JPH09241673A - Hard stock and production of hard stock-containing plastic oil and fat composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hard stock capable of providing a margarine not causing the oozing of a liquid even at a high temperature, suppressing the occurrence of graining, excellent in melt in the mouth and spread at a low temperature by a specific method. SOLUTION: A mixed oil of (A) 5-15wt.% of a liquid oil (e.g. a colza oil or a soybean oil having a high content of a polyfunctional unsaturated fatty acid residue), (B) behenic acid, its ester or oils and fats containing behenic acid, etc.,(C) oils and fats derived from a palm oil (preferably ones containing 40-70wt.% of a palmitic acid residue) and (D) laurin-based oils and fats (preferably ones containing 35-55wt.% of a lauric acid residue) is treated with a lipase having specificity at the 1, 3 positions (e.g. a lipase derived from a fungus belonging to the genus Rhizopus and selectively transesterified. The amount of the component C blended is preferably 45-60wt.% and that of the component D is preferably 20-40wt.%. The preferable fatty acid composition of the hard stock is 45-55wt.% of a 16-20C saturated fatty acid residue, 10-22wt.% of a 12C saturated fatty acid residue, 6-10wt.% of a polyfunctional unsaturated fatty acid residue and 0.5-5wt.% of a 22C saturated fatty acid residue.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hard stock and a method for producing a hard stock-containing plastic oil / fat composition.

[0002]

2. Description of the Related Art Generally, in order to produce table margarine for household use and fat spread, as a fat and oil mixture thereof, a high melting point portion (melting point 40 to 45 ° C.) and an intermediate melting point portion (melting point 30 to 37 ° C.) are used.
C.) and a low melting point portion (oil and fat that is liquid at room temperature), and three types of hardness and fat are mixed and used. Of these three types of fats and oils, the high-melting point part is called the hard stock, which is important for the physical properties of margarine and fat spreads, such as low-temperature spreadability, high-temperature liquid oil stainability, melting in the mouth, and graining properties. Be greatly involved in.

Hardened oil obtained as a result of hydrogenating liquid oil is mostly used as the oil and fat as the hard stock, but margarine and spread that satisfy all the physical properties throughout the year in regions where climate changes greatly in four seasons are used. No hard stock has been developed that can be manufactured.

Recently, oils and fats which have been subjected to selective transesterification using a 1,3-specific lipase have been proposed (Japanese Patent Laid-Open No. Sho 61-242)
61-95098), such a selective transesterified oil / fat preserves the basic symmetric structure of palm-based oils / fats, that is, the property of being easily β-crystallized, and when used for margarine or fat spread, it is quickly grained. Has the drawback that

[0005]

As described above, according to the prior art, the stain resistance of the liquid oil by leaving it in a place where the room temperature is high, the good spreadability and the meltability in the mouth immediately after taking out from the refrigerator, and the high temperature and the low temperature. There is no hard stock that can produce margarine or fat spread that has resistance to graining due to the cycle of
Today, there is a demand for hard stock that positively affects the physical properties of such margarines and fat spreads.

The present inventor, as a result of diligent research in view of such circumstances, found that a specific proportion of a liquid oil and behenic acid or its ester, a fat and oil derived from palm oil, and a lauric fat and oil in a 1,3-position is unique. The present invention has been completed based on the finding that a hard stock having a favorable influence on the above-mentioned physical properties can be obtained by selectively transesterifying with a sex lipase.

[0007]

Means for Solving the Problems That is, the present invention provides a blended oil of 5 to 15% by weight of liquid oil, behenic acid or its ester or fats and oils containing them and palm oil-derived fats and oils and lauric fats and oils. A method for producing a hard stock, which comprises selectively transesterifying by acting a 3-position specific lipase, and blending the hard stock with a fat and a liquid oil having a melting point of 30 to 37 ° C. A method for producing a plastic oil / fat composition characterized by the above. In the following description, "%" and "parts" mean% by weight and parts by weight, unless otherwise specified.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid oil used in the production of the hard stock in the present invention has many polyunsaturated fatty acid residues, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil, rice bran oil, Examples thereof include corn oil, safflower oil, kapok oil, sesame oil, evening primrose, and the like, alone or in combination, and any of these may be used.

The amount of the liquid oil used is 5 to 15% of the total amount of the blended oil as a hard stock. If the amount of the liquid oil is too small, the spreadability at low temperature becomes poor, and if it is too large, the separation of the liquid oil at high temperature, Grain resistance is poor.

Behenic acid or its ester means any of behenic acid existing as a free fatty acid and an ester of a monohydric or dihydric or higher polyhydric alcohol, for example, a fatty acid ester such as ethyl alcohol, methyl alcohol, ethylene glycol or glycerin. It can be used even in the form of.

Further, the oil and fat derived from palm oil is an oil and fat containing 35% or more of palmitic acid residues, preferably 40 to 70%, and palm oil itself or a fractionated oil obtained by fractionating the palm oil, Alternatively, any of those hardened oils may be used. Furthermore, lauric oils and fats are oils and fats containing 35% or more, preferably 35 to 55% of lauric acid residues, and palm oil, palm kernel oil itself or a fractionated oil obtained by fractionating the same, or those Any of the above hardened oils may be used.

In the present invention, the above behenic acid residues are
Behenic acid or its ester in an amount of 0.5 to 5% and oils and fats derived from palm oil are 45 to 60%, and lauric oils and oils are 20 to 40%.
It is preferable to mix at a ratio of 10% to obtain a compounded oil as a hard stock. If the amount of behenic acid residue is too small, the resistance to spot formation at high temperatures deteriorates, and if it is too large, melting in the mouth tends to deteriorate. If the amount of palm oil-derived fats and oils is too small, spreadability at low temperatures and the occurrence of graining tend to be poor, and if it is too large, melting in the mouth tends to be poor. Further, if the amount of lauric oil and fat is less than the above range, melting in the mouth tends to be poor, and if it is too large, spreadability at low temperatures and graining resistance tend to deteriorate. In addition, since palm oil-derived fats and oils and lauric fats and oils may be obtained as fractionated oils having different fatty acid compositions depending on the fractionation method and fractionation conditions, it is ultimately necessary to judge by the composition of fatty acid residues. preferable.

The preferred fatty acid composition of hardstock is
45 to 55% of saturated fatty acid residues having 16 to 20 carbon atoms, of which palmitic acid residues are particularly 30 to 50%, preferably 30 to 40%
%, Saturated fatty acid residues having 12 carbon atoms are 10 to 22%, and polyunsaturated fatty acid residues are 6 to 10%.
%, The saturated fatty acid (behenic acid) residue having 22 carbon atoms is 0.
It is 5 to 5%. If the fatty acid composition deviates from the above ranges, the desired physical properties of margarine or fat spread produced using the hard stock tend to be unobtainable.

Hard stock is triglyceride 1,3
It can be obtained by a known enzyme transesterification method using a lipase having specificity for the position. Examples of the lipase include lipases derived from Rhizopus, lipases derived from Mucor, pancreatic lipase, rice bran lipase and the like. Although it is possible to use these enzymes alone to carry out a selective transesterification reaction, they are usually used after being adsorbed on a support such as diatomaceous earth, alumina or activated carbon. Further, JP-A-56-127087 and JP-A-62-134
A well-adjusted dry enzyme such as No. 090 has activity without addition of water, and can suppress the production of side reaction products such as diglyceride during the reaction to a low level. The reaction is batch type or continuous type, in the presence or absence of solvent, at 20 to 70 ° C.
The temperature range.

The obtained selective transesterified oil can be used as it is as a hard stock, but by appropriately adding an emulsifier such as glycerin fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, polyglycerin fatty acid ester and lecithin. You can leave it.

The hard stock thus obtained is blended with a fat and a liquid oil having a melting point of 30 to 37 ° C. to produce a plastic fat composition such as household margarine and fat spread. be able to. As the fats and oils having a melting point of 30 to 37 ° C., liquid hardened fats which are generally used, selective or non-selective transesterified oils or fractionated oils thereof can be used, but palm oil or a fractionated oil thereof is particularly preferable. It is preferable to use them in combination.

Further, as the liquid oil, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil, rice bran oil, corn oil, safflower oil, kapok oil, which are exemplified as the liquid oil used in the production of hard stock, Examples thereof include sesame oil, evening primrose and the like, alone or in combination, and any of these may be used.

To produce a plastic oil / fat composition, the above hard stock is mixed with 10 to 30% of oil and fat in the middle melting point of 20 to 40% and liquid oil of 40 to 70%. Can be manufactured by kneading and kneading according to a conventional method. If the mixing ratio of the hard stock is less than the above range, the resistance to spot formation of the liquid oil at high temperature tends to be poor, and if it is too large, the spreadability and meltability at low temperature tend to be poor. Further, if the amount of the fats and oils in the mid-melting point of the melting point of 30 to 37 ° C is too small, the spreadability and the meltability in the mouth at low temperatures become poor, and if it is too large, the stain resistance of the liquid oil at high temperatures tends to become poor. Furthermore, if the amount of liquid oil is too small, the spreadability at low temperatures tends to be poor, and if it is too large, stains of liquid oil at high temperatures tend to deteriorate.

The plastic oil / fat composition produced by using the hard stock according to the present invention has no stain of liquid oil at high temperature, suppresses the generation of graining, melts in the mouth, and has good spreadability at low temperature. It has excellent physical properties, but especially excellent in spreadability at low temperatures and graining resistance.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts and% mean weight basis.

Example 1 and Comparative Example 1 Preparation of Hard Stock 55 parts of palm stearin (iodine value 33), 38 parts of extremely hardened palm kernel oil, 5 parts of soybean oil, and 2 parts of extremely hardened oil of haiersin rapeseed oil were mixed. Then, this was subjected to selective transesterification using an enzymatic agent having 1,3-position specificity and then purified to obtain a hard stock having a melting point of 42 ° C.

The above hard stock has 16 to 20 carbon atoms.
48% saturated fatty acid residues, 18% saturated fatty acid residues with 12 carbon atoms, 6% polyunsaturated fatty acid residues with 18 or more carbon atoms, and 1% behenic acid residues. there were.

Preparation of Plastic Oil / Fat Composition (Fat Spread) In a ratio of 65 parts of palm oil, 32 parts of soybean oil, 3 parts of hyacinth rapeseed oil and an extremely hydrogenated oil, sodium methylate was used as a catalyst for non-selective transesterification. Melting point (melting point 34 ° C)
And the above-prepared hard stock, palm oil, and soybean oil were blended in the ratios shown below, and a fat spread was produced by a conventional method using a combinator. Further, as a fat and oil for comparison, soybean hydrogenated oil (melting point 42 ° C.) whose melting point and SFC were adjusted so as to approximate to hard stock was similarly used. As the emulsifier, 0.3% of each of stearic acid monoglyceride and lecithin was added.

Fat spread (oil and fat content 70%) Oil and fat blending Example 1 Comparative Example 1 ──────────────────────────────── ─── Hard stock (melting point 42 ℃) 25 ── Hardened soybean oil (melting point 42 ℃) ── 25 Mid melting point transesterified oil (melting point 34 ℃) 15 15 Palm oil (melting point 37 ℃) 10 10 Soybean oil 50 50 ───────────────────────────────────

The results of a stain spread test of liquid oil at 30 ° C. of fat spread are shown below. The numbers indicate the height of the liquid oil that was cut out after cutting the fat spread into 40 mm x 40 mm x 40 mm, put it in a plastic container, and left it at 30 ° C overnight.

Liquid oil stain test at 30 ° C. Liquid oil stain amount Shape retention ────────────────────────────── ───── Example 1 2 mm No change Comparative Example 1 22 mm Lower part collapsed ──────────────────────────────── ──

From the above results, the fat spread using the hard stock of Example 1 showed good heat resistance. On the other hand, the fat spread using the hardened soybean oil having a melting point and an SFC similar to each other was remarkably inferior in heat resistance at 30 ° C.

The hardness of these fat spreads at each temperature by a rheometer is shown below. Rheometer measurement value * 5 ° C. 10 ° C. 20 ° C. ────────────────────────── Example 1 560 420 140 Comparative Example 1 900 500 500 100 ─ ───────────────────────── * Fudo Kogyo Co., Ltd., unit: g / 0.785cm2

As can be seen from the above results, the fat spread of Example 1 has a hardness at low temperature which is soybean oil 42 ° C.
It was very soft and showed good shape-retaining property at high temperature, and this fat spread had good spreadability immediately after it was taken out from the refrigerator, and maintained its shape-retaining property even when left at room temperature.

Next, the results of the panel test of melting in the mouth will be shown. The test was carried out by 20 panelists by the three-point comparison method. As a result, 4 were discriminated between Example 1 and Comparative Example 1, and the other 16 were indistinguishable. In addition, among the 4 persons who are discriminated, the number of persons who consider the example 1 to be better is 3
There was one person who gave the result of Comparative Example 1 as good, and no difference in melting in the mouth was observed between them.

From the above results, the fat spread obtained in Example 1 has a great feature that it has good spreadability at low temperature, which is important as physical properties, has good melting property in the mouth, and has heat resistance at high temperature. It was good and had a good quality not found in conventional margarine or fatpread.

The occurrence of graining was clearly observed in Comparative Example 1 after storage at 5 ° C. for 4 months, whereas it was not observed in Example 1 even after storage for 6 months.

Examples 2 to 3 and Comparative Examples 2 to 5 Preparation of Hard Stock Hard stock was prepared by the following formulation. Combination 2 Actual 3 Ratio 2 Ratio 3 Ratio 4 Ratio 5 ───────────────────────────────────── Palm stearin 55 47 57 58 60 50 Extremely hardened palm kernel oil 38 35 38 40 40 20 Soybean oil 5 10 5 ── ── 20 Hyersine rapeseed oil Extremely hardened oil 2 8 ── 2 ── 10 ────────── ──────────────────────────── C16-C20 saturated fatty acid residues 48 50 48 50 50 51 C12 saturated fatty acid residues 18 17 18 19 19 10 C18 or higher unsaturated fatty acid residue 6 9 6 3 3 16 C22 saturated fatty acid residue 1 4 ── 1 ── 5 ─────────────────── ──────────────────

Preparation of Plastic Oil / Fat Composition (Fat Spread) A fat spread was produced in the following blending ratio in the same manner as in the previous example. Fat spread (oil and fat content 70%) Oil and fat mixture ─────────────────────────────────── Hard stock 25 Medium melting point Transesterified oil (melting point 34 ° C) 15 Palm oil (melting point 37 ° C) 10 Soybean oil 50 ─────────────────────────────── ────

The hardness of these fat spreads at each temperature by a rheometer is shown below. Rheometer measurement value * 5 ° C 10 ° C 20 ° C ────────────────────────────────── Example 2 560 420 140 Example 3 500 410 180 Comparative Example 2 550 410 120 Comparative Example 3 1110 810 310 Comparative Example 4 1020 760 250 Comparative Example 5 520 400 130 130 ─────────────────── ─────────────── * Fudo Kogyo Co., Ltd., unit: g / 0.785cm2

As described above, the effect of the polyunsaturated fatty acid residue, as can be seen from the results of Comparative Examples 3 and 4, shows that the fat spread tends to be harder when the content is less than 5%. Moreover, even if it exceeds 15%, there is no significant effect on hardness alone.

Generation of graining due to storage 1 month 3 months 6 months ──────────────────────────── Example 2 None None None None Implementation Example 3 No No No No Comparative Example 2 Yes Yes Yes Yes Comparative Example 3 No No No No Comparative Example 4 Yes Yes Yes Yes Comparative Example 5 No Some Yes Yes Yes ───────────────────── ────────

As can be seen from Comparative Example 2 and Comparative Example 4, the effect of behenic acid on the occurrence of graining is that graining does not include behenic acid regardless of whether or not liquid oil is blended. Occurs. This is because symmetric triglyceride is preserved in the selective transesterification by 1,3-specific lipase, which is considered to be the cause of graining, but the inclusion of behenic acid maintains fine crystals. Presumed to be done. As can be seen from Example 3 and Comparative Example 5, the effect of the content of polyunsaturated acid shows that even if the content of behenic acid is high, the content of polyunsaturated acid exceeds 10%. Tends to occur.

Liquid oil stain test at 30 ° C. Liquid oil stain amount Shape retention ────────────────────────────── Example 2 1 mm No change Example 3 2 mm No change Comparative Example 2 6 mm Slightly collapsed Comparative Example 3 2 mm No change Comparative Example 4 2 mm No change Comparative Example 5 21 mm Lower part collapsed ───────── ───────────────────────

As a result of the above, the influence of polyunsaturated acid and behenic acid on the spotting of liquid oil is as shown in Examples 2 and 3 if the content of polyunsaturated acid is within the claimed range. Although it is not affected by behenic acid, when behenic acid is not contained as in Comparative Examples 2 and 5, and when the content of polyunsaturated acid exceeds 10%, even if behenic acid is contained,
Blemishing tends to be worse.

Evaluation of melting in the mouth

As can be seen from Examples 2 and 3 and Comparative Examples 2, 3 and 4, the effect of each fatty acid residue on the dissolution in the mouth was found to be as follows. It has a good melting in the mouth, but those that do not contain it tend to worsen.
Further, as can be seen from Comparative Example 5, even if the liquid oil contains a polyunsaturated acid residue, those containing a large amount of behenic acid tend to have poor melting in the mouth. Is determined to be 5%.

[0043]

INDUSTRIAL APPLICABILITY As described above, in the hard stock according to the present invention, the plastic oil / fat composition produced by using the hard stock has no stains of the liquid oil even though the temperature is high, and the occurrence of graining is suppressed. It has the effect of melting in the mouth and exhibiting good physical properties in spreadability at low temperatures, and is particularly excellent in spreadability at low temperatures and graining resistance.

Claims (4)

[Claims] 1. A mixed oil of 5 to 15% by weight of liquid oil, behenic acid or an ester thereof, or an oil or fat containing them, and an oil or fat derived from palm oil or a lauric oil or fat is allowed to act with a 1,3-position specific lipase. A method for producing a hard stock, which comprises selectively transesterifying. 2. The method according to claim 1, wherein 45 to 60% by weight of oil and fat derived from palm oil and 20 to 40% by weight of lauric oil and fat are blended. 3. The fatty acid composition of the hard stock is 45 to 55% by weight of saturated fatty acid residues having 16 to 20 carbon atoms, 10 to 22% by weight of saturated fatty acid residues having 12 carbon atoms, and polyvalent. 3. The method according to claim 1, wherein the unsaturated fatty acid residue is mixed in an amount of 6 to 10% by weight and the saturated fatty acid residue having 22 carbon atoms is added in an amount of 0.5 to 5% by weight. 4. A method for producing a plastic oil / fat composition, which comprises blending the hard stock according to any one of claims 1 to 3 with an oil / fat having a melting point of 30 to 37 ° C. and a liquid oil. .