oil / fat composition comprising at least one selected from the group consisting of the oil / fat composition according to claim 1 and at least one other animal / vegetable oil / fat and animal / vegetable processed oil / fat.
7. 飽和脂肪酸の総含有率が 4 8重量%〜 5 2重量%で、 炭素数 1 2以下の飽 和脂肪酸を 1 2. 5重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸を 4重 量%〜 1 4重量%含有する油脂混合物をランダムエステル交換することにより、 上昇融点が 2 9. 0 ± 1. 5°Cで、 2 0°Cのぺネトレ一シヨン値が 1 1 0 ± 2 2 である油脂組成物を製造する油脂組成物の製造方法。 7. Saturated fatty acids having a total content of saturated fatty acids of 48% to 52% by weight and having a carbon number of 12 or less 12.5% to 16% by weight and saturated fatty acids having a carbon number of 20 or more The fat and oil mixture containing 4% by weight to 14% by weight is subjected to random transesterification, so that the rising melting point is 29.0 ± 1.5 ° C and the penetration value at 20 ° C is 1 1 A method for producing an oil / fat composition for producing an oil / fat composition of 0 ± 22.
8. 飽和脂肪酸の総含有率が 68重量%〜 7 5重量%で、 炭素数 1 2以下の飽 和脂肪酸を 1 1重量%〜 1 6重量%及び炭素数 2 0以上の飽和脂肪酸を 5重量% 〜20重量%含有する油脂混合物をランダムエステル交換することにより、 上昇 融点が 38. 0 ± 1. 5°C、 20 °Cのべネトレーシヨン値が 2 5 ± 5である油脂 組成物を製造する油脂組成物の製造方法。 8. The total content of saturated fatty acids is 68% to 75% by weight, 11% to 16% by weight of saturated fatty acids having 12 or less carbon atoms and 5% by weight of saturated fatty acids having 20 or more carbon atoms. % By weight is subjected to random transesterification of an oil or fat mixture containing 20 to 20% by weight to produce an oil or fat composition having a rising melting point of 38.0 ± 1.5 ° C and a penetration value of 25 ± 5 at 20 ° C. A method for producing an oil and fat composition.
9. 飽和脂肪酸の総含有率が 79重量%〜8 2重量%で、 炭素数 1 2以下の飽 和脂肪酸を 1 2重量%〜 1 7重量%及び炭素数 2 0以上の飽和脂肪酸を 8重量% 〜24重量%含有する油脂混合物をランダムエステル交換することにより、 上昇 融点が 43. 0 ± 1. 5で、 30°Cのベネトレ一シヨン値が 25 ± 7である油脂 組成物を製造する油脂組成物の製造方法。  9. Total content of saturated fatty acids is 79% to 82% by weight, saturated fatty acids having 12 or less carbon atoms are 12% to 17% by weight, and saturated fatty acids having 20 or more carbon atoms are 8% by weight. % By weight of a fat / oil mixture containing from 24% to 24% by weight, the resulting fat / oil mixture having a rising melting point of 43.0 ± 1.5 and a nettlence value at 30 ° C. of 25 ± 7 is produced. A method for producing the composition.
1 0. 油脂混合物として、 構成脂肪酸としてのトランス異性体含有率が 3重量 %以下となるものを用いてなる請求項 7〜 9のいずれかに記載の油脂組成物の製 造方法。  10. The method for producing an oil / fat composition according to any one of claims 7 to 9, wherein a fat / oil mixture having a trans isomer content as a constituent fatty acid of 3% by weight or less is used.
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JP2000129286A (en) 2000-05-09
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ID29259A (en) 2001-08-16

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