JPS59174700A - Butter-like fat and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fats suitable for the production of emulsions such as shortenings and margarines or low calorie spreads, and processes for their production.

The present invention particularly relates to fats that have butter-like properties and a reduced tendency towards graininess.

Batter-like properties are here understood to mean plasticity and elasticity substantially corresponding to those of natural putter. These properties and measurements are described by Davies.

J, C, J, Dairy Re5eaSch 8
, 245 (1937): Prentice, T.H.
The Rhqology of Margari
nqand Cnmpoun6 CookingFat
s, Part ■(Res.

Rep 37) and Part n (Res,
Rep, 69).

1956, The Br1tish FoOdMa
Nufacturing■nd, Res, Ass,
It is described in For example, the plasticity of fat is about 1000 g/c.
It can be evaluated by slowly inserting a 7rrtn diameter rod into a fat having a C-value of tr12 and measuring the degree of ring formation. The fat can also be evaluated by an expert panel for difunctionality, visual appearance, and extensibility for similarity to putter.

Roughness is here understood to be the occurrence of triglyceride aggregates with a melting point as high as 25° C. and a size of more than about 30 microns. These triglyceride aggregates consist primarily of mixed crystals of triglycerides, which may be in any combination of: POP
/PPO, PP010PO.

PO310PO, PO31080, POPloSO, 5
O810PO.

MO8/○PO, 5O81088, POP/5PO-,
SO8/PSO.

MPM, /PMP, MSM/SMS, CIQM
M/MrlloM, PPP/○PO, PPP/PP
O, including PPP/POP. In the symbols, P represents palmitic acid, 0 represents oleic acid, S represents stearic acid, and M represents myristic acid.

Slightly rough fat mixtures with a tendency to grittiness are characterized by a grainy fat (1) and unsaturated fatty acid residues in the trans configuration (AO
C8 Interim Method CD l 4-. It has been found that it can be produced by total mixing with an effective amount of Zulacchi-inhibiting fat (11) containing 5 niobium.

Gritty fats (1) generally consist of triglycerides that satisfy the following requirements: (a) 0.2≦PUP: PPU <1.6, where PUP consists of two palmitic acid residues and a cis-configuration. PPU is the mole % concentration of symmetric triglycerides from one oleic or linoleic acid residue, and PPU is the asymmetric triglyceride from two palmitic acid residues and one oleic or linoleic acid residue in cis configuration. is the mole % concentration of

(b) Sa3 < (PUP + PPU) =
7. In the formula, Sa represents C□6-c24 saturated fatty acid,
U represents an oleic or linoleic acid residue in the cis configuration, Sa3 represents the mol% concentration of triglycerides of six 016-24 saturated fatty acid residues, and E'U'P
and PPU have the same meaning as above.

The fat exhibiting graininess (1) has a fat rich in palmitic acid residues 0ii) defined later herein and a C111-24 undecorated fatty acid substantially free of trans-fatty acids, or a trans-fatty acid. by random transesterification of triglycerides having small to moderate levels (e.g., less than about 60% by weight of unsaturated fatty acids in the trans-configuration).

Mixtures of random transesterified and non-esterified fats (1) can also be used to adjust the PUP/PPU-triglyceride ratio.

Detack-inhibiting fat (II) is soybean oil, sunflower oil,
Safflower oil, peanut oil, rapeseed oil, rice oil, wheat germ oil,
Liquid oils, such as olive oil, corn, rocosi oil or mixtures thereof, are preferably prepared using a sulfur-poisoned nickel catalyst with a level of unsaturated fatty acid residues in the trans configuration ranging from 30 to 70% by weight O. 26 under suitable conditions to obtain trans fatty acid levels in the range of 45-67% by weight.
It is a fat obtained by hydrogenation with a melting point in the range of ~64°C.

The effective proportion of fat (11) corresponds in most cases to a ratio of fat (11) to fat (1) of 0.01 to 0.2.

The fat mixture according to the invention contains 70-99% by weight of fat (1
1, 1 to 19 weight percent slip resistance-blocking fat (11)
and from 0 to 20% by weight of a non-hydrogenated vegetable liquid oil containing at least 20% by weight, preferably 40% or more of linoleic acid. The total concentration of various components is 100%.

This liquid oil is used to adjust consistency and mouthfeel, and increases essential fatty acid levels in the final product.

According to the present invention, the method for producing a buttery uniform fat that has a low tendency to exhibit deformity is a method for producing a butter-like fat having a low tendency to exhibit deformity.
1) and 30 to 70 unyawa fatty acids in trans-coordination.
Random transesterification of an effective amount of the volatility-inhibiting fat (4) containing from % by weight of I-liglyceride.

Preferred homogeneous fats according to the invention that have a low tendency to exhibit unevenness are fats in which at least 20% by weight of fatty acid residues are palmitic acid (i.e., fats in which at least 60% by weight of fatty acid residues are comprised of 18 to 24 fatty acids). Has a full length of carbon atoms, 6
0-70% by weight of fatty acid residues are produced by total random transesterification of fats in the trans configuration (++1).

The mixture to be transesterified is a fat selected from the group consisting of palm fat, cottonseed fat, cocoa butter fat, lard fat, tallow fat, herring fat, putter fat and 7-lactones of these fats in hydrogenated or non-hydrogenated form. (i
it) and soybean oil, sunflower oil, peanut oil, rapeseed oil, rice oil, wheat germ oil, olive oil, cotton oil hydrogenated under trans-promoting conditions to a melting point range of 26-67°C, preferably 28-64°C. and another whole fat selected from the group consisting of corn oil and corn oil. In this mixture, the initial (palmitic) fat is preferably present in a proportion ranging from 50 to 90% by weight, and the trans-fat is present in a proportion ranging from 10 to 50% by weight.

According to a preferred embodiment of the process of the invention, the transesterification mixture comprises a high-melting fraction enriched in triglycerides from 6 saturated fatty acids with a chain length of 16 to 24 carbon atoms and its triglycerides from 6 9-hydrate fatty acids. f, fractionated under conditions to obtain a low melting olein fraction containing less than 7% by weight.

Of course, it is also possible to fractionate the full fat mixture of transesterified and non-esterified components and remove the high melting triglycerides from the six saturated fatty acids.

Random transesterification uses standard catalysts such as alkali metals, their hydroxides or alkoxides,
It can be carried out applying substantially anhydrous conditions, reduced pressure (e.g. 2 rranHg) and relatively high temperatures (e.g. 90-110°C).

The fractionation can be carried out by various methods known per se, for example by dry fractionation (without the use of solvents), by wet fractionation (using organic solvents) or by fractionation involving the use of aqueous surfactant solutions. .

The fractionation and separation of the various fractions is preferably carried out without the use of a solvent at a temperature in the range 28-38°C, preferably 30-36°C.

Fractionation involves first heating the fat to 45-65°C, then cooling the fat preferably to 60-66°C with stirring, holding the fat at that temperature for several hours, and then separating the low melting point olein fraction from the high melting point fraction. separation is performed.

It is useful to carry out the fractionation under conditions such that the triglyceride level from the three saturated fatty acids in the low melting point olein fraction is in the range of 0 to 7% by weight, preferably 0 to 4% by weight.

The obtained olein can be used according to the invention alone or as a butter-like fat mixture or butter-like emulsion, respectively.

The fat mixture according to the invention is characterized by the following fatty acid composition: palmitic acid: 16-46% by weight, stearic acid = 4-12% by weight, CI6-C24 un9ated fatty acids in trans configuration = 5-35
% by weight, preferably 7-25% by weight, 20-15% by weight, preferably 0-10% by weight of C8-14 fatty acids, and the remainder of the fatty acids are substantially all cis-unsaturated fatty acids. ~C24
It consists of fatty acids, and the fatty acid content is 100%.

The fat mixture according to the present invention contains 5 to 15 mol% of PUP as defined above, 5 to 15 mol% of PPU as defined above, provided that the PUP/PPU ratio is in the range of 0.2 to 1.6. Condition: 0 to 5 mol% triglyceride from three 08-C249 Japanese fatty acids, C1B) triglyceride from lance fatty acid and one oleic acid or linoleic acid'f
! : 5 to 20 mol%, 1 piece C. - Total 10-25 mol% of triglycerides from two identical or different fatty acids consisting of a C24-bonded fatty acid and linoleic acid or oleic acid, two C. ~C
Triglycerides from 24 saturated olofatty acids and 1 018 trans fatty acid and 1 C16-C24#!
It is characterized by containing 2 to 10 mol% of triglycerides derived from Japanese fatty acids, two C fatty acids, and trans fatty acids.

A water-in-oil emulsion, particularly margarine, which has a less tendency to exhibit sluggishness and has butter-uniform properties, can be prepared according to the present invention by emulsifying the fat mixture obtainable by the above method with an aqueous phase and using the resulting emulsion. It can be produced by cooling and texturing to obtain a plastic tin thread. The aqueous phase may contain additives customary for margarine, such as emulsifiers, salts and flavors.

Oil-soluble additives such as flavoring compounds, vitamins, etc. can be included in the fat phase. Generally, the proportion of the fatty phase in margarine varies from about 75 to 85 N% by weight of the emulsion depending on local legal requirements for margarine. Alternatively, higher proportions of the aqueous phase can be employed in the production of low-fat spreads, which can contain as much as 35% fat by weight.

Emulsions, especially margarine hA, J, ρ.

Margarine J. Anderson and P.N. Williamq.
PreSs 1965. The usual closed type tubular surface scraper Jf described on pages 246 et seq. It can be manufactured using a di-exchanger. British Patent No. 639.743, No. 650,481
The Votator device described in US Pat. Alternatively, the emulsion can be produced by the phase inversion method described in GB 1.215,868 or by the customary cooling drum of the above-mentioned book by Aoderson and Williams.

In order to obtain the consistency of natural butter, the fat mixture according to the invention has the following fat solids profile (J, A,
O, C, 8, 1971C48), 7 pages, A, J.

HightOn and others! 7NMR-value)): N10 = 40-6O N20 = 15-30 N30'' 0-7° The invention is illustrated in the following and Table A% B and C.

Example I 74% by weight of palm oil, 21% by weight of soybean oil hydrogenated to a melting point of 66°C using a freshly precipitated Ni-catalyst and hydrogenated to a melting point of 31°C using a sulfur-poisoned N1 catalyst. The mixture containing 5% by weight of added peanut oil and less than 0.01% by weight of water was subjected to random transesterification at 90 °C in a stirred vessel maintained under a vacuum of 2 mm N9 and in the presence of 0.1% sodium methoxide. did. 2
After 0 minutes, the mixture was cooled and the vacuum was released. The catalyst was destroyed by washing the mixture with water and the fat was then dried.

Fractionation of the transesterification mixture is accomplished by first heating the fat to about 55°C and then cooling to 328°C, a temperature that results in the separation of the lower melting liquid olein hexalactone from the higher melting fraction. I went without saying anything.

Ma lf ') y Ha 84% by weight olein and 1
It was prepared and evaluated from a 6wt% aqueous phase. The scores for smoothness and plasticity are shown in Table A.

Example ■ Example I was repeated. However, this time we started with 70% by weight palm oil and 60% soybean oil hydrogenated to a melting point of 66° C. using the full sulfur-poisoned N1 catalyst.

Margarine was prepared and evaluated from 84 M% oleic and 16% by weight aqueous phase. The roughness and plasticity scores are shown in Table A.

Comparative Example ■ Example I except that the hydrogenation of both soybean oil and peanut oil was carried out using a freshly precipitated N1 catalyst and at an elongation that brought the level of trans fatty acids in the total fat product to less than 5% by weight. ' was repeated. Margarine was made from 84% by weight oleic and 16% by weight aqueous phase.

The plasticity score for margarine was 4.

After 6 weeks of storage at 15°C, the consistency score for these margarines was 5.

COMPARATIVE EXAMPLE ■ Example Nff1 was repeated, except that the hydrogenation of soybean oil was carried out with freshly precipitated N1 catalyst under elongation such that the level of trans fatty acids in the total fat product was less than 5% by weight. Margarine contains 84% oleic and 16% by weight
% of the aqueous phase.

The plasticity score for these margarines is 4 and the grittiness score for these margarines is 6 at 15°C.
5 after week storage.

Example 1 Mixture k 2 containing 78 M% palm oil and 22% by weight soybean oil hydrogenated with a freshly precipitated Ni catalyst to a melting point of 66° C., less than 0.01% by weight water
Random transesterification was carried out at 90° C. in a stirred vessel maintained at a vacuum of mm N9 and in the presence of 0.1% by weight random methoxide.

After 20 minutes the mixture was cooled and the vacuum was released. The catalyst was destroyed by washing with mixed gold water and the fat was then dried.

Fractionation of the transesterification mixture was carried out without the use of solvents by first heating the fat to about 55°C and then cooling it to 62°C, a temperature at which separation of the lower melting liquid olein hexalactone from the higher melting fraction took place. Ta.

The fat admixture contains 90% by weight of the low melting point (oleic) fraction and the sulfur-poisoned N1 catalyst'k O,2 at 180 °C.
% by weight and 55% by weight trans fatty acid level (AO
61°C to obtain C8W standard method Ccl i 4-61)
It was prepared from 10% by weight high trans peanut oil hydrogenated to the melting point of .

Example ■ The procedure of Example ■ was repeated starting from a mixture of 78 M% palm oil and 22% by weight soybean oil hydrogenated to a melting point of 66°C.

Fractionation was performed at 64°C.

The fat admixture contains a low melting point (oleic) fraction of 90 wt.
Manufactured from % high trans peanut oil by weight.

Example V The procedure of Example 1 was repeated starting from a mixture of 78% by weight palm oil and 22% by weight soybean oil hydrogenated to a melting point of 36°C.

Fractionation was performed at 34°C.

The fat admixture was prepared from 85 M% low melting point (oleic) fraction and IF4Ji% (D high tran y, -3-seed oil (m-p-2 60°C)).

Example I Starting from a mixture of 78% by weight of palm oil and 22% by weight of soybean oil hydrogenated to a melting point of 66°C
The procedure was repeated.

Fractionation was performed at 34°C.

The fat mixture was hydrogenated to a low melting point (oleic) fraction of 85% by weight and a melting point of 62°C15.
% soybean oil by weight.

Margarine was produced starting from various fat-mixed products 75\ obtained in Examples 1 to 2. Table B shows the evaluation of the stickiness and plasticity of various margarines.

Example ■ The procedure of Example 1 was repeated starting from 78% by weight palm oil and 22% by weight soybean oil hydrogenated with freshly precipitated N1 catalyst to a melting point of 36°C.

The fat blend was prepared from 82% by weight of the low melting point (oleic) fraction, 10% by weight of high trans peanut oil hydrogenated to a melting point of 61°C and 8% by weight of non-hydrogenated sunflower oil.

S of the olein fraction obtained at a fractionation temperature of 62 °C
The a3 content was 6.5 mol%. The trans content of the high trans peanut oil (inhibitor) was 55% by weight.

The fat solids profile of the fat admixture in terms of NMR-values is: IqlO = 42-5, N20 = 1 6.5, N3
0 = 2.9, N35 = 0.1.

The margarine made from this fat blend had a softness score of 2 at 15°C (after 6 weeks of storage) and a plasticity score of 6.7.

The fatty acid and triglyceride compositions of the fat blends are shown in Table C.

Example ■ A mixture of 70% by weight palm oil and 60% by weight soybean oil hydrogenated under trans-promoting conditions was randomly transesterified as described in I.

The transesterification mixture was fractionated into high melting stearin and low melting olein at 62°C. 92% by weight of this olein was mixed with 8TL% of non-hydrogenated sunflower oil to obtain a margarine fat blend.

Fatty acid composition and triglyceride composition are shown in Table C.

Margarine made from fat admixtures has a slippery score of 2.5 at 15°C (after 6 weeks storage) and a plasticity score of 3.
．． It was 5.

(Note) Deluctability score (maximum storage period of 6 weeks at 15°C) 1 5 = Very high and exhibits a degree of latitude 4 = High and exhibits a degree of latitude 6 = Acceptable and exhibits a degree of latitude 2 = Slight Plasticity score: 5-; Same as natural butter 4 = Almost same as natural butter 3 = Good plasticity 2 = Below average 1=poor plasticity table CP=palmitic acid U-oleic acid or linoleic acid (cis-coordination) H=C
8-C2' is a saturated fatty acid E = elaidic acid Continuation of page 1 Priority claim @ January 31, 1983 ■ United Kingdom (GB
)■8302575 @February 4, 1983■United Kingdom (GB) 8303099 0 Inventor Thiofil Reiske Hamburg, Federal Republic of Germany 61 Paulusolgestrasse 62 Ei Procedural Amendment (Toge) 1988 6 Mon//day Mr. Commissioner of the Japan Patent Office 1, Indication of the case, Patent Application No. 14566 of 1982, 2, Name of the invention, Bata uniform fat and its manufacturing method 3, Relationship with the supplementary iE case, Patent applicant 4, Agent 5, date of amendment order (Showa year, month, day 6), number of inventions increased by amendment 7, specification subject to amendment 8, content of amendment: engraving of the specification as attached (no change in content)

Claims (1)

[Scope of Claims] (1) Butter-like fat with little tendency to exhibit slippage, comprising palmitic acid residues in the range of 16 to 48 weight percent, 4 to 1
stearic acid residues in the range of 2% by weight, 016-024 non-candied fatty acid residues in the trans configuration in the range of 5 to 65% by weight, C8 to C, in the range of 0 to 15% by weight, fatty acid residues, fatty acids A fat as described above, characterized in that the remainder of the residues consists essentially of C16-C24 all-cis unamicable fatty acid residues. (2) Triglycerides at the following levels: 5-15 mol% PUP. 5 to 15 mol% PPU, provided that the PUP/PPU concentration ratio is in the range of 0.2 to 1.6.
Triglycerides from 0-5 mol% of 6 OCS-C24 saturated fatty acids, 5-20 mol% of 1 OCS-C24 saturated fatty acids, 1
triglyceride from 10 to 25 mol % of 1 C16-C24 rotatable fatty acid and linoleic or oleic acid, from 10 to 25 mol% Triglycerides from two identical or different fatty acids, 2-10 mol% of two C6-C24 saturated olofatty acids and one C18
- triglycerides from trans fatty acids and one 0□6 to C24 saturated fatty acid and two C. -Triglyceride from trans fatty acids, (in the above, PUP is two palmitic acid residues-
and a symmetrical triglyceride from one oleic or linoleic acid residue in the cis-configuration, ppu Id
2. A fat according to claim 1, characterized in that it comprises an asymmetric triglyceride of 2 palmitic acid residues and one oleic or linoleic acid residue in cis-configuration. (3) Use of an effective amount of a texture-inhibiting fat (11) consisting essentially of triglycerides derived from unsaturated fatty acids in the trans-configuration to the fat (1) that tends to exhibit texture. (4) Fat (1) has the following requirements: (a) 0.2 <PUP: PPU <1.6,
In the formula, PUP and PPU represent the mol% concentration of triglyceride as defined in claim 2, (b) Sa3 <(PUP 0 PPU ) −7,
In the formula, Sa represents a C16-C24 sandstone fatty acid, U represents an oleic acid or linoleic acid residue in a cis-configuration, and Sa3 represents six saturated carbon atoms. The anti-skid fat according to claim 6, consisting of a mixture of all triglycerides represented by mol % mtx-+ of triglycerides from ~C24 fatty acids, and PUP and PPU having the same meanings as above. use. (5) Zuracchi-inhibiting fat (11) at 26-34°C
Claim 6, wherein the fat is obtained by hydrogenating an oil under suitable conditions to obtain a residual amount of trans-configured unsaturated fatty acids ranging from 30 to 70% by weight to a melting point in the range of . Use of anti-grain fats. (6) The level of unsaturated fatty acid residues in the trans-configuration is 4
Use of anti-slip fat according to claim 5 in the range of 5 to 67% by weight. (7) The ratio of fat (11) to fat (1) is 0.01~
Use of an anti-grainy fat according to claim 3 in the range of 0.2. (8) Fat (1) is 70 to 99% by weight of the total fat mixture;
Fat (11) constitutes 1-19M%, the remainder being 10°
at least 20% by weight of substantially solid fat in C
consisting of O~2ON amount% of oil containing linoleic acid residues,
Use of the anti-grainy fat according to claim 6. (9) In a method for producing a butter-uniform fat that has a low tendency to show sloppy properties, the fat (1) that tends to show sluggish properties as defined in claim 4 is a fat with an unsaturated fatty acid content of 30 to 70%. A process as described above, characterized in that the random transesterification is carried out with an effective amount of a slip-blocking fat (11), the weight percent of which is in the trans-configuration. 0D Fats (iii) in which at least 20% by weight of fatty acid residues are palmitic acid residues, at least 60% by weight of fatty acid residues have a chain length f of 18 to 24 carbon atoms, and 30 to 70% by weight 10. The method of claim 9, wherein the fatty acid residues are randomly transesterified with fats in the trans-configuration. (11) fats selected from the group consisting of hydrogenated or non-hydrogenated palm oil, cottonseed oil, cocoa butter, lard, tallow, herring fat, putter fat and horns of these fats (lli), and 26-676C Soybean oil, sunflower oil, peanut oil, hydrogenated to a melting point in the range of
Fat selected from the group consisting of rapeseed oil, rice oil, wheat germ oil, olive oil, cottonseed oil and corn oil (11)
11. The method of claim 10, comprising randomly transesterifying a mixture of. (+21) Random transesterification of a mixture of 50-90% by weight of a fat in which at least 20% by weight of fatty acid residues consists of palmitic acid and 10-50% by weight of a fat rich in trans fatty acids (11) 10. (13) Rich high melting point 7 of triglycerides from 3 saturated fatty acids having a chain length of 16 to 24 carbon atoms.
11. The method of claim 10, comprising fractionating the transesterification mixture under conditions suitable to obtain a low melting point olein fraction containing 7% by weight less triglycerides from lactone and three saturated fatty acids. 14. A method according to claim 13, wherein the αa fractionation is carried out without the use of a solvent at a temperature in the range from 28 to 68<0>C. (15) A method for producing a patter-like water-in-oil emulsion spread that has less tendency to exhibit lubricity, using the fat according to claim 1 or 2, or claim 9. A method as described above, characterized in that the fat produced according to any one of paragraphs 14 to 14 is emulsified in an aqueous phase, the emulsion obtained is cooled and texturized to obtain a plastic water-in-oil emulsion spread. (16) The fat according to claim 1 or 2,
or a water-in-oil emulsion spread containing fat prepared according to any one of claims 9 to 14.