JP2017014301A - Polymer compound and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound adding excellent crystallization promotion property to oil and fat and an application thereof.SOLUTION: The polymer compound is expressed by a specific structure consisting of a [phosphorous acid-glycerol-hydroxy fatty acid-fatty acid] structural unit where a polymer unit consisting of hydroxy fatty acid by ester polymerizing glycerol and fatty acid is further polymerized with phosphoric acid via an ester bond with average polymerization degree of the structural unit of 0 to 100 and molecular weight of 3,000 to 100,000.SELECTED DRAWING: None

Description

  The present invention relates to a novel polymer compound, and more particularly to the polymer compound having excellent crystallization promoting activity and use thereof.

  In recent years, edible fats and oils such as frying oil, margarine, stew fat and oil, and chocolate fats and oils that do not contain trans fatty acids or have low trans fatty acids have been widely used. This type of fat tends to slow crystallization behavior. As a result, workability at the time of food production is deteriorated, and the quality of the product is deteriorated. For example, in the donut frying oil, the crystallization behavior of the blended fats and oils is important for improving sugar crying and stickiness of the fried donut. In order to improve the filling state during the production of shortening or margarine, it is effective to promote the crystallization of the blended fat / oil. In the process of pouring melted roux for stew or curry roux into a container and solidifying it while cooling, quick crystallization of stew or curry fat is effective for shortening the working time. In the case of coated chocolate, if the melted chocolate dough does not dry well, it takes time to dry, and workability such as the need to increase cooling is also deteriorated. The shorter the time to dry, the better, but the workability decreases even if the viscosity increases from the beginning. Therefore, in order to improve the workability of the coated chocolate, appropriate management of the crystallization of the blended fats and oils is important.

  Conventionally, an emulsifier is blended to promote crystallization of fats and oils. For example, Patent Document 1 discloses an oily fat polymer compound containing a sorbitan fatty acid ester having an esterification rate of 28 to 60% and a sorbitol-type content of 20 to 40%. However, when an emulsifier is added to the frying composition, the crystal promotion effect may be extremely reduced by heating.

JP2009-209350

  The objective of this invention is providing the substance which accelerates | stimulates crystallization of fats and oils, and the composition containing it. This invention is also providing the foodstuff manufactured using the said substance or composition.

As a result of intensive studies on the above problems, the present inventors have found that the following problems can be solved. That is, the present invention has the chemical formula (1):
[Wherein, X ¹ , X ² and X ³ are each independently a hydroxyl group removed from a carboxyl group of a hydroxy fatty acid having 18 to 28 carbon atoms which may have one carbonyl group in the chain; R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a residue excluding a hydrogen atom, each independently a hydrogen atom or a carboxyl of a fatty acid which may have one carbonyl group in the chain a group given by removing hydroxyl groups from the _base, m 1, _{m 2} and _{m 3} are independently an average number of moles of 0 to 15, n is an average polymerization degree of 0 to 100, n is 2 In the above case, a plurality of X ³ , a plurality of R ³ , and a plurality of m ₃ may be the same or different from each other], and the molecular weight is 3,000 to 100,000 I will provide a. In this specification, the term “polymer compound” is used with the intention of including a mixture thereof.

  The weight ratio of the hydroxy fatty acid is preferably 5 to 45:10 to 40:20 to 65: 5 to 40 in the order of C18: C22: C24: C28.

  The ratio of the hydroxy fatty acid having one carbonyl group in the chain to the whole hydroxy fatty acid is preferably 15 to 70% by weight.

  The ratio of the hydroxy fatty acid having 24 carbon atoms having a carbonyl group in the chain to the whole hydroxy fatty acid having a carbonyl group in the chain is preferably 80% by weight or more.

  The ratio of the hydroxy fatty acid to the total of the hydroxy fatty acid and the fatty acid is preferably 20 to 90%.

  The number of carbon atoms of the fatty acid is preferably 16 to 28.

  The present invention also provides a composition containing 0.003% by weight or more of the polymer compound.

  The present invention also provides an oil and fat composition containing 0.0003 wt% to 1 wt% or more of the polymer compound and having an iodine value of 40 or more.

  The present invention also provides a food using a composition containing 0.003% by weight or more of the polymer compound.

  The present invention also provides a food using the oil and fat composition containing 0.0003 wt% to 1 wt% or more of the polymer compound and having an iodine value of 40 or more.

  When the polymer compound of the present invention is blended in fats and oils, the crystallization promoting activity of fats and oils is remarkably improved as compared with conventional emulsifiers. This activity is determined by measuring the SFC (solid fat content) of a test fat composition containing the polymer compound of the present invention in a base oil under a certain condition (for example, 25 ° C. to 40 ° C. after 20 minutes). Can be evaluated. A high SFC after 20 minutes means high activity.

  The oil and fat composition for frying to which a conventional emulsifier is added has an extremely low crystallization promoting property at a frying oil temperature of 170 to 190 ° C. On the other hand, the oil and fat composition to which the polymer compound of the present invention is added has an excellent feature that the crystallization promoting property is not impaired even when heated at a high temperature.

  Utilizing the above properties, the polymer compound of the present invention can be applied to various uses. For example, addition to frying oil for donuts improves the crying, stickiness and texture of fried donuts. In the production of shortening / margarine, the uniformity and filling state during stirring and kneading are improved by the crystallization promoting action from the beginning. Coated chocolates that do not dry well will have longer drying times or require enhanced cooling. The shorter the drying time, the better. However, when the viscosity increases from the beginning, the workability of the coating decreases. The polymer compound of the present invention can accelerate the drying of the base dough for the coated chocolate and increase the working efficiency. Work can also be done with soft chocolate dough.

It is process drawing which extracts, concentrates and refine | purifies the high molecular compound of this invention from edible fats and oils. It is a GPC chart of the chloroform extraction part of the Example according to this invention. It is a GPC chart of the chloroform extraction part of the Example according to this invention. Fraction No. in the figure. 1-4 correspond to the polymer compound of the present invention. It is a MALDI / TOF / MS chart of the polymer compound of the present invention. From this chart, it can be seen that the active substance is a polymer compound having a repeating unit of 380 Da. The 14 Da interval means the CH ₂ interval. It is mass spectral data obtained by ionizing trimethylsilylated C22: 0 hydroxy fatty acid methyl with EI. From the library search of the mass spectrum, the structure of C22: 0 hydroxy fatty acid methyl was identified. FIG. 4 is a ¹ H NMR chart (600 MHz) measured by dissolving the polymer fraction of FIG. 3 in deuterated chloroform. FIG. 4 is a ¹ H NMR chart (600 MHz) measured by dissolving fraction 2 in FIG. 3 in deuterated chloroform. Methylene protons (2H) bonded to hydroxyl groups of hydroxy fatty acids are observed at 4.0 ppm to 4.1 ppm, and methylene protons (4H) bonded to hydroxyl groups of glycerin are observed at 4.1 ppm to 4.4 ppm. It can be seen from the proton ratio which is the peak area ratio that the molar ratio of hydroxy fatty acid: glycerin is 1.8: 1. 4 is a ¹ H NMR chart (600 MHz) of fraction 3 in FIG. 3. 4 is a ¹ H NMR chart (600 MHz) of fraction 4 in FIG. 3. The time-dependent change of SFC in 25 degreeC of the oil-fat composition (Example 3) according to this invention containing 1 weight% of PTS (polymer compound concentration: 0.07 weight%) is shown. For comparison, the time-dependent change in SFC of an oil / fat composition to which 1 wt% of additive-free (Comparative Example 3), rapeseed extremely hard oil (Comparative Example 4) or tripalmitin (Comparative Example 5) is added is also shown. The SFC of the composition of the present invention is not different from the comparative example in the initial stage, and increases more rapidly than the other examples when a certain period of time elapses. Therefore, according to the present invention, not only the crystallization of fats and oils is promoted, but also a certain amount of working time can be ensured until the SFC rapidly increases. It is the graph which plotted the crystallization rate represented by SFC for 20 minutes at 40 degreeC with respect to the PTS density | concentration.

Hereinafter, embodiments of the present invention will be described in detail. The polymer compound of the present invention has the chemical formula (1):
[Wherein, X ¹ , X ² and X ³ are each independently a hydroxyl group removed from a carboxyl group of a hydroxy fatty acid having 18 to 28 carbon atoms which may have one carbonyl group in the chain; R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a residue excluding a hydrogen atom, each independently a hydrogen atom or a carboxyl of a fatty acid which may have one carbonyl group in the chain a group given by removing hydroxyl groups from the _base, m 1, _{m 2} and _{m 3} are independently an average number of moles of 0 to 15, n is an average polymerization degree of 0 to 100, n is 2 In the above case, the plurality of X ³ , the plurality of R ³ , and the plurality of m ₃ may be the same or different from each other] and have a molecular weight of 3,000 to 100,000. The polymer compound may be a single type or a mixture of two or more types.

The polymer compound of the present invention has a polymer unit (X ^{1 to} X ³ ) composed of a hydroxy fatty acid that undergoes ester polymerization between glycerin and a fatty acid. That is, X ^{1 to} X ³ are residues obtained by removing a hydroxyl group from a carboxyl group of a hydroxy fatty acid having 18 to 28 carbon atoms which may have one carbonyl group in the chain, and removing a hydrogen atom from the hydroxyl group. is there. This residue is represented by the following formula (2):
[Wherein, x is an integer of 0 to 25, y is 0 or 1, z is an integer of 0 to 25, provided that the sum of x, y and z is 15 to 25]
It is indicated by the repeating unit.

X ^{1 to} X ³ may be the same as or different from each other. Further, when m _{1 to} m ₃ are 2 or more, the repeated X ^{1 s} , X ^{2 s,} or X ^{3 s} may be the same as or different from each other. Furthermore, when n is 2 or more, the plurality of X ³ may be the same as or different from each other.

m _{1 to} m ₃ mean the average number of moles of the repeating unit X. m _{1 to} m ₃ also mean the average number of moles of hydroxy fatty acid ester-bonded to 1 mole of glycerin. m ₁ ~m ₃ is 0 to 15, preferably 10 to 1, more preferably 7 to 1, more preferably from 6-1. m _{1 to} m ₃ may be the same as or different from each other. Furthermore, when n is 2 or more, the plurality of m ₃ may be the same as or different from each other.

  Hydroxy fatty acid (FA-OH) has 18 to 28 carbon atoms. The hydroxy fatty acid can be a hydroxy saturated fatty acid (eg, C18: 0-OH), or a hydroxy unsaturated fatty acid having one or more double bonds in the chain (eg, C18: 1-OH). Preferably it is a hydroxy saturated fatty acid.

  The weight ratio of the hydroxy fatty acid is preferably 5 to 45:10 to 40:20 to 65: 5 to 40 in the order of C18: C22: C24: C28, particularly preferably 5 to 30:10 to 30:30. ~ 65: 5-30.

  In the present specification, a hydroxy fatty acid having one carbonyl group in a chain is referred to as an oxo-hydroxy fatty acid (oxo-FA-OH). The ratio of the oxohydroxy fatty acid to the whole hydroxy fatty acid is preferably 15 to 70% by weight, more preferably 20 to 50% by weight.

  The ratio of oxohydroxy fatty acid having 24 carbon atoms (oxo-C24-OH) to the whole oxohydroxy fatty acid is preferably 80% by weight or more. The upper limit is not particularly limited and is 100% by weight or less. More preferably, the ratio of the oxohydroxy saturated fatty acid having 24 carbon atoms (oxo-C24: 0-OH) to the entire oxohydroxy fatty acid is 90% by weight or more.

  The ratio of the hydroxy fatty acid to the total of the hydroxy fatty acid and the fatty acid is preferably 20 to 90% by weight, more preferably 25 to 90% by weight.

R ^{1 to} R ⁵ are residues obtained by removing a hydroxyl group from a hydrogen atom or a carboxyl group of a fatty acid (FA) which may have one carbonyl group in the chain, and represented by the following formula (3):
[Wherein, x is usually an integer of 0 to 25, y is 0 or 1, and z is usually an integer of 0 to 25, provided that the sum of x, y and z is usually 13 To 25, and R is a hydrogen atom]
Indicated by

R ^{1 to} R ⁵ may be the same as or different from each other. Furthermore, when n is 2 or more, a plurality of R ³ may be the same or different from each other.

  The number of carbon atoms of the fatty acid is preferably 16 to 28. The fatty acid may be a saturated fatty acid (eg C18: 0) or an unsaturated fatty acid having one or more double bonds in the chain (eg C18: 1). The weight ratio of the fatty acids is preferably 5-40: 5-50: 5-35: 5-45: 5-55, particularly preferably 5-30: C16: C18: C22: C24: C28. 5-40: 5-25: 5-35: 5-45.

  In the present specification, a fatty acid having one carbonyl group in a chain is referred to as an oxo fatty acid (oxo-FA). The ratio of the oxo fatty acid to the total fatty acid is preferably 5 to 40% by weight, particularly preferably 5 to 30% by weight.

  The ratio of the oxo fatty acid having 24 carbon atoms (oxo-C24) to the whole oxo fatty acid is preferably 80% by weight or more. The upper limit is not particularly limited and is 100% by weight or less. More preferably, the ratio of the oxo saturated fatty acid having 24 carbon atoms to the total oxo fatty acid is 90% by weight or more.

  In the polymer compound of the present invention, a structural unit in which glycerin and a hydroxy fatty acid are ester-bonded is further polymerized via phosphoric acid and an ester bond. The average degree of polymerization (n) of the structural unit consisting of [phosphoric acid-glycerin-hydroxy fatty acid-fatty acid] is 0 to 100, preferably 0 to 50, more preferably 0 to 30, and further preferably 1 to 25. Yes, particularly preferably 1-15.

  The molecular weight of the polymer compound of the present invention is 3,000 to 100,000, preferably 5,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5, 000-17,500.

  The polymer compound of the present invention or a composition containing the same is obtained by chemically synthesizing the compound represented by the chemical formula (1) using a conventional method, extracting and purifying it from a natural plant such as palm fruit, or like a palm-based oil or fat. It can also be extracted and purified from various processed oils and fats. The palm fruit preferably contains a kernel part.

  A method for extraction and purification from natural plants will be described below. First, palm fruits, especially seed coats, are boiled in high-temperature water and then deactivated with lipase. If necessary, use a blender to make the components easier to extract. The shredded product is refluxed at a high temperature in an organic solvent such as chloroform and toluene to extract the polymer compound in the organic solvent. The temperature of the organic solvent during reflux is usually 30 to 120 ° C, preferably 50 to 110 ° C. After extraction, insoluble matter is filtered and the organic solvent is removed to obtain a polymer compound. The obtained polymer compound may be subjected to molecular weight fractionation methods such as gel permeation chromatography and ultrafiltration to select a fraction having a polystyrene equivalent molecular weight of 3,000 to 100,000.

  Next, a method for extracting and purifying the polymer compound of the present invention from the processed oil and fat will be described with reference to FIG. The raw material fats and oils are preferably palm oils and fats such as palm stearin and palm super stearin obtained by fractionating palm oil. In particular, palm super stearin (PSS) having an iodine value of 10 to 17 is preferable.

  First, raw material fats and oils are subjected to a separation process. The fractionation may be either dry fractionation or solvent fractionation. After melting the raw oil and fat at the melting temperature or higher, the temperature is gradually lowered, and the SFC of the slurry is 20% by weight or less, preferably 0.2 to 18% by weight, more preferably 0.2 to 10% by weight, Crystallization is preferably performed at 0.2 to 5% by weight, and most preferably 0.2 to 2% by weight.

  The yield of the hard part represented by [hard part weight / (hard part weight + liquid part weight)] is 26% by weight or less, preferably 0.3-25% by weight, more preferably 1.0-15% by weight. The slurry is fractionated so that For separation, pressure filtration is performed with a filter press, belt press or the like. At the time of fractionation, the fractional efficiency value represented by hard part yield / slurry SFC is preferably 10 or less, more preferably 1.0 to 8.0, and particularly preferably 1.2 to 7.0. A composition comprising a hard part obtained by fractionating palm super stearin is called palm triple stearin (referred to as PTS). The PTS usually contains about 0.005 to 1% by weight of the polymer compound of the present invention.

  The polymer compound in the PTS is further concentrated in the organic solvent washing / extraction step shown in FIG. First, in order to remove triglyceride from PTS, mixing is performed at a ratio of 500 ml of chloroform to 100 g of PTS. The PTS mixture is allowed to stand at a temperature of 15 ° C. to 25 ° C. for 6 to 22 hours, and then insoluble components are filtered through a cylindrical filter paper to obtain a chloroform insoluble portion remaining on the filter paper.

  In order to further remove triglyceride and diglyceride from the chloroform-insoluble portion remaining on the cylindrical filter paper, the chloroform-insoluble portion is washed while refluxing hexane at 55 ° C. to 65 ° C. with a Soxhlet extraction apparatus. A hexane insoluble portion remaining on the cylindrical filter paper without being dissolved in hexane is obtained.

  In order to obtain a polymer compound from the hexane insoluble part remaining on the cylindrical filter paper, extraction is performed with chloroform at 50 to 60 ° C. using a Soxhlet extraction apparatus. By this operation, a chloroform-dissolved part (hereinafter referred to as chloroform extract) is obtained.

  The chloroform extract is fractionated by an appropriate molecular weight fractionation method, and a polymer compound having a polystyrene-equivalent molecular weight of 3,000 to 100,000 is recovered.

  The present invention also provides a composition comprising the polymer compound of the present invention. The lower limit of the content of the polymer compound in the composition is 0.003% by weight, preferably 0.005% by weight, more preferably 0.008% by weight, still more preferably 0.01% by weight, particularly preferably. Is 0.03% by weight. The upper limit of the content of the polymer compound in the composition is not particularly defined and is determined according to the use of the composition, but is, for example, 100% by weight or less.

  The composition of the present invention preferably contains 0.0003 wt% to 1 wt%, more preferably 0.0003 wt% to 0.5 wt% of the polymer compound of the present invention, and has an iodine value of 40 or more. It may be a composition. The lower limit of the iodine value of the oil and fat composition is preferably 42 or more, more preferably 45 or more. Although the upper limit of the iodine value of an oil-and-fat composition is not specifically limited, Preferably it is 120 or less, More preferably, it is 100 or less, More preferably, it is 75 or less. When the iodine value of the oil and fat composition is 40 or more, the effect can be obtained with a small amount of the polymer compound.

  The composition of the present invention is a concentrate obtained after fractionation of PSS and contains a polymer compound in an amount of 0.003% by weight or more, for example, a hard part (PTS) after dry fractionation, a 20 ° C. chloroform insoluble part of PTS, It may be a 20 ° C. chloroform-dissolving part of PTS, a hexane-insoluble part of the chloroform-insoluble part, a hexane-soluble part of the chloroform-insoluble part, a chloroform extraction part of the hexane-insoluble part, and a chloroform-insoluble part of the hexane-insoluble part. These concentrates contain triglycerides, diglycerides, monoglycerides and the like usually contained in fats and oils in addition to the polymer compound of the present invention. Table 1 shows the polymer compound concentration of each concentrate.

  An oil and fat composition containing a polymer compound and a base oil has an excellent crystallization promoting action. And industrial utilization is very high at the point which can ensure a certain work period (for example, 1-4 minutes) until crystallization is accelerated | stimulated rapidly.

  The content of the polymer compound in the oil and fat composition to which the polymer compound is added is usually 0.00003 wt% or more, preferably 0.00005 wt% or more, more preferably 0.0001 wt% or more. On the other hand, the upper limit is preferably 0.002% by weight, more preferably 0.001% by weight, and still more preferably 0.0008% by weight in terms of preserving physical properties other than the crystallization characteristics of fats and oils.

  When the oil and fat composition uses a diluted polymer compound (for example, the concentrate in Table 1) instead of the polymer compound, the content of the concentrate is determined according to the concentration of the polymer compound. The proportion of the concentrate is usually 0.05 to 20% by weight.

  The said base oil is decided according to the use of an oil-fat composition. When the fat composition is, for example, a frying oil for frozen food, the base oil is a fat having a melting point of 10 ° C or higher, preferably 15 to 40 ° C. If the melting point is less than 10 ° C., crystals may not be formed or may become very slow. Examples of fats and oils with a melting point of 10 ° C. or higher include palm oil, palm oil, palm kernel oil, monkey fat, cacao fat, shea fat and fractionated oils and hardened oils of beef fat, pork fat, milk fat, fish oil and fats And hydrogenated oils of soybean, rapeseed oil, rice oil, corn oil, cottonseed oil, safflower oil, sunflower oil, olive oil, sesame oil, or transesterified oils thereof.

  The base oil has an iodine number (also referred to as IV) of 30 to 65, particularly palm oil and / or palm fractionated oil of IV 30 to 60, random transesterified oil of palm oil and lauric oil and / or hydrogenated oil thereof, It may be at least one selected from the group consisting of oils that are liquid at room temperature, palm kernel oil and palm kernel fractionated oil, and hardened oil of palm kernel oil and palm kernel fractionated oil.

  The palm-based fats and oils include palm oil, palm oil fractionated oil, transesterified oil, hardened oil, processed oil and fat subjected to two or more treatments selected from fractionation, transesterification and hydrogenation. Palm fractionated oil includes palm olein, palm super olein, palm stearin and the like.

  Preferable examples of the transesterified oil are palm-based fats and oils, random transesterified fats and oils of palm-based fats and lauric fats and / or hardened oils thereof. Laurin-based fats and oils mean fats and oils whose main constituent fatty acid is lauric acid having 12 carbon atoms, such as palm kernel oil and palm oil. Palm-based oils and lauric oils are preferably transesterified at a weight ratio of 20:80 to 70:30, particularly preferably 30:70 to 60:40. The transesterification reaction may be either a method using lipase as a catalyst or a method using a metal catalyst such as sodium methylate.

  Preferable examples of the hardened oil include palm hard oil, palm kernel hard oil, and the like. You may perform the hardening reaction of the said hardened oil at any time before transesterification and after transesterification.

  Examples of oils that are liquid at room temperature include soybean oil, rapeseed oil, rice oil, corn oil, cottonseed oil, safflower oil, sunflower oil, olive oil, sesame oil, palm super olein (IV 65 or higher), and the like. These can be used alone or in combination of two or more. Preferred are soybean oil, rapeseed oil, corn oil, cottonseed oil, safflower oil, and palm super olein (IV 65 or higher).

  The ratio of the palm oil of IV30-65 and / or palm fractionation oil is 40 weight% or more normally with respect to the whole base oil, Preferably it is 50-100 weight%.

  The ratio of the random transesterified oil and / or its hardened oil of palm oil and lauric oil is usually 10 to 80% by weight, preferably 10 to 60% by weight, and more preferably, based on the whole base oil. 10 to 40% by weight.

  The proportion of oil that is liquid at normal temperature is usually 0 to 40% by weight, preferably 10 to 40% by weight, more preferably 10 to 30% by weight, based on the entire base oil.

  When the base oil is a blended oil containing palm oil having an iodine value of 30 to 65 and / or palm fractionated oil and oil that is liquid at room temperature, it is usually 50 to 90% by weight, preferably 60% based on the whole base oil. It is preferable to include palm oil and / or palm fractionated oil having an iodine value of 30 to 65% by weight of 90% by weight and oil that is liquid at normal temperature of 10 to 50% by weight, preferably 10 to 40% by weight.

  When the base oil is a palm oil having an iodine value of 30 to 65 and / or a palm fractionated oil, a random transesterified oil of palm oil and lauric oil and / or a hardened oil thereof, On the other hand, it is usually 20 to 70% by weight, preferably 30 to 70% by weight of palm oil and / or palm fractionated oil having an iodine value of 30 to 65, and usually 10 to 60% by weight, preferably 10 to 40% by weight. It is preferable to include a random transesterified oil of palm oil and lauric oil and / or a hardened oil thereof.

  In the case where the base oil is a blended oil containing palm oil having an iodine value of 30 to 65 and / or palm fractionated oil, random transesterified oil of palm oil and lauric oil, and oil that is liquid at room temperature, the whole base oil Usually 20 to 70% by weight, preferably 30 to 70% by weight of palm oil of 30 to 65 iodine and / or palm fractionated oil, usually 10 to 60% by weight, preferably 10 to 40% by weight Oils obtained by random transesterification of palm oils and lauric oils and / or hardened oils thereof, and oils that are liquid at normal temperature, usually 10 to 40% by weight, preferably 10 to 40% by weight, are included.

  When the base oil is a blended oil of palm kernel hard oil and palm kernel olein, it is usually 30 to 80% by weight, preferably 30 to 60% by weight of palm kernel hard oil, and usually based on the whole base oil. 20 to 70 wt%, preferably 40 to 70 wt% palm kernel olein.

  In addition to the polymer compound and the base oil, additives known in the art can be added to the oil and fat composition of the present invention within a range that does not impair the effects of the present invention. Examples of additives include other edible oils and fats; emulsifiers such as lecithin, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, polyglycerol fatty acid ester; antioxidants such as tocopherol and vitamin C palmitate Thickeners such as pectin, carrageenan, xanthan gum, carboxymethylcellulose (CMC), guar gum, gum arabic, locust bean gum, karaya gum, tamarind gum, tara gum, kifarselan, casein soda, alginate, agar, gum elemi, gum canada, gum damar Stabilizer; Coloring agent; Flavor such as milk flavor, vanilla flavor, vanilla essence; glucose, maltose, sucrose, lactose, trehalose, malt Triose, palatinose, reduced palatinose, xylitol, erythritol, maltitol, sorbitol, isomerized liquid sugar, sugar syrup, etc .; salt; Dairy products such as fresh cream, milk fat, milk fat preparations and the like.

  The oil and fat composition of the present invention can be obtained by mixing a polymer compound, a base oil, and appropriate additives at a predetermined ratio. These components may be mixed simultaneously, or the polymer compound may be mixed with a part of the base oil and then mixed with the remaining components.

  The polymer compound or composition of the present invention is a composition for frying a donut, fried bread, snack confectionery, instant noodles, side dish, etc. based on its excellent crystallization promoting action, a composition for margarine or shortening, Applications to various compositions such as stew, curry composition and chocolate composition are expected.

  The present invention also provides a food using the above polymer compound or a composition containing 0.0003% by weight or more of the polymer compound. Examples of foods include donuts, fried bread, snacks, instant noodles, side dishes, margarine, shortening, stew roux, curry roux, chocolate, confectionery coated or coated with chocolate, and the like.

  The amount of the composition of the present invention to be mixed with food is appropriately determined according to the concentration of the polymer compound in the composition, the type of food, the addition conditions, and the like.

Hereinafter, the present invention will be described in more detail by showing Examples and Comparative Examples of the present invention. However, the present invention is not limited to the following examples.
[Example 1] (Purification of polymer compound)
The raw palm oil was subjected to the dry fractionation step shown in FIG. 1 and the organic solvent washing / extraction step to extract and purify the polymer compound.

1. Dry fractionation process Using a 10 kg scale fractionation pilot apparatus (Laboratory scale pilot fractionation, De Smet), IV12 palm super stearin (MEWAHOLEO INDUSTRIES SDN.BHD., Hereinafter referred to as PSS) was dry fractionated. First, 9.02 kg of PSS was completely dissolved at 70 ° C., and then the water temperature was gradually lowered to 60 ° C. to precipitate crystals.

  During the crystallization, the SFC of the slurry was measured by the following procedure. 2 ml of a sample was put in a glass tube, and the amount of crystals was measured with an NMR analyzer (NMS120 minispec, manufactured by BRUKER). When the slurry SFC reached 0.5%, the slurry was sent to a lab filter and pressure-filtered to 15 bar to obtain 371 g of a hard part (PTS) and 8650 g of a liquid part (hereinafter referred to as “PSS-OL”). Got. The yield of the hard part calculated by the weight of the hard part / (weight of the hard part + weight of the liquid part) was 4.1% by weight. The fractionation efficiency calculated by the yield of the hard part / slurry SFC was 8.9.

2. Organic Solvent Cleaning / Extraction Step The PTS was subjected to the organic solvent cleaning / extraction step of FIG. 1 to concentrate the polymer compound in the PTS.

2.1 Chloroform washing at 20 ° C. 100 g of the above PTS was dissolved in 330 ml of chloroform, allowed to stand at 20 ° C. for 6 to 17 hours, and then filtered through a cylindrical filter paper (Whatman 603, inner diameter 48 mm × 145 mm, manufactured by Whatman). 10.25 g of chloroform insoluble part was obtained on the filter paper.

2.2 Washing with hexane at 60 ° C. Place 10.25 g of the chloroform-insoluble part together with the cylindrical filter paper in the extraction part of the Soxhlet extractor and reflux the triglyceride contained in the chloroform-insoluble part with 55 ml of hexane for 2 hours. Removed with hexane at 0 ° C. After washing, a hexane insoluble part remaining on the filter paper was obtained.

2.3 Chloroform extraction at 50-60 ° C. The hexane-insoluble part was refluxed with 500 ml of chloroform in a Soxhlet extractor in the same manner as above to obtain 0.0561 g of a chloroform extract.

2.4 GPC fraction 1 of chloroform extraction part
0.0561 g of the chloroform extract was dissolved in 10 ml of chloroform and fractionated by GPC (Gel Permeation Chromatography). Fractionation conditions are as follows.
Instrument: 1200 series HPLC System (manufactured by Agilent Technologies)
GPC column: TSKgel G2500H _XL , 7.8 mm I.G. D. × 30cm, particle size 5μm (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Mobile phase: Chloroform flow rate: 1 ml / min

  A GPC chart is shown in FIG. The fraction corresponding to the polymer compound in the GPC chart in FIG. 2 was collected (polymer compound A in FIG. 2).

2.5 GPC fraction 2 of chloroform extraction part
The chloroform extract was dissolved in chloroform and fractionated by GPC. Fractionation conditions are as follows.
Instrument: 1200 series HPLC System (manufactured by Agilent Technologies)
GPC column: TSKgel G4000H _XL , 7.8 mm I.G. D. × 30cm, particle size 5μm (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Mobile phase: Chloroform flow rate: 1 ml / min

  A GPC chart is shown in FIG. No. in the GPC chart of FIG. Fractions corresponding to 1-5 (fractions 1-5) were collected individually. Moreover, what collected fractions 1-5 together was also obtained (it is called a polymer fraction).

  Table 2 shows the polystyrene equivalent molecular weight of fractions 1 to 5. The polystyrene equivalent molecular weights in the table were obtained by GPC analysis of Shodex STANDARD SM-105 (manufactured by Showa Denko KK), which is a standard polystyrene product (the molecular weight of the standard product was measured by the light scattering method). Calculated based on retention time.

  As will be described later, fractions 1 to 4 have crystallization promoting activity. Therefore, fractions 1 to 4 were collected as the polymer compound of the present invention.

3. 3. Structural analysis of polymer compound 3.1 MALDI / TOF / MS analysis For the structural analysis of a polymer compound, the polymer compound was subjected to MALDI / TOF / MS. The MALDI / TOF / MS analysis followed the following conditions.
Equipment: AXIMA-TOF2 (Shimadzu Corporation)
Laser: Nitrogen laser (wavelength: 337 nm)
Matrix: Disranol cation agent: Sodium trifluoroacetate

  FIG. 4 shows a MALDI / TOF / MS chart of the polymer compound. As seen in FIG. 4, the polymer compound had a repeat unit of 380 Da. This repeating unit was mainly derived from oxohydroxy fatty acid (C24: 0-OH) by GC / MS analysis shown below.

The polymer compound was subjected to methanolysis by reacting with a 14% boron trifluoride methanol complex solution at 80 ° C. for 8 hours. The methanolized sample was reacted with a trimethylsilylating agent (TMSI-H, manufactured by GL Science Co., Ltd.) at 60 ° C. for 1 hour. After the obtained decomposition product was dissolved in methanol / acetone = 1/1, the constituent components were identified by GC / MS. The measurement conditions for GC / MS are as follows.
Instrument: JMS-700V mass spectrometer (manufactured by JEOL Ltd.)
6890 series GC System (manufactured by Agilent Technologies)
Column: CP-TAP CB for Triglycerides, 0.25 mm ID × 25 m,
Membrane pressure 0.1μm (Varian)
Carrier gas: Helium gas 1.7ml / min
Column temperature: 200 ° C. (1 min) -5 ° C./min-355° C. (10 min)
Inlet temperature: 350 ° C
Interface temperature: 350 ° C
Sample solution injection volume: 1 μl
Split ratio: 1:10
Ionization method: EI
Measurement ion: positive ion ionization current: 300 μA
Electron acceleration voltage: 70 eV
Ion source temperature: 340 ° C
Ion acceleration voltage: 10 kV
Scanning range: m / z 35-800

  FIG. 5 shows mass spectral data of trimethylsilylated 22-carbon hydroxy saturated fatty acid methyl. Similarly, hydroxy fatty acids having 18, 24, and 28 carbon atoms and fatty acids having 16, 18, 22, 24, 26, and 28 carbon atoms were also identified by GC / MS.

3.2 GC / FID analysis The hydroxy fatty acid derivatives and fatty acids identified by the above GC / MS were quantified by GC / FID. The GC / FID conditions are shown below.
Equipment: 6890 series GC System (manufactured by Agilent Technologies)
Column: CP-TAP CB for Triglycerides, 0.25 mm ID × 25 m,
Membrane pressure 0.1μm (Varian)
Carrier gas: Helium gas 1.7ml / min
Column temperature: 200 ° C. (1 min) -5 ° C./min-355° C. (10 min)
Inlet temperature: 350 ° C
Detector temperature: 365 ° C
Sample solution injection volume: 1 μl
Split ratio: 1:50

The results of GC / FID analysis are shown in Table 3.

  From the results of GC / MS and GC / FID, it can be said that the polymer compound has C16 to C28 fatty acid and oxo fatty acid, and C18 to C28 hydroxy fatty acid and oxo fatty acid as constituent fatty acids.

3.3 NMR Measurement The polymer fraction shown in FIG. 3 was dissolved in deuterated chloroform, and ¹ H NMR (600 MHz) was measured (FIG. 6). Furthermore, Fraction 2, Fraction 3 and Fraction 4 were each dissolved in deuterated chloroform, and ¹ H NMR (600 MHz) was measured (FIGS. 7 to 9).

  In the NMR chart of fraction 2, fraction 3 and fraction 4, a peak of methylene proton (4H) bonded to the hydroxyl group of glycerin is observed at a position of 4.1 ppm to 4.4 ppm. From this, the polymer compound has glycerin as a structural unit.

3.4 Phosphorus analysis The phosphorus content of the polymer compound was determined in accordance with “Standard Fat Analysis 2.4.11-1996 Phospholipids”. As a result, the phosphorus content of the polymer compound was 1.2%. This value corresponds to about 343 times the phosphorus content of PTS (0.0035%). When the polymer compound is concentrated from PTS, phosphorus is also concentrated, so that the polymer compound has phosphoric acid as a structural unit.

3.5 Determination of the chemical structure of the polymer compound From the above analysis results, the polymer compound contains a fatty acid, hydroxy fatty acid, glycerin, and phosphoric acid that may have one carbonyl group in the chain as a structural unit. Was found to include as. Therefore, the chemical formula of the polymer compound is represented by the formula (1):
[Wherein, X ¹ , X ² and X ³ are each independently a hydroxyl group removed from a carboxyl group of a hydroxy fatty acid having 18 to 28 carbon atoms which may have one carbonyl group in the chain; R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a residue excluding a hydrogen atom, each independently a hydrogen atom or a carboxyl of a fatty acid which may have one carbonyl group in the chain a group given by removing hydroxyl groups from the _base, m 1, _{m 2} and _{m 3} are independently an average number of moles of 0 to 15, n is an average polymerization degree of 0 to 100, n is 2 In the above case, the plurality of X ³ , the plurality of R ³ , and the plurality of m ₃ may be the same or different from each other.
It was estimated that. The validity of the chemical formula (1) was verified by calculating the estimated phosphorus content of the polymer compound and comparing the calculated value with the actually measured value.

3.5.1 Formula (1) using average degree of polymerization (m) derived from ¹ H NMR of polymer compound
First, from the constituent fatty acids shown in Table 3, oxoC24: 0-OH as a representative hydroxy fatty acid (X) constituting the polymer compound and C22: 0 as a representative fatty acid (R) were extracted.

Next, the average degree of polymerization (m) of the hydroxy fatty acid ester-bonded to the hydroxyl group of glycerin of the polymer compound is determined from the molar ratio of FA-OH / glycerin in ¹ H NMR. Specifically, CH2 (4.0-4.1 ppm, 2H) bonded to the hydroxyl group of hydroxy fatty acid in the NMR chart of the polymer compound shown in FIG. 6 and CH2 (4.1 bonded to the hydroxyl group of glycerin). The molar ratio of hydroxy fatty acid and glycerin was determined from the integral ratio of the peak at -4.4 ppm, 4H). The molar ratio was 4.2. From this, the average degree of polymerization (m) becomes 4.2.

Chemical formulas of polymer compounds (I) to (IV) using the parameters obtained above and having n number of 1 to 4 are shown below.
[Wherein, X is a residue of an oxohydroxy saturated fatty acid ester having 24 carbon atoms, and R is a residue of a saturated fatty acid ester having 22 carbon atoms. ]

The molecular weight and phosphorus content of the polymer compounds (I) to (IV) were estimated. The results are shown in Table 4.

  The phosphorus contents (calculated values) of the polymer compounds (I) to (IV) were in the range of 0.91 to 1.19%. This range substantially coincides with 1.2% of the actually measured value. This confirms the validity of the chemical formula (1) of the polymer compound.

3.5.2 Chemical formula (1) using average degree of polymerization (m) derived from ¹ H NMR of each fraction of the polymer compound
As in 3.5.1, from the constituent fatty acids shown in Table 3, oxoC24: 0-OH as a representative hydroxy fatty acid (X) constituting the polymer compound, and C22: 0 as a representative fatty acid (R) Extracted.

Next, in order to determine the average degree of polymerization (m) of hydroxy fatty acids in fractions 2 to 4, the molar ratio of hydroxy fatty acid to glycerin was determined from the NMR chart. In addition, since the yield of fraction 1 was low, the molar ratio in fraction 1 was not determined. The results are shown in Table 5.

The molar ratio (b) of each fraction in Table 5 was weighted according to the ratio of each fraction and integrated. As a result, the average degree of polymerization (m) was 3.86. This value almost coincides with the degree of polymerization of 4.2 from ¹ H NMR data of the polymer compound fraction.

A chemical formula of the polymer compound was created using the parameters obtained above and the n number obtained so as to obtain the average molecular weight of each fraction. The chemical formula of the polymer compound of fraction 2 is shown below.
[Wherein, X is a residue of an oxohydroxy saturated fatty acid ester having 24 carbon atoms, and R is a residue of a saturated fatty acid ester having 22 carbon atoms. ]

The chemical formula of the polymer compound of fraction 3 is shown below.
[Wherein, X is a residue of an oxohydroxy saturated fatty acid ester having 24 carbon atoms, and R is a residue of a saturated fatty acid ester having 22 carbon atoms. ]

The chemical formula of the polymer compound of fraction 4 is shown below.
[Wherein, X is a residue of an oxohydroxy saturated fatty acid ester having 24 carbon atoms, and R is a residue of a saturated fatty acid ester having 22 carbon atoms. ]

From the above chemical formula, the phosphorus content in fractions 2 to 4 was estimated. The results are shown in Table 6.

  The phosphorus content (c) of each fraction in Table 6 was weighted according to the ratio and integrated. As a result, the phosphorus content (calculated value) of the polymer compound was 1.15%. This value almost coincides with 1.2% of the measured value. Even when the number of n in fraction 3 was 2 or 3, the calculated value almost coincided with the actually measured value. This further confirms the validity of the chemical formula (1) of the polymer compound.

[Example 2] Crystallization promoting activity of polymer compound The crystallization promoting activity of the polymer compound of the present invention was compared with that of a conventional emulsifier. An oil and fat composition was prepared by mixing 0.0005 parts by weight of the polymer compound A and 99.995 parts by weight of base oil A composed of IV52 palm refined oil. For comparison, a comparative oil and fat composition in which 0.01 part by weight of an emulsifier shown in Table 7 and 99.99 parts by weight of base oil A were mixed instead of the polymer compound A was also prepared. The SFC of the above oil and fat composition was measured at 25 ° C. for 20 minutes. The results are shown in Table 7.

Emulsifier (1): Tetraglycerin hexabehenate (Product name Poem J-46B, manufactured by Riken Vitamin Co., Ltd.)
Emulsifier (2): hexaglycerin octastearate (product name: Sunfat PS-68, manufactured by Taiyo Chemical Co., Ltd.)

  From Table 7, it can be seen that the oil / fat composition containing the polymer compound of the present invention has a good crystallization accelerating activity even though the amount added is smaller than that of the comparative oil / fat composition.

[Example 3] Change with time of crystallization promotion activity of polymer compound Using PTS (polymer compound concentration 0.07 wt%), the behavior of the crystallization promotion activity of the polymer compound with respect to time was examined. First, 1 part by weight of PTS and 99 parts by weight of the base oil A were mixed to prepare an oil and fat composition. The concentration of the polymer compound in the oil / fat composition is 0.0007% by weight. For comparison, no PTS added (Comparative Example 3), 1 part by weight of rapeseed hard oil (Yokoseki Yushi Kogyo Co., Ltd., Comparative Example 4) instead of PTS, or tripalmitin (Wako Pure Chemical Industries, Ltd., A comparative fat composition was also prepared by mixing Comparative Example 5) with 99 parts by weight of base oil A.

  The SFC of the above oil and fat composition was measured at 25 ° C. × 4 to 20 minutes. After complete dissolution at 80 ° C., 2 ml of the oil and fat composition was placed in a glass container. And after making it melt | dissolve completely at 100 degreeC, it hold | maintained for 60 minutes with a 60 degreeC constant temperature water bath. Furthermore, after leaving for 4 to 20 minutes in a 25 degreeC thermostat, the amount of the precipitated crystal | crystallization was measured with the NMR analyzer. The results are shown in FIG.

  FIG. 10 shows that the oil / fat composition containing the polymer compound of the present invention does not differ from the comparative oil / fat composition until the 25 ° C. SFC is about 0 to 4 minutes, but increases rapidly thereafter. This characteristic remarkably improves workability in terms of early crystallization while ensuring a working time at the beginning of production.

[Example 4] Preferred range of molecular weight of polymer compound affecting crystallization promoting activity The preferred range of molecular weight observed from the crystallization promoting activity (hereinafter sometimes referred to as "activity") of the polymer compound was examined.

  The rate of increase in activity of each fraction relative to the crystallization promoting activity of PTS was determined. First, a correlation equation between the PTS concentration and SFC at 40 ° C. for 20 minutes was obtained. The SFC at 40 ° C. for 20 minutes was measured in the following procedure for the oil and fat composition in which PTS, PSS refined product and base oil B were blended in the proportions shown in Table 8. 2 g of the composition was heated at a temperature of 100 ° C. for 1 hour to dissolve the composition. The lysate was held at a temperature of 60 ° C. for 1 hour. Then, it cooled to the temperature of 40 degreeC and hold | maintained for 20 minutes, and measured SFC in 40 degreeC as a crystallization rate. The results are shown in Table 8.

PSS refined product: PSS (manufactured by IV15 MEWAHOLEO INDUSTRIES SDN.BHD.) Decolorized and deodorized for the purpose of reducing polymer compounds Base oil B: Blend of palm oil and palm kernel oil in a weight ratio of 50:50 Oil prepared by hydrogenation and transesterification of oil by conventional methods

FIG. 11 shows a correlation diagram in which the X axis is PTS concentration (%) and the Y axis is 40 ° C. SFC (%). Between the 40 ° C. SFC and the PTS concentration, the following correlation equation:
The relationship shown by exists.

Next, the activity increase rate (PTS ratio) of the polymer compound or its fraction based on the crystallization promoting activity of PTS was determined using the following formula.
Z: Rate of increase in crystal accelerating activity (PTS ratio)
X: PTS concentration (%) obtained by applying SFC (measured value) of the composition to the above correlation equation
Y: Polymer compound concentration (%) in the composition

Table 9 shows the activity increase rate (PTS ratio) of the polymer compound and fractions 1 to 4.

  From Table 9, it can be seen that the molecular weight of the polymer compound is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of crystallization promoting activity.

[Examples 5 to 6] Addition test of frying oil of polymer compound The crystallization promoting activity after high-temperature heating of fried oil to which the polymer compound of the present invention was added was examined. First, 1 part by weight of PTS (polymer compound concentration: 0.07% by weight) was mixed with 99 parts by weight of base oil C or base oil D to prepare an oil and fat composition. The concentration of the polymer compound in the oil / fat composition is 0.0007% by weight. For comparison, a comparative oil and fat composition to which PTS was not added or an emulsifier (1) or (2) was added was prepared.

The influence of the activity when the oil composition was heated was examined. 250 g of the obtained oil and fat composition was placed in a magnetic dish and heated to a temperature of 190 ° C. Before heating, 24 hours after heating, and 48 hours after heating, the oil and fat composition was sampled, and SFC after 25 minutes at 25 ° C. was measured. The SFC reduction rate is expressed by the following formula:

Sought by. The results are shown in Table 10.

Emulsifier (1): Tetraglycerin hexabehenate (Product name Poem J-46B, manufactured by Riken Vitamin Co., Ltd.)
Emulsifier (2): hexaglycerin octastearate (product name: Sunfat PS-68, manufactured by Taiyo Chemical Co., Ltd.)
Base oil C: Palm oil (IV52) and palm olein (IV56) are blended oils of 70:30 on a weight basis Base oil D: Palm stearin (IV32), palm oil (IV52) and rapeseed oil on a weight basis 20: 40:40 blended oil

  In contrast to conventional emulsifiers, the crystallization accelerating activity is reduced by heating, whereas the oil and fat composition containing the polymer compound of the present invention shows a decrease in crystallization accelerating function even when heated under the frying conditions. I can't.

  The above results indicate that immediately after frying the donut, the donut oil crystals cover the surface of the donut, thus effectively preventing sugar crying. Furthermore, if the crystallization is fast, sugar can be worked in a short time after fried donuts, leading to a reduction in work time. That is, as shown in Comparative Example 7 and Comparative Example 8, in the oil and fat composition in which crystallization is promoted by adding an emulsifier, the crystallization speed is extremely reduced by heating at a high temperature, and the working efficiency of sugar removal is improved. Is not expected. On the other hand, the oil and fat composition containing the polymer compound of the present invention does not show a decrease in the crystallization rate due to high-temperature heating as shown in Examples 5 and 6, leading to a reduction in time to sugaring and improving work efficiency. Useful.

Claims (10)

Chemical formula (1):
[Wherein, X ¹ , X ² and X ³ are each independently a hydroxyl group removed from a carboxyl group of a hydroxy fatty acid having 18 to 28 carbon atoms which may have one carbonyl group in the chain; R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a residue excluding a hydrogen atom, each independently a hydrogen atom or a carboxyl of a fatty acid which may have one carbonyl group in the chain a group given by removing hydroxyl groups from the _base, m 1, _{m 2} and _{m 3} are independently an average number of moles of 0 to 15, n is an average polymerization degree of 0 to 100, n is 2 In the above case, the plurality of X ³ , the plurality of R ³ , and the plurality of m ₃ may be the same or different from each other.
And a high molecular compound having a molecular weight of 3,000 to 100,000.   2. The polymer compound according to claim 1, wherein the weight ratio of the hydroxy fatty acid is 5 to 45:10 to 40:20 to 65: 5 to 40 in the order of C18: C22: C24: C28.   The polymer compound according to claim 1, wherein the ratio of the hydroxy fatty acid having one carbonyl group in the chain to the whole hydroxy fatty acid is 15 to 70% by weight.   The high molecular compound of Claim 3 whose ratio with respect to the said whole hydroxy fatty acid of the C24 hydroxy fatty acid which has a carbonyl group in a chain | strand is 80 weight% or more.   The high molecular compound of Claim 1 whose ratio with respect to the sum total of the said hydroxy fatty acid and the said fatty acid of the said hydroxy fatty acid is 20 to 90%.   The polymer compound according to claim 1, wherein the fatty acid has 16 to 28 carbon atoms.   A composition comprising 0.003% by weight or more of the polymer compound according to claim 1.   An oil or fat composition comprising 0.0003 wt% to 1 wt% of the polymer compound according to claim 1 and having an iodine value of 40 or more.   A food using a composition containing 0.003% by weight or more of the polymer compound according to claim 1.   The foodstuff containing the oil-and-fat composition which contains 0.0003 weight%-1weight% of the high molecular compound of Claim 1, and an iodine value is 40 or more.