JP2002038190A - Plastic fat oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilized plastic fat oil composition that has a wide range of plasticity and causes no change in the hardness with days. SOLUTION: The objective plastic fat oil composition includes the fat oil of direct β-type crystals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a plastic oil composition such as margarine and shortening using an oil which is a direct β-type crystal, preferably a fine crystal.

[0002]

2. Description of the Related Art
Fats and oils used for plastic fats and oils such as margarine and shortening are "margarine shortening lard" (P3
24, written by Kimitoshi Nakazawa: Published by Korin Co., Ltd. “Margarine and shortening are defined as plastics that have crystalline fat at room temperature, so their physical properties are mainly related to consistency, plasticity and crystal structure. I do. Physically, the crystalline state of Alfa is waxy (like acetoglyceride), B
Eta is a coarse crystal, and Beta-prime is a fine grain. In melting point, Alfa, Beta-prime, B
It becomes higher in the order of eta. The preferred crystalline state of margarine and shortening composition is called beta-prime. ], The crystal state is considered to be good in β-prime type, and it has been used.

[0003] β-prime type fat crystals take fine crystals, contribute to emulsion stability, and exhibit good consistency. On the other hand, since the β-prime type crystal is a metastable form in terms of energy, there is a drawback that a transition phenomenon to a more energy stable β-type crystal occurs when storage conditions are not appropriate. Since this β-type crystal is the most stable type, it does not cause any further transition phenomenon, but it generally has a large crystal size, forms coarse crystal grains called graining or bloom, and has a rough texture and poor touch. Present and have no product value at all.

[0004] Among the β-type crystals passing through the β-prime type, those having a relatively small crystal size are also known. For example, V-type crystals of cocoa butter correspond to this, and are substantially SO 2
It is a β2-type crystal of a symmetric triglyceride such as S or POS. However, in order to obtain a β-type crystal having such a relatively small crystal size, it is necessary to go through a special heat treatment step called tempering, or to cool to a predetermined temperature and then add a specific component serving as a crystal nucleus. A complicated process was required. As a result, in the quenching plasticizing step for producing ordinary plastic oils and fats, the crystals are not actually obtained. The V-type crystals of cocoa butter have poor plasticity.

[0005] On the other hand, even the β-prime type and most stable type fats and oils tend to harden over time, so that the method of depositing crystals and the method of storage must be carefully controlled.

In order to solve the above-mentioned problems, various proposals have been made so far for the purpose of obtaining fine crystals which are stable in terms of energy. Tokiko Sho 51-9763
Japanese Patent Application Publication No. JP-A-2002-115139 discloses a method for obtaining a β-type crystal by setting a specific triglyceride ratio. Japanese Patent Publication No. 58-13128 discloses a method for suppressing the graining of fats and oils by a transesterification reaction.
Japanese Patent No. 295271 discloses methods for maintaining fine crystals by blending a high melting point fat or oil.

However, the method disclosed in Japanese Patent Publication No. 51-9763 requires a tempering operation to obtain a β-type crystal.
According to the method of JP-295271, the obtained composition tends to be hardened with time, and the plastic oil / fat composition was not sufficiently satisfactory in terms of stability.

Accordingly, an object of the present invention is to provide a plastic oil / fat composition which has a wide plasticity range and whose hardness does not change over time.

[0009]

According to the present invention, the above object has been achieved by a plastic fat composition containing a fat which is a direct β-type crystal, preferably a fine crystal.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the plastic fat composition of the present invention will be described in detail.

The present invention relates to a plastic fat composition containing a fat which is a direct β-type crystal.

The above-mentioned fat or oil which is a direct β-form crystal is not supposed to take the β-prime form which is metastable in terms of energy, but to the most stable form due to the packing state of triglyceride molecules which is the essence of the crystallization phenomenon of fats and oils. Refers to fats and oils in which only β-type crystals exist. That is, the fats and oils which are the direct β-type crystals used in the present invention are precipitated as β-type crystals under any cooling conditions. Strictly speaking, immediately after the precipitation of the crystal, it once passes through the α-type crystal, but since this α-type crystal is very unstable in terms of energy, it rapidly transitions to the β-type crystal, and substantially β Exists as a type crystal. In addition, fats and oils which are direct β-type crystals in the present invention do not require special heat treatment such as tempering in the fat and oil crystallization step.

In the present invention, it is necessary to contain the above-mentioned fats and oils which are the direct β-type crystals, and when only fats and oils which are not the direct β-type crystals, for example, only the β-prime type most stable fats and oils are used, It tends to become harder on a daily basis, and is not preferable as a plastic fat composition unless the crystal precipitation method and storage method are carefully controlled.

In the present invention, the β-type crystal is preferably a fine crystal. The above-mentioned fine crystals mean that the crystals of fats and oils are fine, and mean that the crystals do not feel rough when touched or touched, and are preferably 20 μm or less, more preferably 10μ
m, most preferably 3 μm or less in size. The size indicates the length of the maximum portion of the crystal.

It is preferable that the plastic fat composition of the present invention substantially contains the fine crystals as described above. The term “substantially” means that 90% by weight or more of fine crystals are contained in all the direct β-type crystals.

When a fat or oil crystal having a crystal size of more than 20 μm is used, it is easy to feel rough when touching or touching the mouth, and it is difficult to retain the liquid oil component, which causes oil bleeding of the product. In the case of a water-in-oil type emulsion having an aqueous phase component easily, the aqueous phase component may not be maintained in a three-dimensional structure formed by fat crystals.

In the present invention, it is essential to use fats and oils which are directly β-type crystals. Even in the case of fine crystals, fats and oils that are not directly β-type crystals, for example, when fats and oils that pass through β-prime type crystals are used, the β-prime type crystals are metastable in terms of energy. Is not appropriate, the more stable energetically stable β
There is a risk of causing a transition phenomenon to a type crystal. Since the resulting β-form crystals are fat crystals having a size exceeding 20 μm, they are completely unfavorable as plastic fat compositions for the reasons described above. In addition, in the case of using a fat and oil that is the finest crystal, and is the most stable form of β-prime type fat and does not cause crystal transition to β-type, it tends to become harder over time, and as a plastic fat and oil composition, Is not sufficiently satisfactory in terms of stability.

Any kind of fats and oils can be used as long as they are fine crystals and are directly β-type crystals that do not pass through the β-prime type.

Examples of such fats and oils include palm oil, palm kernel oil, coconut oil, corn oil, cottonseed oil, soybean oil,
Various vegetable oils such as rapeseed oil, rice oil, sunflower oil, safflower oil, beef tallow, milk fat, lard, cocoa butter, fish oil, whale oil, shea butter, monkey fat, mango fat, cocoum fat, illipe fat, animal fats and oils These may include one or more selected from processed fats and oils which have been subjected to one or more treatments selected from hydrogenation, fractionation and transesterification. Among them, soybean oil, sunflower oil, shea butter, shea fractionated oil,
It is preferable to use an oil or fat obtained by subjecting one or more selected from monkey fat fractionated oils to one or more treatments selected from hydrogenation, fractionation and transesterification. More preferably, high oleic sunflower hardened oil, hardened oil of shea fractionated soft oil or hardened oil of this hardened oil, hardened oil of monkey fractionated soft oil or hardened oil of this hardened oil, soybean extremely hardened oil and sunflower oil It is desirable to use a combination of a softened fractionated oil of a transesterified oil and a hardened fractionated shear oil.

In the plastic fat composition of the present invention, the fat or oil which is the above-mentioned direct β-type crystal crystal is preferably 5% by weight or more, more preferably 10% by weight or more, and most preferably the total fat content of the plastic fat composition. Uses 30% by weight or more. If the content of the fat or oil that is a direct β-type crystal is less than 5% by weight based on the total fat or oil content of the plastic fat or oil composition, the content of the fat or oil becomes 2
Β-type crystals having a size exceeding 0 μm tend to appear, and tend to become harder over time.

In the plastic fat composition of the present invention, fats and oils which are not directly β-type crystals may be used. When a fat or oil that is not a direct β-form crystal is used, the fat or oil that is not a direct β-form crystal is preferably 95% by weight or less, more preferably 90% by weight or less, and most preferably 70% by weight or less, in the total fat content of the plastic fat composition. It is.

Other components that can be contained in the plastic fat composition of the present invention include, for example, water, an emulsifier, a thickener, a salting agent such as sodium chloride and potassium chloride, acetic acid, lactic acid, gluconic acid and the like. Acidulants, sugars and sugar alcohols, stevia, sweeteners such as aspartame, β-carotene, caramel, coloring agents such as red yeast rice pigment, tocopherols,
Antioxidants such as tea extract, vegetable protein eggs such as wheat protein and soy protein and various processed egg products, water, flavors, dairy products, seasonings, pH adjusters, food preservatives, shelf life improvers, fruits,
Food materials and food additives such as fruit juice, coffee, nut paste, spices, cacao mass, cocoa powder, cereals, beans, vegetables, meat, seafood, and the like.

Examples of the emulsifier include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, glycerin organic acid fatty acid ester, polyglycerin fatty acid ester, polyglycerin condensed ricinoleate, calcium stearoyl lactate, stearoyl lactic acid Examples thereof include sodium, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, lecithin, saponins and the like, and one or more selected from these can be used. The amount of the emulsifier is not particularly limited, but is preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight in the plastic fat composition of the present invention. Further, in the plastic fat composition of the present invention,
If the emulsifier is not required, the emulsifier need not be used.

Examples of the thickening stabilizer include guar gum, locust bean gum, carrageenan, gum arabic, alginic acids, pectin, xanthan gum, pullulan, tamarind seed gum, psyllium seed gum, crystalline cellulose, carboxymethylcellulose, methylcellulose, agar, glucoside. Examples thereof include mannan, gelatin, starch, and modified starch, and one or more selected from these can be used. . The amount of the thickening stabilizer is not particularly limited, but is preferably 0 to 10% by weight, more preferably 0 to 5% by weight in the plastic fat composition of the present invention. In the plastic fat composition of the present invention, the thickening stabilizer may not be used if the thickening stabilizer is not required.

Next, a method for producing the plastic fat composition of the present invention will be described. The method for producing the plastic fat composition of the present invention is not particularly limited, and an oil phase containing fat or oil, which is a β-type crystal, and an aqueous phase if necessary are mixed and emulsified. Then, it is desirable to perform a sterilization process next. The sterilization method may be a batch type in a tank or a continuous type using a plate type heat exchanger or a scraping type heat exchanger. Next, it is plasticized by cooling. In the present invention, the cooling condition is preferably-
0.5 ° C./min or more, more preferably −5 ° C./min or more. At this time, rapid cooling is preferable to slow cooling,
In the present invention, even with slow cooling, take a fine β-type crystal,
It is possible to obtain a stable plastic oil / fat composition having a wide plasticity range and its hardness does not change over time. Examples of the cooling device include a closed-type continuous tube cooler, for example, a margarine manufacturing machine such as a voter, a combinator, and a perfector, a plate-type heat exchanger, and the like. No.

Further, in any of the production steps for producing the plastic oil composition of the present invention, nitrogen or air may or may not be included.

The obtained plastic oil composition of the present invention may be either a margarine type or a shortening type, and its emulsified form is water-in-oil type, oil-in-water type,
And double emulsion type.

The plastic fat composition of the present invention is used for kneading, filling, sanding, topping, etc. in bakery products such as bread, confectionery bread, danish, shoe, donut, cake, cookie, hard biscuit, waffle, scone, etc. Can be used for spread. In addition, the amount of the plastic oil composition of the present invention used in the above-mentioned applications varies depending on the application, and is not particularly limited.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A high oleic sunflower oil was used as a raw material, and hydrogenation was carried out using a nickel catalyst to give a melting point of 4.
A hardened oil (a) at 0 ° C. was obtained. The presence or absence of crystal transition of the hardened oil (a) was confirmed by DSC. As a result, it was found that the oil was a direct β-type crystal fat which did not take the β-prime type. For confirmation, the cured oil (a) was completely melted at a temperature of 60 ° C. or higher, and then crystallized at 5 ° C. and subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26. A strong diffraction line corresponding to the interplanar spacing of Angstrom was obtained, and it was confirmed that the fat crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

70% by weight of the hardened oil (a) and soybean oil 3
0% by weight, and 0.5% by weight of stearic acid monoglyceride and 0.1% by weight of lecithin as an emulsifier were mixed and dissolved in 81% by weight of an oil phase, 16% by weight of water, 1% by weight of sodium chloride, skim milk powder 2 % By weight as a water-in-oil emulsion (b) by a conventional method, and a quenching plasticizing step (−20 ° C./min or more)
To obtain margarine. The obtained margarine was a fine fat or oil crystal having a size of 3 μm or less under an optical microscope, and it was confirmed by X-ray diffraction measurement that it took β-form. Moreover, the obtained margarine has a rheometer value of 5 g at 1000 g / cm.
² and wider softer plastic range even at low temperatures, 1 from the production
After 5 months, the rheometer value at 5 ℃ is 1000g / c.
The oil and fat composition was stable without changing its hardness over time as m ² .

Example 2 Although the cooling rate in the ordinary quenching plasticizing step is -20 ° C./min or more, the emulsion (b) used in Example 1 was cooled more slowly (cooling rate: T
(1 ° C./min). The obtained margarine has a fine β of 3 μm or less as in ordinary quenching plasticization.
Take a type crystal, and the rheometer value at 5 ° C is 1200 g / c.
m ² , it is soft even at low temperatures and has a wide plasticity range.
It was a stable oil / fat composition having a hardness of cm ² and no change over time.

[Example 3] Shea fractionated soft oil was used as a raw material,
Hydrogenation was performed using a nickel catalyst to obtain a hardened oil (c) having an iodine value of 59. The presence or absence of crystal transition of the hardened oil (c) was confirmed by DSC, and as a result, it was a direct β-type crystal fat and oil which did not take β-prime type. For confirmation, add 6 hardened oils (c).
After complete melting at a temperature of 0 ° C. or more, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26. As a result, a strong diffraction line corresponding to a plane spacing of 4.6 Å was obtained. Was obtained, and it was confirmed that the fat crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

70% by weight of the above hardened oil (c) and soybean oil 3
0% by weight, and 0.5% by weight of stearic acid monoglyceride and 0.1% by weight of lecithin as an emulsifier were mixed and dissolved in 81% by weight of an oil phase, 16% by weight of water, 1% by weight of sodium chloride, skim milk powder 2 % By weight as a water-in-oil emulsion (d) by a conventional method, and a quenching plasticizing step (−20 ° C./min or more)
To obtain margarine. The obtained margarine was a fine fat or oil crystal having a size of 3 μm or less under an optical microscope, and it was confirmed by X-ray diffraction measurement that it took β-form. Moreover, the obtained margarine has a rheometer value of 5 g at 1000 g / cm.
² and wider softer plastic range even at low temperatures, 1 from the production
After 5 months, the rheometer value at 5 ℃ is 1000g / c.
The oil and fat composition was stable without changing its hardness over time as m ² .

Example 4 The cooling rate in the ordinary quenching plasticizing step is -20 ° C./min or more. However, the emulsion (d) used in Example 3 was cooled more slowly (cooling rate: T
(1 ° C./min). The obtained margarine has a fine β of 3 μm or less as in ordinary quenching plasticization.
Take a type crystal, and the rheometer value at 5 ° C is 1100 g / c.
m ² , it is soft even at low temperatures and has a wide plastic range, and the rheometer value at 5 ° C. after one month from the production is 1100 g /
It was a stable oil / fat composition having a hardness of cm ² and no change over time.

Example 5 Monkey fractionated soft oil was used as a raw material.
Hydrogenation was performed using a nickel catalyst to obtain a hardened oil (e) having an iodine value of 38. The presence or absence of crystal transition of the hardened oil (e) was confirmed by DSC. As a result, it was a direct β-type crystal fat which did not take the β-prime type. For confirmation, hardened oil (e)
After complete melting at a temperature of 0 ° C. or higher, X-ray diffraction measurement was performed on a crystal precipitated at 5 ° C. in the range of 2θ: 17 to 26. A strong diffraction line corresponding to a plane spacing of 4.6 Å was obtained. Was obtained, and it was confirmed that the fat crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

70% by weight of the above hardened oil (e) and soybean oil 3
0% by weight, and 0.5% by weight of stearic acid monoglyceride and 0.1% by weight of lecithin as an emulsifier were mixed and dissolved in 81% by weight of an oil phase, 16% by weight of water, 1% by weight of sodium chloride, skim milk powder 2 % By weight as a water-in-oil emulsion (f) by a conventional method, and a quenching plasticizing step (−20 ° C./min or more)
To obtain margarine. The obtained margarine was a fine fat or oil crystal having a size of 3 μm or less under an optical microscope, and it was confirmed by X-ray diffraction measurement that it took β-form. The obtained margarine had a rheometer value of 5300C of 1300 g / cm.
² and wider softer plastic range even at low temperatures, 1 from the production
The rheometer value at 5 ℃ after 1 month is 1300g / c
The oil and fat composition was stable without changing its hardness over time as m ² .

Example 6 Although the cooling rate in the ordinary quenching plasticizing step is -20 ° C./min or more, the emulsion (f) used in Example 5 was cooled more slowly (cooling rate: T
(1 ° C./min). The obtained margarine has a fine β of 3 μm or less as in ordinary quenching plasticization.
Take a type crystal, and the rheometer value at 5 ° C is 1500 g / c.
m ² , it is soft even at low temperatures and has a wide plastic range, and the rheometer value at 5 ° C. after one month from the production is 1500 g /
It was a stable oil / fat composition having a hardness of cm ² and no change over time.

Example 7 Monkey fractionated soft oil was used as a raw material,
Hydrogenation in the presence of DL-methionine was performed to obtain a hardened oil having an iodine value of 54, and the hardened oil was fractionated by dry fractionation to obtain a fractionated hard oil (g). The fractionated hard part oil (g) was checked for the presence or absence of crystal transition by DSC. As a result, it was a direct β-type crystal fat which did not take the β-prime type. For confirmation, the fractionated hard part oil (g) was completely melted at a temperature of 60 ° C. or higher, and then crystallized at 5 ° C. to obtain 2θ:
When X-ray diffraction measurement was performed in the range of 17 to 26,
A strong diffraction line corresponding to the interplanar spacing of 4.6 angstroms was obtained, and it was confirmed that the fat crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

An oil obtained by mixing 35% by weight of the fractionated hard oil (g) and 65% by weight of soybean oil, and mixing and dissolving 0.5% by weight of monoglyceride stearate and 0.1% by weight of lecithin as an emulsifier. A 81% by weight phase, 16% by weight of water, 1% by weight of salt, and 2% by weight of skim milk powder are made into a water-in-oil type emulsion (h) by a conventional method, and a quenching plasticizing step (-20 ° C / min or more) To obtain margarine. The obtained margarine was fine oil and fat crystals having a size of 3 μm or less under an optical microscope, and it was confirmed by X-ray diffraction measurement that it took β-form. The obtained margarine had a rheometer value of 5300C of 1300 g / c.
m ² , it is soft even at low temperatures and has a wide plastic range, and the rheometer value at 5 ° C. after 1 month from the production is 1300 g /
It was a stable oil / fat composition having a hardness of cm ² and no change over time.

Example 8 The cooling rate in the usual quenching plasticizing step is -20 ° C./min or more. However, the emulsion (h) used in Example 7 was cooled more slowly (cooling rate: T
(1 ° C./min). The obtained margarine has a fine β of 3 μm or less as in ordinary quenching plasticization.
Take a type crystal, and the rheometer value at 5 ° C is 1500 g / c.
m ² , it is soft even at low temperatures and has a wide plastic range, and the rheometer value at 5 ° C. after one month from the production is 1500 g /
It was a stable oil / fat composition having a hardness of cm ² and no change over time.

Example 9 A mixture obtained by mixing soybean extremely hardened oil and sunflower oil at a weight ratio of 1: 4 was used as a raw material.
A transesterification reaction was performed in the presence of a sodium methoxide catalyst to obtain a reaction oil. Next, this reaction oil was fractionated by solvent fractionation to obtain a fractionated soft part oil. This fractionated soft oil 80
% By weight and 20% by weight of the shea fractionated hard oil were mixed to obtain a mixed oil (i). The presence of crystal transition in the mixed oil (i) was confirmed by DSC. As a result, the mixed oil (i) was a direct β-type crystal fat without the β-prime type. For confirmation, mix oil (i) with 6
After complete melting at a temperature of 0 ° C. or more, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26. As a result, a strong diffraction line corresponding to a plane spacing of 4.6 Å was obtained. Was obtained, and it was confirmed that the fat crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

80% by weight of the above mixed oil (i) and soybean oil 2
0% by weight, and 0.5% by weight of stearic acid monoglyceride and 0.1% by weight of lecithin as an emulsifier were mixed and dissolved in 81% by weight of an oil phase, 16% by weight of water, 1% by weight of sodium chloride, skim milk powder 2 % By weight as a water-in-oil emulsion (j) by a conventional method, and a quenching plasticizing step (−20 ° C./min or more)
To obtain margarine. The obtained margarine was a fine fat or oil crystal having a size of 3 μm or less under an optical microscope, and it was confirmed by X-ray diffraction measurement that it took β-form. The obtained margarine had a rheometer value of 900 g / cm ^{2 at} 5 ° C.
It is soft even at low temperatures and has a wide plastic range. The rheometer value at 5 ° C. after one month from the production is also 900 g / cm ^2.
And the oil composition was stable with no change in hardness over time.

Example 10 The cooling rate in the ordinary quenching plasticization step is -20 ° C./min or more. However, the emulsion (j) used in Example 9 is cooled more slowly (cooling rate: Under cooling at -1 ° C / min). The obtained margarine has fine β-type crystals of 3 μm or less, and has a rheometer value at 5 ° C. of 1000 g / m.
cm ² , it is soft even at low temperatures and has a wide range of plasticity.
/ Cm ² , which was a stable oil / fat composition without change in hardness over time.

Example 11 70% by weight of the hardened oil (a) used in Example 1 and 30% by weight of soybean oil were mixed and subjected to a quenching plasticizing step (at -20 ° C./min or more) to obtain a shortening. Was. The resulting shortening is under an optical microscope,
It is a fine oil and fat crystal of 3 μm or less.
We confirmed that we took the mold. Rheometer value also obtained shortening 5 ° C. wide plasticity range softer at 1100 g / cm ² and a cold rheometer value of 5 ° C. even 1100 g / cm ² and day by day at one month after elapsed from manufacture The oil composition was stable without changing the hardness.

Example 12 The cooling rate in the ordinary quenching plasticizing step is -20 ° C./min or more. However, 70% by weight of the hardened oil (a) used in Example 11 and 30% by weight of soybean oil are used. Under the slower cooling conditions (-1 ° C. /
Min) under cooling. The obtained shortening takes a fine β-type crystal of 3 μm or less in the same manner as in ordinary quenching plasticization, and has a rheometer value of 1200 g / cm at 5 ° C.
² and wider softer plastic range even at low temperatures, 1 from the production
After 5 months, the rheometer value at 5 ℃ is 1200g / c.
The oil and fat composition was stable without changing its hardness over time as m ² .

Example 13 Using fish oil as a raw material, hydrogenation was performed using a nickel catalyst to obtain a hardened fish oil having a melting point of 35 ° C. When this fish oil-hardened oil was checked for the presence or absence of crystal transition by DSC, it was a β-prime type fat.
For confirmation, this fish oil-hardened oil was completely melted at a temperature of 60 ° C or higher, and then crystallized at 5 ° C.
When X-ray diffraction measurement was performed in the range of 26, a strong diffraction line corresponding to an interplanar spacing of 4.2 angstroms was obtained, and it was confirmed that the fat crystals had β-prime type.

This hardened oil of fish oil (70% by weight) and 30% by weight of the hardened oil (a) used in Example 1 were mixed and subjected to a quenching plasticizing step (-20 ° C./min or more) to obtain a shortening. The resulting shortening was 3 μm under an optical microscope.
The following fine oil and fat crystals were confirmed to be of the β type in X-ray diffraction measurement. The resulting shortening is 5 ° C
Has a rheometer value of 800 g / cm ² , which is soft even at a low temperature and has a wide plasticity range.
Has a rheometer value of 800 g / cm ² , which is a stable oil and fat composition whose hardness does not change over time.

Example 14 The cooling rate in the usual quenching plasticizing step is -20 ° C./min or more. However, 70% by weight of the hardened fish oil used in Example 13 and 30% by weight of the hardened oil (a) The mixture was cooled under slower cooling conditions (to a cooling rate of -1 ° C).
/ Minute) under cooling. The obtained shortening has a fine β of 3 μm or less as in the case of ordinary quenching plasticization.
Take a type crystal, and the rheometer value at 5 ° C is 1000 g / c.
m ² , it is soft even at low temperatures and has a wide plasticity range.
It was a stable oil / fat composition having a hardness of cm ² and no change over time.

[Comparative Example 1] Using fish oil as a raw material, hydrogenation was performed using a nickel catalyst to obtain a hardened fish oil having a melting point of 45 ° C. When this fish oil-hardened oil was checked for the presence or absence of crystal transition by DSC, it was a β-prime type fat. For confirmation, this fish oil-hardened oil was completely melted at a temperature of 60 ° C or higher, and then crystallized at 5 ° C.
When X-ray diffraction measurement was performed in the range of 6, a strong diffraction line corresponding to a 4.2 angstrom spacing was obtained.
It was confirmed that the fat and oil crystals had β-prime type.

A mixture of 55% by weight of this hardened fish oil and 45% by weight of soybean oil, and 81% by weight of an oil phase obtained by mixing and dissolving 0.5% by weight of monoglyceride stearate and 0.1% by weight of lecithin as an emulsifier. 16% by weight of water, 1% by weight of salt, and 2% by weight of skim milk powder were made into a water-in-oil emulsion by a conventional method, and subjected to a quenching plasticizing step (-20 ° C / min or more)
I got margarine. X-ray diffraction measurement confirmed that the obtained margarine was in a β-prime form.

This margarine was prepared at 5 ° C. immediately after production.
Was 2000 g / cm ² , whereas after one month, the rheometer value at 5 ° C. was 3000 g / cm ^2.
g / cm ² , and it is recognized that it hardens over time,
The oil composition was poor in stability.

[Comparative Example 2] Using corn oil as a raw material, hydrogenation was performed using a nickel catalyst to obtain a hardened corn oil having a melting point of 36 ° C. When this corn hardened oil was checked for the presence of crystal transition by DSC, it was found to be a β-prime type oil. For confirmation, this hardened corn oil was completely melted at a temperature of 60 ° C. or higher, and then crystallized at 5 ° C.
When the X-ray diffraction measurement was performed in the range of θ: 17 to 26, a strong diffraction line corresponding to a 4.2 Å interplanar spacing was obtained, and it was confirmed that the fat and oil crystals had β-prime type.

This hardened corn oil 70% by weight and soybean oil 30
Of oil phase, in which 0.5% by weight of stearic acid monoglyceride and 0.1% by weight of lecithin are mixed and dissolved as an emulsifier, 81% by weight of water, 16% by weight of water, 1% by weight of salt, and 2% of skim milk powder % To a water-in-oil type emulsion by a conventional method, and subjected to a quenching plasticizing step (−20 ° C./min or more),
I got margarine. X-ray diffraction measurement confirmed that the obtained margarine was in a β-prime form.

Further, at the point immediately after the quenching plasticization, the margarine exhibited fine crystals of 5 μm or less under an optical microscope, but after one month, the margarine was transformed into coarse crystals having a size of 30 μm, and was very rough. There is no product value to feel the stickiness. At the same time, this margarine has a rheometer value of 5 ° C. of 1500 immediately after its production.
g / cm ² , whereas after one month, the rheometer value at 5 ° C. became 2400 g / cm ² , and the oil composition was found to be harder over time, and was poor in stability. .

Comparative Example 3 The melting point of 45 ° C. used in Comparative Example 1
Was mixed with 32% by weight of a fractionated hard oil and 50% by weight of soybean oil. This mixed oil is DSC
As a result, the presence or absence of crystal transition was confirmed. For confirmation, this mixed oil
After being completely melted at the above temperature, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26. The X-ray diffraction measurement corresponds to the plane spacing of 4.2 Å and 4.6 Å. A strong diffraction line was obtained, and it was confirmed that the fat and oil crystals had a mixture of β-prime type and β-type.

81% by weight of an oil phase obtained by mixing and dissolving 0.5% by weight of stearic acid monoglyceride and 0.1% by weight of lecithin as an emulsifier in this mixed oil, 16% by weight of water, 1% by weight of salt, and 2% by weight of skim milk powder Was converted into a water-in-oil type emulsion by a conventional method, and subjected to a quenching plasticizing step (-20 ° C./min or more) to obtain margarine. X-ray diffraction measurement confirmed that the obtained margarine was a mixture of β-prime type and β-type.

Further, at the point immediately after the quenching plasticization, the margarine exhibited fine crystals of 5 μm or less under an optical microscope, but after one month, the margarine was transformed into coarse crystals having a size of 30 μm. There is no product value to feel the stickiness. At the same time, this margarine has a rheometer value of 900 g at 5 ° C. immediately after production.
/ Cm ² , but after one month, the rheometer value at 5 ° C. became 2800 g / cm ² , and it was confirmed that the composition became harder over time, and the oil composition was poor in stability. Also, its plasticity range was extremely narrow and unsatisfactory.

As is evident from these results, in Comparative Examples 1 and 2 using β-prime crystalline fats and oils, there was a change over time and there was a problem in terms of crystal stability. Although the composition shown in Comparative Example 3 partially showed β-type crystals,
Since it was not a direct β-type crystal nor a fine crystal, the crystal stability was poor and the plastic range was extremely narrow.

On the other hand, the compositions of Examples 1 to 12 using oils directly as β-type crystals are soft even at low temperatures,
It was a fat / oil composition having a wide plasticity range and having no change in hardness over time and excellent in crystal stability. Furthermore, even in the compositions of Examples 13 and 14 in which the fats and oils which are β-type crystals and the fats and fats which are β-prime type crystals are used in combination, the hardness is soft at a low temperature, has a wide plastic range, and changes over time. It was an oil and fat composition which was excellent in crystal stability without performing.

[0061]

The plastic fat composition of the present invention is directly β-type crystal and preferably contains fine fats and oils, is soft even at low temperature, has a wide plastic range, and can be used over time. It is a stable oil and fat composition without change in hardness.

[Procedure amendment]

[Submission date] September 29, 2000 (2009.2)
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

Example 1 A high oleic sunflower oil was used as a raw material, and hydrogenation was carried out using a nickel catalyst to give a melting point of 4.
A hardened oil (a) at 0 ° C. was obtained. The presence or absence of crystal transition of the hardened oil (a) was confirmed by DSC. As a result, it was found that the oil was a direct β-type crystal fat which did not take the β-prime type. For confirmation, the cured oil (a) was completely melted at a temperature of 60 ° C. or more, and then crystallized at 5 ° C., and subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26 ° . A strong diffraction line corresponding to the interplanar spacing of 6 Å was obtained.
It was confirmed that the mold was adopted. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

[Example 3] Shea fractionated soft oil was used as a raw material,
Hydrogenation was performed using a nickel catalyst to obtain a hardened oil (c) having an iodine value of 59. The presence or absence of crystal transition of the hardened oil (c) was confirmed by DSC, and as a result, it was a direct β-type crystal fat and oil which did not take β-prime type. For confirmation, add 6 hardened oils (c).
After complete melting at a temperature of 0 ° C. or higher, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26 °. As a result, strong diffraction corresponding to the interplanar spacing of 4.6 Å was obtained. A line was obtained, and it was confirmed that the fat and oil crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

Example 5 Monkey fractionated soft oil was used as a raw material.
Hydrogenation was performed using a nickel catalyst to obtain a hardened oil (e) having an iodine value of 38. The presence or absence of crystal transition of the hardened oil (e) was confirmed by DSC, and as a result, it was a direct β-type crystal fat and oil which did not take β-prime type. For confirmation, hardened oil (e)
After complete melting at a temperature of 0 ° C. or higher, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26 °. As a result, strong diffraction corresponding to the interplanar spacing of 4.6 Å was obtained. A line was obtained, and it was confirmed that the fat and oil crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

Example 7 Monkey fractionated soft oil was used as a raw material,
Hydrogenation in the presence of DL-methionine was performed to obtain a hardened oil having an iodine value of 54, and the hardened oil was fractionated by dry fractionation to obtain a fractionated hard oil (g). The fractionated hard part oil (g) was checked for the presence or absence of crystal transition by DSC. As a result, it was a direct β-type crystal fat which did not take the β-prime type. For confirmation, the fractionated hard part oil (g) was completely melted at a temperature of 60 ° C. or higher, and then crystallized at 5 ° C. to obtain 2θ:
When X-ray diffraction measurement was performed in the range of 17 to 26 degrees ,
A strong diffraction line corresponding to the interplanar spacing of 4.6 angstroms was obtained, and it was confirmed that the fat crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

Example 9 A mixture obtained by mixing soybean extremely hardened oil and sunflower oil at a weight ratio of 1: 4 was used as a raw material.
A transesterification reaction was performed in the presence of a sodium methoxide catalyst to obtain a reaction oil. Next, this reaction oil was fractionated by solvent fractionation to obtain a fractionated soft part oil. This fractionated soft oil 80
% By weight and 20% by weight of the shea fractionated hard oil were mixed to obtain a mixed oil (i). The presence of crystal transition in the mixed oil (i) was confirmed by DSC. As a result, the mixed oil (i) was a direct β-type crystal fat without the β-prime type. For confirmation, mix oil (i) with 6
After complete melting at a temperature of 0 ° C. or higher, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26 °. As a result, strong diffraction corresponding to the interplanar spacing of 4.6 Å was obtained. A line was obtained, and it was confirmed that the fat and oil crystals had β-form. When the size of the fat crystals was observed with an optical microscope, the crystals were fine crystals of 3 μm or less.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

Example 13 Using fish oil as a raw material, hydrogenation was performed using a nickel catalyst to obtain a hardened fish oil having a melting point of 35 ° C. When this fish oil-hardened oil was checked for the presence or absence of crystal transition by DSC, it was a β-prime type fat.
For confirmation, this fish oil-hardened oil was completely melted at a temperature of 60 ° C or higher, and then crystallized at 5 ° C.
When X-ray diffraction measurement was performed in the range of 26 degrees , it was found that 4.2
A strong diffraction line corresponding to the angstrom plane spacing was obtained, and it was confirmed that the fat crystals had β-prime type.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction contents]

[Comparative Example 1] Using fish oil as a raw material, hydrogenation was performed using a nickel catalyst to obtain a hardened fish oil having a melting point of 45 ° C. When this fish oil-hardened oil was checked for the presence or absence of crystal transition by DSC, it was a β-prime type fat. For confirmation, this fish oil-hardened oil was completely melted at a temperature of 60 ° C or higher, and then crystallized at 5 ° C.
When X-ray diffraction measurement was performed in the range of 6 degrees , a strong diffraction line corresponding to a 4.2 angstrom interplanar spacing was obtained, and it was confirmed that the fat and oil crystals had β-prime type.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction contents]

[Comparative Example 2] Using corn oil as a raw material, hydrogenation was performed using a nickel catalyst to obtain a hardened corn oil having a melting point of 36 ° C. When this corn hardened oil was checked for the presence of crystal transition by DSC, it was found to be a β-prime type oil. For confirmation, this hardened corn oil was completely melted at a temperature of 60 ° C. or higher, and then crystallized at 5 ° C.
When X-ray diffraction measurement was performed in the range of θ: 17 to 26 degrees , a strong diffraction line corresponding to a 4.2 angstrom plane spacing was obtained, and it was confirmed that the fat and oil crystals had β-prime type.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

Comparative Example 3 The melting point of 45 ° C. used in Comparative Example 1
Was mixed with 32% by weight of a fractionated hard oil and 50% by weight of soybean oil. This mixed oil is DSC
As a result, the presence or absence of crystal transition was confirmed. For confirmation, this mixed oil
After being completely melted at the above temperature, a crystal precipitated at 5 ° C. was subjected to X-ray diffraction measurement in the range of 2θ: 17 to 26 °. The results corresponded to the plane spacing of 4.2 Å and 4.6 Å. A strong diffraction line was obtained, and it was confirmed that the fat crystals had a mixture of β-prime type and β-type.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11C 3/12 C11C 3/12 (72) Inventor Toru Kajimura 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Inside the Denka Kogyo Co., Ltd. (72) Inventor Koji Shishido 7-35, Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. (72) Shoji Marusen 7-35, Higashiogu Arakawa-ku, Tokyo No. Asahi Denka Kogyo Co., Ltd. (72) Inventor Kazuaki Suzuki 7-2-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. (72) Toshiyuki Hirokawa 7-2 Higashiogu, Arakawa-ku, Tokyo 35 Asahi Denka Kogyo Co., Ltd. (72) Inventor Toru Nezu 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F-term (reference) 4B026 DC06 DG01 DG11 DH03 DH10 DP04 DX02 4H 059 BC03 BC13 CA06 CA34 CA35 DA30

Claims (8)

[Claims] 1. A plastic fat composition containing fats and oils which are directly β-type crystals. 2. The plastic fat composition according to claim 1, wherein the direct β-form crystal exists substantially as fine crystals. 3. The maximum length of the fine crystal is 20
The plastic fat composition according to claim 2, which is not more than μm. 4. The plastic fat or oil composition according to claim 1, wherein the fat or fat which is the direct β-type crystal is contained in an amount of 5% by weight or more based on the total fat and oil content. 5. The composition according to claim 1, which is of a margarine type.
5. The plastic fat composition according to 3 or 4. 6. The method according to claim 1, which is of a shortening type.
5. The plastic fat composition according to 2, 3 or 4. 7. A method for producing a plastic fat composition, comprising cooling and plasticizing an oil phase containing fats or oils that are directly β-type crystals. 8. Bakeries using the plastic fat composition according to any one of claims 1 to 6.