USRE19425E

USRE19425E - Margarine and process for produc

Info

Publication number: USRE19425E
Authority: US
Publication date: 1935-01-15

Description

Reissued Jan. 15, 1935 UNITED STATES PATENT OFFICE,

mem- AND PROCESS FOR PRODUC- ING THE SAME Benjamin 1:. Harris, cum, m.

No Drawing.

No. 1,917,254, dated July Original 11, 1933, Serial No. 474,808, August 9, 1930. Application for reissue December 1, 1934, Serial No. 155,01: '30 Claims.

5 filed February 27, 1930.

In spite of the improvements in materials and processes for producing margarine, and for the formation of more stable margarine emulsions, even the better grades of margarine have suffered in the past from the separating out of water after the margarine has been produced, this separation being known in the trade as weeping", or "leaking, or "sweating. This weeping has occurred in the past at, all stages in the storage, sale, and use of margarine. This required the use of high grade, relatively expensive moisture'retalning packages to prevent leaking of the margarine in shipment. As a consequence also, it has been difficult to ship margarine by parcel post or other similar means. And most objectionably, when margarine is cut or spread, it does not present a dry butter-like appearance, and its texture, due to the separating out of small globules of water, is not of the best. A disadvantage in margarine occasioned by the same tendency is the fact that it has been impossible to regulate, with dependability, the amount of 'moisture contained in the margarine.

The principal object of my'present invention is to improve margarine with respect to the objections above set out.

Another object is to prevent the weeping margarine.

Another object is to produce a margarine having a definite predetermined moisture content and which will substantially retain the same mo sturewontent during all conditions of manufacture, sale and use thereof.

Another object is to improve the texture of margarine when used as a spread or in other ways.

In connection with the improvements in margarine according .to the objects hereinabove set out, I have discovered certain groups of com,- pounds which I characterize as hydrophyllic lipins, which have the capacity in a marked degree when used in relatively small proportions as addition agents of aiding in the retention of moisture in margarine and improving the character of the margarine in other respects. In general these substances may be saidto be the higher acyl and alkyl and similar innocuous derivatives of various poly-hydroxy compounds, and may be represented by the general formula (RO)vX(OH)-a(H)= wherein 0" and "H" are oxygen and hydrogen respectively 12, "w" and "2 are relatively (0H) and (R0), wherein "R is an acyl, alkyl or some other substantially lipophillic group, and wherein the ratio of "w to "v" is at leastone. Preferably the acyl and alkyl groups contain at least twelve carbons. I shall now describe more fully the nature of my compounds, the manner of their manufacture and use, and how they'difl'er from other compounds of somewhat similar character.

filed February 27, 1930, I described a large group of substances having balanced hydrophile and lipophile groups which are of great value in preventing the spattering of margarine during frying, and improving the character thereof in other respects. In general it may be said that these anti-spatterers are lipins to which have been added by synthesis or in other ways, hydrophyllic groups suflicient to impart hydrophyllic tendencies to a portion of the resulting molecule so that the resulting compound comprises balanced" lipophile and hydrophile o According to the theory established in the copending application referred to, these compounds orientate themselves at the water-oil interface of the emulsion in such a way as to mOdify the surface tension characteristics or produce other unexplained results which have an effect in' markedly reducing the spattering which normally. occurs when margarine is heated in an open pan.

The substances of my present invention are similar in many respects to the anti-spattering compounds, but differ essentially in this: that the hydrophyllic character of' the molecule is not sufficiently pronounced to have an anti-spattering effect. These hydrophyllic lipins, incapable of preventing spattering of margarine, can be used in the margarine when suitably introduced and in proper proportions for the'purpose of preventing weeping by holding the moisture more securely than is possible without their use. They also permit, better control of the margarine to produce a uniform product having a predetermined substantially constant amount of moisture.

Examples compounds which can be .used

in accordanc with the present invention are ethylene glycol, monomelissyl diethylene glycol,

monopalmityl glycerol, mono-oleyl diethylene glycol, mono-oleyl glycerol, diethylene glycol mono-stearate, 1,6-dilauryl diglycerol, and their equivalents. I also include in this group alkyl and acyl derivatives of sugars such as dextrose,

poly-glycerols and ,similar hydroxy compounds which have suflicient of the hydroxy groups sucrose, and derivatives of mannitol, sorbitol,

In my copending application, Serial No. 475,622,

wetting to balance'.

sub-classes which contain many important compounds, and to which I wish to direct particular attention. The first sub-class comprises hydrophyllic, higher alkyl and acyl derivatives of poly-. hydroxy compounds which contain more than one free OH group, but which will not prevent spattering. More specifically, under this group are the hydrophylllc stearic acidesters of polyhydroxy compounds containing more than one free OH group. -Of this class, the compound with which I have obtained the most satisfactory re sults in my experimental work, is monostearyl glycerol.

The second sub-class of compounds are the hydrophyllic alkyl and acyl derivatives of .glycols. These compounds may have only one free OH group or they may have more than one free OH group, but the number of OH groups should not be suflicient to impart too marked a hydrophylllc character to the molecule. The most important example under this class is monostearyl diethylene glycol, (diethylene glycol monostearate).

' As a specific example of the operation of my invention, a good grade of vegetable margarine can be produced in accordance with the following formula: 990 pounds of cocoanut oil (melting point 76 -F.), 630 pounds of hardened vegetable oil(me1ting point 110 F.), 180 pounds of cotton seed oil, 24 pounds of monostearyl glycerol, and 100 gallons of cultured milk. The oleaginous'materials and milk are emulsified, crystallized, and treated in any of the usual ways to produce the final margarine product. when using this formula the hydrophyllic lipin viz:

monostearyl glycerol may be emulsified directly with the other ingredients in the liquid stage. It maybe said however, that in general, certain precautions must be observed in the manner of introducing the hydrophyllic lipin, and these precautions will be treated of hereinafter.

Another formula also making use of a monostearyl glycerol is as follows: 800 pounds of cocoanut oil, (melting point 76 F.), 2.5 pounds of cottonseed oil (melting point 140 F.), 8.5 pounds H of monostearyl glycerol, 50 to gallons of cultured milk. In this formula also, the hydrophyllic lipin may be introduced in the emulsion in the liquid stage, or it may be introduced at. another stage in the manufacture of this margarine, as will be described.

Margarine containing animal fat may be produced in accordance with the foliowing formula: 640 pounds of oleostearine, 640 pounds of lard, 240 pounds liquid cottonseed oil, pounds of hydrogenated cocoanut oil and approximately 56 gallons of cultured milk. To this is added approximately 1% of.monostearyl glycerol, introduced in a suitable manner.

In introducing my hydrophylllc lipins into the margarine I have,'as previously indicated, found that certain precautions must be observed. In other words, when the hydrophyllic lipins are used in margarine they may be productive of.

inferior results or may lead to difllculties in maintaining the proper emulsion unless handled carefully. The margarines described above are habitually prepared with the oleaginous subthe hydrophylllc lipin in the used should not be great enough, radically to alter the physicalappearance, consistency or texture of the margarine.

As an instance of the behavior of these hydrophylllc lipins in margarine, monostearyl glycerol serves as an example. Proportions of this substance greater than approximately l% of the total weight of the margarine can be introduced into the margarine in the liquid stage before crystallizing only with extreme caution. If the amount used in this way is much in excess of 1 the emulsion tends to be destroyed entirely. However, ii the monostearyl glycerol is introduced into the margarine by blending it into the plastic mass after crystallization, or by working it in on the butter worker, or by introducing it in some other manner after crystallization, the amount may be considerably in excess of 1% and good results obtained.

As I have previously stated, proportions of hydrophyllic lipin greater than approximately 1% should not be used with the usual types of margarine, but if the lipin is blended into the margarine the proportions may be substantially increased. I have found however, that for most purposes the best percentage is approximately /2% of hydrophyllic lipin based upon the weight of the margarine, ties as low as of 1% have such a marked eilect upon the characteristics of the final product that even this small amount can satisfaction. V

- It is my theory that the function of the hydrophyllic lipin in margarine is not entirely to increase and stabilize the emulsion but to absorb interstitial moisture or milk which exists between the margarine particles, and to aid the emulsion asfa whole to absorb moisture and so to prevent leakiness of the margarine and maintain a drier product. The actual facts are that a margarine produced by the above methods and with the formula: above set out, will resist leaking of aqueous material during storage and ageing. Furthermore, the cutting and spreading characteristics are better than in the case of margarine made with the ordinary oleaginous materials.

It is not to be supposed that all substances of the general class described are suitable for use in accordance with my invention. For example, there are carboxylic esters of hydroxy substances containing unesterified hydroxy groups which are be used with great not sufliciently hydrophylllc to offer any marked and I have found that quanti- In order that those skilled in the art may practice my invention without difliculty, I wish to disclose the preferred manner in which I have employed my hydrophyllic lipins with the best results. First, any good grade of margarine .is produced in -a suitable mannerand progressed to the stage of blending, which may be carried out in any of the usual blending equipment. The

l6 tinued while thesubstances are allowed to cool margarine in the following way.

- paste.

- proximately of the final product.

hydrophyllic lipin is added to the margarine on theblender, being prepared for additionto the 3 pounds of monostearyl glycerol is emulsified with 4 pounds of sweet milk or water, the monostearyl glycerol being melted for the purpose of. preparing the emulsion. More specifically, as to the manufacture of this emulsion, the .monostearyl glyceroland milk are both-heated to approximately 160 F. and the monostearyl glycerol introduced into a beater having a wire loop whip. The hot milk is then introduced slowly with constant beating, taking about four to five minutes to. introduce all of the milk. Beating is then conto a sufficiently low temperature to produce a If care is not taken during the emulsification or if the paste emulsion is cooled too quickly the product may be "sandy". This does not prevent it from being used, but it does impair its effectiveness somewhat.

' This paste emulsion after cooling has the consistency of a heavy thick cream, the milk being the continuous phase. If. desired it can be further thinned by the addition of milk or water, but in any case a product having the desired consistency suitable to permit its addition to the margarine in the blender, should be employed. This paste emulsion is then introduced into the margarine. The amount of the paste introduced into the margarine in accordance with my preferred practice should be such that the hydrophyllic lipin dispersed therein 'will be ap- My invention can be practiced with all types of margarine such, for example, as the product known as puff paste in the baking industry. This product consists of a relatively high melting point oleaginous material and either water or milk, emulsified therein. (Water is usually employed in the present practice.) It is used in making what is known as' puff pastry" which consists of a number of thin layers 'of batter separated by the oleaginous paste. In producing the layers they are folded over on themselves repeatedly, each time with a layer of the oleaginous paste separating the layers of batter, and rolled out, the process being continued until a very large number of layers finally results, sometimes 1500.to 1800 layers in an article a portion of an inch in thickness. The function of the puff paste is to act as a lubricant to separate the layers of batter and to hold moisture between the layers so that when the pastry is baked the vaporization of the moisture will put! the layers up and produce a nutty. final product manytimes'the thickness of the. original unbaked'article.

I have found that by means of my invention moisture is prevented from leaking from the oleaginous portion of the paste, with the result that a better paste product is obtained and very much better results are obtained in the final baked product. I have actually produced considerable puff pastry made with paste employing my invention and have found that the results are better in that-sogginess is reduced and a are emulsified with the water and milk (in the usual manner), stabilized by crystallization in a cold medium, and the monostearyl glycerol introduced in the form of a paste by blending as described above.

The term margarine, as used herein, is meant to include all types of edible or culinary plastic emulsions of oleaginous and aqueous substances. The oleaginous substance used may be of vegetable or animal origin, or mixed, and the aqueous substance may be sweet milk, soured or cultured mi k, plain water, brine, or in fact, any edible aqueous medium.

It is obvious that I am not required to restrict my invention to the use of any specific hydrophyllic lipin, or the use thereof with any par- While many details of the invention are disclosed for the purpose of enabling those skilled in the art to practice the same, the scope of the invention is defined in the appended claims.

What I claim as new and desire to protect by Letters Patent of the United States is:-

1. Ass new article of manufacture, a substantially non-leaking margarine comprising oleaginous and aqueous constituents,' and-having included'therein as an addition substanca a relatively small amount of a hydrophyllic lipin iii the form of a derivative of a polyhydroxy substance, said hydrophyllic lip'in being incapable of reducing spattering in margarine and being represented by the general formula (R0) ox(0H)w(H)z wherein O and "H are oxygen and hydrogen respectively, "1:", w and z are relatively small whole numbers, "X" represents the carbon skeleton of a polyhydroxy substance with groups (0H)" and (RO)", wherein R. is an acyl, alkyl or some other substantially lipophile group with at least sixteen carbon atoms, and wherein the ratio of "w" to "v is at least one.

2. As a new article of manufacture, a substantially non-leaking margarine comprising oleaginous and aqueous constituents and including as an addition subs ance at relatively small amount of a hydrophyllic lipin incapable of reducing spattering of the margarine, said hydrophyllic lipin being in the form of a relatively high molecular weight fatty acid ester of a water soluble polyhydroxy substance, the fatty acid ester having more than one unesterified hydroxyl group and the fatty acid radical having at least 18 carbon atoms.

3. As a' new article of manufacture, margarine comprising oleaginous and aqueous constituents andhaving included therein as an addition substance a relatively small amount of a hydrophyllic lipin incapable of reducing spattering ofthe margarine, said hydrophyllic lipin being a higher alkyl derivative of a polyhydroxy compound, the final reaction compound having more than one free hydroxyl group.

4. As a new article of manufacture, a margarine comprising oleaginous and aqueous constituents and having included therein as an addition substance a relatively small amount of a hydrophyllic lipin incapable of reducing spatter- -ing of the margarine, said hydrophyllic lipin being stearic acid ester of a polyhydroxy substance, the final reaction compound having more than one free hydroxyl group.

5. As a new article of manufacture, a margarine comprising oleaginous and aqueous constituents and having included therein as an addition subglycerol.

6. As a new article of manufacture, amargarinecomprising oleaginous and aqueous materials, and

having included therein as an addition substance not more than 1% of monostearyl glycerol.

7. As a new article of manufacture, a margarine comprising oieaginou's and aqueous constituents and having included therein as an addition sub stancea relatively small'amount of a higher mono-alkyl or higher mono-acylderivative of a.' glycol, said derivatives being incapable of reducing margarine, said hydrophyllic lipin being represented by the general formula (nonxmn) (mwherein and H" are oxygen and hydrogen respectively, "12, 141" and "z" are relatively small -whole numbers, X" represents the carbon skeleton of a polyhydroxy substance with groups "(OI-I) and (B0) wherein "R" is an acyl. aliryl or some other substantially lipophile group with at least twelve carbon atoms, and wherein the ratio of w" to "o'f is at least one.

10. The method of improving margine having oleaginous and aqueous constituents to prevent weeping thereof, which comprises first producing a margarine in plastic form, and then introducing into the margine a chemical compound incapable of reducing spattering and represented by the general formula (R0) vX(OH) (H) 3 wherein O? and H are oxygen and hydrogen respectively, "0",

w and 2" are relatively small whole numbers,

X" represents the carbon skeleton of a polyhydroxy substance with groups (011) and (B0) wherein R" is an acyl, alkyl or some other substantially lipophile group with at least twelve carbon atoms, and wherein the ratio of "w" to "v is. at least one, except monolaurin and monomyristin in proportions below 11. The method of improving margarine having oleaginous and aqueous constituentsto prevent weeping thereof, which comprises first producing a margarine in plastic form, forming a paste of achemical compound incapable of reducing spattering and represented by the general formula wherein 0" and H are oxygen and hydrogen respectively, 12", w and "z" are relatively small whole numbers, X represents the carbon skeleton of a polyhydroxy substance with groups (0K) and (B0) wherein "R" is an acyl, alkyl or some other substantially lipophile group with at least twelve carbon atoms, and, wherein the ratioof to "v" is at least one, except monolaurin and monomyristin in proportions below 3 and then blending or kneading the paste into the margarine.

12. Asa new article of manufacture, margarine having oleaginous'and aqueous constituents and having included therein not more than one per cent of a hydroplnrllic lipin incapable of re- 19,425 stance a relatively small amount of monostearyl ducing spatteringof themargarine, said hydrophyllic lipin being represented by the general formula.

(RD)'ox(oH)m(H): v wherein O and "H are oxygen and hydrogen respectively, 0, w" and ".2" are relatively small whole numbers, X" represents the carbon skeleton of a polyhydroxy substance with groups at least sixteen carbon atoms, and wherein the ratio of in to "0 is at least one.

13. As a new artiele'of manufacture, a substantlally non-leaking plastic margarine-like edible emulsion of semi-solid consistency, having'an- ,oleaginous phase and an aqueous phase, and having included therein as an addition substance a relatively small amount of a hydrophyllic lipin in the form of a derivative of a polyhydroxy substance, said hydrophyllic lipin being incapable of reducing spattering in margarine, and being rep resented by the general formula (R0) vx(OH)w(H)z wherein "O" and H" are oxygen-and hydrogen respectively, 0", w and 2" are relatively small whole numbers. "X" represents the carbonskeleton of a. polyhydroxy substance with groups '(OH) and "(B0) wherein R" is an acyl, alkyl or some other substantially lipophile group with atleast sixteen carbon atoms, and wherein the ratio of w" to v" is at least one.

14. The method of producing .an improved margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materials, crystallizing said fluid emulsion in a 'cold medium, reducing the crystallized emulsion to plastic form, and blending into the plastic product a relatively small amount of 'a hydrophillic lipin in the form of a derivative of a polyhydroxy substance, said hydrophillic lipin being incapable of reducing spattering in margarine and being represented by the general formula (aonmomwm);

wherein O and H are oxygen and hydrogen respectively, 12, 10" and z are relatively small whole numbers, "X" represents the carbon-skeleton of a polyhydroxy substance with groups margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materials, crystallizing said' fluid emulsion in a cold medium, reducing 'the crystallized emulsion to plastic form, forming an aqueous paste of 'a hydrophillic lipin in the form of a derivative of a polyhydroxy substance, said hydrophillic lipin being incapable of reducing spattering in margarine and beingrepresented by the general formula (acumen) 10(11):

wherein "O" and "H" are oxygen and hydrogen respectively, 12, "w" and z are relatively small whole numbers, "1! represents the carbon skeleton of a polyhydroxy substance with groups (OH)" and (R0), wherein R is an acyl,.

alkyl, or some other substantially lipophile group with at least sixteen carbon atoms, and wherein the ratio of w'to "v is at least one, and

blending said paste into the said plastic margarine emulsion.

16. The method of producing an improved margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materials, crystallizing said fluid emulsion in a-cold medium, reducing the crystallized emulsion to plastic form, forming an aqueous paste of a hydrophillic lipin-in the form of a derivative of a polyhydroxy substance, said hydrophillic lipin being incapable of reducing spattering in margarine and being represented by the general for- -mula (Ronmomsu-i). I

paste into the said plastic margarine emulsion.

17. The method of producing an improved margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materials, crystallizing said fluid emulsion in a cold medium, reducing the crystallized" emulsion to plastic'form, forming an aqueous paste of a hydrophilliclipin in the form oi. a derivative of a polyhydroxy substance, said hydrophillic lipin being incapable of reducing spatterlng in margarine and being represented by the general formula (RO)sx(OH)w(I-I)l wherein 0" and H are oxygen and hydrogen respectively, "1), "w" and "z" are relatively small whole numbers, X" represents the carbon skeleton of a polyhydroxy substance with groups (0H)" and (R0), wherein R" is an acyl, alkyl or some other substantialy lipophile group with at,least sixteen carbon atoms, and wherein the ratio of "w" to v is at least one, thinning said paste with an amount of milk, and blending the resulting thinned paste into the said plastic'margarine emulsion.

18. The method of producing an improved margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materials, crystalliz ing said fluid emulsion in a cold medium, reducing the crystallized emulsion to plastic form, forming an aqueous paste of a fatty acid'monoglyceride wherein the fatty acid radical has at least sixteen carbon atoms, and

blending said aqueous paste with the said plastic margarine emulsion.

19. The method of producing an improved I margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materials, crystallizing said fluid emulsion in a cold medium, reducing the crystallized emulsion to plastic form, forming an aqueous paste of a fatty acid monoglyceride wherein the fatty acid radical has at least sixteen carbon atoms, thinning said paste with an amount of milk, and blending the thinned paste into the said plastic margarine emulsion.

20. The method of producing an improved margarine which comprises forming a fluid margarine'emulsion of oleaginous and aqueous materials crystallizing said fluid emulsion-in a cold medium, reducing the crystallized emulsion to plastic form,'fo'rming an aqueous paste includ-- ing a proportion of monostearyl glycerol, and blending said paste into the plastic margarine emulsion.

21. The method of producing an improved margarine which comprises forming a fluid margarine emulsion of'oleaginous and aqueous materials, reducing the emulsion to plastic form, and blending into the plastic product a relatively small amount. of a hydrophillic lipin in the form hydrophillic lipin' being incapable of reducing spattering in margarine and being represented by the general formula wherein "O" and "H" are oxygen and hydrogen respectively, "11, w and 2"are relatively small whole numbers, "X" represents the carbon skeleton of a polyhyd'roxy substance with groups "(OH)" and (RO)", wherein R" is an acyl, alkyl or some other substantially lipophile group with at least sixteen carbon atoms, and wherein the ration of w" to v is at least one.

22. The method of producing an improved margarine which comprises forming a fluid margarine emulsion of oleaginous and aqueous materialsQreducing the emulsion to plastic form,

forming an aqueous paste of a fatty acid monoglyceride wherein the fatty acid radical has at of a derivative of a polyhydroxy substance, said least sixteen carbon atoms, and blending said aqueous paste with'the said emulsion.

23. The method of producing an improved margarine which comprises forming a fluid emulsion of aqueous material and oleaginous material of vegetable origin, reducing said fluid emulsion to plastic form, and blending into the plastic margarine monoglyceride of a fatty acid with sixteen carbon atoms. v

24. The method of producing an improved margarine which comprises forming a fluid emulsion of aqueous material and oleaginous material of vegetable origin, consisting predominantly of cocoanut oil, reducing said fluid emulsion to plastic form, and blending into the plastic margarine monoglyceride of a fatty acid with sixteen carbon atoms.

25. As a new article of manufacture, a substantially non-leaking margarine comprising a plastic emulsion of oleaginous and aqueous ma-" plastic margarine the fatty acid radical has at least sixteen carbon atoms. v

26. An improved substantially non-leaking margarine comprising a plastic emulsion of aqueous material and oleaginous material of vegetable origin and including a proportion of a monoglyceride of a fatty acidwith at least sixteen carbon atoms.

27. An improved substantially non-leaking margarine comprising a plastic-emulsion of aqueous material and oleaginous material of hydroxy substance, the hydrophillic lipin being incapable of reducing sputtering in margarine,

and being represented by the general formula v (R0)X(OH)-(H)= wherein "O" and "H" are oxygen and hydrogen respectively, 0, w ,and"z" are relatively small whole numbers. x represents the carbon skeleton of a poly-hydronsubstance, with groups "(OH)" and (R0)" wherein .R is an aeyl,

alkyl or some other substantially lipophile group with at least twelve carbon atoms, and wherein the ratio of 10" to "v" is at least one, and blending said paste into the plastic margarine in an amount so that the hydrophiliic lipin content of the margarine will'be between $5 and 1%.

I 29. The method 01 producing an improved margarine which comprisesrormlnga liquid emulsion of oieaginous and aqueous materials, reducing said liquid emulsion to plastic iorm, forming an aqueous paste including hydrophillic lipin in the form of a derivative of a poly-hydroxy substance, the hydrophillic lipin being incapable of reducing spattering in margarine, and being represented by the general formula (Ronmomum.

wherein "0 and H" are oxygen and hydrogen respectively, v", "10, and "z", are relatively small whole numbers, "1:" represents the carbon skeleton of a poly-hydroxy substance, with groups "(011) and "(B0) wherein "R"-is an acyl, alkyl or some other substantially lipophile group with v at least twelve carbon atoms, and wherein the ratio of '10: to 12" is at least one, and thinning said paste with an. additional amount of aqueous eluding a fatty acid monoglyceride, in which I the fatty acid radical is at-least sixteen carbon to produce asubstantialiy non-leaking product.

BENJAMIN n. mars.

atoms, and blending the paste into the margarine