JP4472621B2 - Soft candy - Google Patents

Description

  The present invention relates to a soft candy.

Soft candy is literally a soft candy and therefore has a problem of being easily attached to teeth. As one means for solving this problem, an emulsifier is conventionally added. For example, soft candy mixed with a polyglycerol fatty acid ester (see Patent Document 1), sucrose fatty acid ester (HLB value 3-7) ), Soft candy containing polyglycerin fatty acid ester and citric acid monoglyceride as essential components (see Patent Document 2), soft candy containing a monoglycerin fatty acid ester having an HLB value of 6.0 or less (see Patent Document 3) A soft candy (see Patent Document 4) containing sorbitan fatty acid ester and HLB11 sucrose fatty acid ester has been proposed.
However, in the above technique, it cannot be said that the problem of soft candy adhering to teeth has been sufficiently solved, and a more effective means has been demanded.
JP 5-7459 A JP-A-5-227893 JP-A-8-38056 Table No. 02/009530, Example 1

  An object of this invention is to provide the soft candy which is excellent in the softness of a chewing and is hard to adhere to a tooth | gear.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that diglycerin fatty acid esters and / or triglycerides in which the content of free polyol is small and the monoester content is limited to a specific range. It has been found that the intended soft candy can be obtained by adding glycerin fatty acid ester to the candy dough, and the present invention has been made based on this finding.

That is, the present invention
(1) Soft candy characterized by containing the following A component and / or B component;
A component: In 100 mass% of diglycerin fatty acid ester, the content of free polyol is 6 mass% or less, and the content of monoester is 35 mass% or more and less than 50 mass%,
B component: It consists of triglycerin fatty acid ester in which the content of free polyol is 6% by mass or less and the content of monoester is 35% by mass or more and less than 50% by mass in 100% by mass of triglycerin fatty acid ester. .

  The soft candy of the present invention is excellent in softness of biting and has extremely little adhesion to teeth.

  The present invention relates to a soft candy characterized by containing the following component A and / or component B as essential components.

A component:
The diglycerin fatty acid ester used as the component A in the present invention is an esterification product of diglycerin and a fatty acid, and is produced by a method known per se such as an esterification reaction.

  As the diglycerin used as a raw material for the diglycerin fatty acid ester used as the component A, a small amount of acid or alkali is usually added to glycerin as a catalyst, and, for example, in an inert gas atmosphere such as nitrogen or carbon dioxide, for example, about The diglycerin mixture whose average polymerization degree of the glycerol obtained by heating at the temperature of 180 degreeC or more and carrying out a polycondensation reaction is about 1.5-2.4, Preferably an average degree of polymerization is about 2.0 is mentioned. Diglycerin may be obtained using glycidol or epichlorohydrin as a raw material. After completion of the reaction, if necessary, treatments such as neutralization, desalting and decolorization may be performed.

  In the component A of the present invention, the diglycerin mixture is purified by a method known per se such as distillation or column chromatography, and diglycerin composed of two molecules of glycerin is about 50% by mass or more, preferably about 85% by mass. High-purity diglycerin having a high concentration of at least% is preferably used.

  The fatty acid used as a raw material for the diglycerin fatty acid ester used as the component A is not particularly limited as long as it is a fatty acid originating from edible animal and vegetable oils and fats. For example, a linear saturated fatty acid having 6 to 24 carbon atoms (for example, , Caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.) or unsaturated fatty acids (eg palmitooleic acid, oleic acid, elaidic acid, Linoleic acid, γ-linolenic acid, α-linolenic acid, arachidonic acid, ricinoleic acid, condensed ricinoleic acid, etc.), preferably one or more selected from saturated or unsaturated fatty acids having 16 to 18 carbon atoms It is a mixture of fatty acids. In particular, it is preferable to use a fatty acid mixture containing about 50% by mass or more, more preferably about 90% by mass or more of palmitic acid and / or stearic acid.

  As a preferred example of the diglycerin fatty acid ester used as component A, the content of free polyol is 6% by mass or less, preferably about 3% by mass or less, and the content of monoester is about 35% by mass or more and 50% by mass. The diglycerin fatty acid ester which is less than% is mentioned. The diglycerin fatty acid ester having such a composition is obtained by esterifying diglycerin and a fatty acid (for example, stearic acid) at a molar ratio of about 1: 0.8 to 1: 1.2, preferably about 1: 1. It can be obtained by removing unreacted diglycerin from the reaction mixture obtained. For example, when 1 mol of diglycerin and 1 mol of fatty acid (eg, stearic acid) are reacted, the estimated content of unreacted diglycerin in the esterification product is about 12 according to the calculation based on the promiscuous distribution rule. The estimated content of the mass% monoester is about 42 mass%. Accordingly, when unreacted diglycerin in an amount corresponding to, for example, about 10% by mass is removed from the reaction mixture obtained by reacting at this charging ratio, the unreacted diglycerin content is calculated to be about 2.4. A diglycerin fatty acid ester having a mass% and a monoester content of about 46.9 mass% is obtained. Unreacted diglycerin can be removed as a polyol containing unreacted diglycerin. Here, the polyol refers to an alcohol having two or more hydroxyl groups in the molecule, and examples thereof include glycerin, diglycerin, triglycerin or tetraglycerin polyglycerin and cyclic glycerin.

  Examples of a method for removing unreacted diglycerin from the reaction mixture include known methods such as liquid-liquid extraction and adsorption separation (see JP-A-7-173380). Preferably, glycerin is added to the reaction mixture. This is a method of mixing and then separating and removing the glycerin phase containing unreacted diglycerin.

  The outline of the production method of the diglycerin fatty acid ester used as the component A is as follows. For example, in a normal reaction vessel equipped with a stirrer, a heating jacket, a baffle plate, etc., diglycerin and fatty acid are charged at a molar ratio of about 1: 1, sodium hydroxide is added as a normal catalyst, and mixed with stirring. Under a gas atmosphere, heating is performed at a predetermined temperature while removing water generated by the esterification reaction out of the system. The reaction temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. The reaction pressure condition is normal pressure or reduced pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 3 hours. The end point of the reaction is usually determined by measuring the acid value of the reaction mixture and about 12 or less. The obtained reaction liquid is a mixture containing unreacted fatty acid, unreacted diglycerin, diglycerin monofatty acid ester, diglycerin difatty acid ester, diglycerin trifatty acid ester, diglycerin tetrafatty acid ester, and the like.

After completion of the esterification reaction, the catalyst remaining in the reaction mixture is neutralized. In that case, when the temperature of esterification reaction is 200 degreeC or more, it is preferable to neutralize after cooling liquid temperature to about 180-200 degreeC. Moreover, when reaction temperature is 200 degrees C or less, you may perform a neutralization process with the temperature as it is. For neutralization of the catalyst, for example, when sodium hydroxide is used as the catalyst and neutralized with phosphoric acid (85% by mass), the amount of phosphoric acid calculated by the neutralization reaction formula (1) shown below is used. The amount of phosphoric acid (85% by mass) divided by 0.85 ^* or more, preferably about 2-3 times the amount obtained by dividing the amount of phosphoric acid calculated by the neutralization reaction formula (1) by 0.85 Of phosphoric acid (85% by weight) is added to the reaction mixture and mixed well. After neutralization, it is allowed to stand at that temperature for about 0.5 hours or more, more preferably for about 1 to 10 hours. If unreacted diglycerin separates into the lower layer, it is removed.
* When the amount of sodium hydroxide used is 1.0 g, it is about 0.96 g.

  Next, the reaction mixture is cooled if necessary and kept at about 60 ° C. or higher and lower than 180 ° C., preferably about 120 ° C. or higher and lower than 180 ° C., more preferably about 130-150 ° C. About 0.5 to 10 times, preferably about 0.5 to 5 times, the amount of glycerin is added relative to the total mass of fatty acids. After thoroughly mixing the reaction mixture and glycerin, leave at that temperature for about 0.5 hours or more, preferably about 1 to 10 hours, and remove the lower layer (glycerin phase containing unreacted diglycerin) separated into two phases Or centrifuge to remove the glycerin phase containing unreacted diglycerin. When there is little addition amount of glycerol with respect to a reaction mixture, removal of unreacted diglycerol will become inadequate. Moreover, when there is too much addition amount of glycerol, it will take time for isolation | separation and removal of a glycerol phase, and it will lead to the fall of productivity, and is unpreferable.

  The diglycerin fatty acid ester obtained by the above treatment is preferably further distilled under reduced pressure to distill off the remaining glycerin, and if necessary, treatment such as desalting, decolorization, filtration is performed, finally, A diglycerin fatty acid ester is obtained in which the free polyol is reduced to less than 6% by mass, preferably about 3% by mass or less, and the monoester is contained in an amount of about 35% by mass to less than 50% by mass. The diglycerin fatty acid ester is excellent in the effect as a surfactant per unit mass because the content of free polyol is small, and further by making the monoester body about 35 mass% or more and less than 50 mass%. In particular, an excellent anti-toothing effect is exhibited as an emulsifier added to soft candy.

B component:
The triglycerin fatty acid ester used as the component B in the present invention is an esterification product of triglycerin and a fatty acid, and is produced by a method known per se such as an esterification reaction.

  As triglycerin used as a raw material for triglycerin fatty acid ester used as component B, a small amount of acid or alkali is usually added to glycerin as a catalyst, and, for example, in an inert gas atmosphere such as nitrogen or carbon dioxide, about A triglycerin mixture having an average degree of polymerization of glycerin obtained by heating at a temperature of 180 ° C. or higher and causing a polycondensation reaction is about 2.5 to 3.4, and preferably an average degree of polymerization of about 3.0. Triglycerin may be obtained using glycidol or epichlorohydrin as a raw material. After completion of the reaction, if necessary, treatments such as neutralization, desalting and decolorization may be performed.

  In the component B of the present invention, the triglycerin mixture is purified by a method known per se such as distillation or column chromatography, and triglycerin composed of 3 molecules of glycerin is about 50% by mass or more, preferably about 85% by mass. High-purity triglycerin having a high concentration of at least% is preferably used.

  The fatty acid used as the raw material of the triglycerin fatty acid ester used as the B component is not particularly limited as long as it is a fatty acid originating from edible animal and vegetable oils and fats, for example, a linear saturated fatty acid having 6 to 24 carbon atoms (for example, , Caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.) or unsaturated fatty acids (eg palmitooleic acid, oleic acid, elaidic acid, Linoleic acid, γ-linolenic acid, α-linolenic acid, arachidonic acid, ricinoleic acid, condensed ricinoleic acid, etc.), preferably one or more selected from saturated or unsaturated fatty acids having 16 to 18 carbon atoms It is a mixture of fatty acids. In particular, it is preferable to use a fatty acid mixture containing about 50% by mass or more, more preferably about 90% by mass or more of palmitic acid and / or stearic acid.

  As a preferred example of the triglycerin fatty acid ester used as component B, the content of free polyol is 6% by mass or less, preferably about 3% by mass or less, and the content of monoester is about 35% by mass or more and 50% by mass. The triglycerin fatty acid ester which is less than% is mentioned. The triglycerin fatty acid ester having such a composition is obtained by esterifying triglycerin and a fatty acid (for example, stearic acid) at a molar ratio of about 1: 0.8 to 1: 1.2, preferably about 1: 1. It can be obtained by removing unreacted triglycerin from the resulting reaction mixture. For example, when 1 mole of triglycerin is reacted with 1 mole of fatty acid (eg, stearic acid), the estimated content of unreacted triglycerin in the esterification product is about 15 according to the calculation based on the promiscuous distribution rule. The estimated content of mass% monoester is about 41 mass%. Therefore, when unreacted triglycerin in an amount corresponding to, for example, about 10% by mass is removed from the reaction mixture obtained by reaction at this charging ratio, the unreacted triglycerin content is calculated to be about 5.6. A triglycerin fatty acid ester having a mass% and a monoester content of about 45.6% by mass is obtained. Unreacted triglycerin can be removed as a polyol containing unreacted triglycerin. Here, the polyol refers to an alcohol having two or more hydroxyl groups in the molecule, and examples thereof include glycerin, diglycerin, triglycerin, tetraglycerin polyglycerin and cyclic glycerin.

  Methods for removing unreacted triglycerin from the reaction mixture include known methods such as liquid-liquid extraction and adsorption separation (see JP-A-7-173380). Preferably, glycerin is added to the reaction mixture. This is a method of mixing and then separating and removing the glycerin phase containing unreacted triglycerin.

  The outline of the production method of the triglycerin fatty acid ester used as the B component is as follows. For example, in a normal reaction vessel equipped with a stirrer, a heating jacket, a baffle plate, etc., triglycerin and fatty acid are charged at a molar ratio of about 1: 1, sodium hydroxide is added as a normal catalyst, and mixed with stirring. Under a gas atmosphere, heating is performed at a predetermined temperature while removing water generated by the esterification reaction out of the system. The reaction temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. The reaction pressure condition is normal pressure or reduced pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 3 hours. The end point of the reaction is usually determined by measuring the acid value of the reaction mixture and about 12 or less. The obtained reaction liquid contains unreacted fatty acid, unreacted triglycerin, triglycerin monofatty acid ester, triglycerin difatty acid ester, triglycerin trifatty acid ester, triglycerin tetrafatty acid ester, triglycerin pentafatty acid ester and the like. It is a mixture.

After completion of the esterification reaction, the catalyst remaining in the reaction mixture is neutralized. In that case, when the temperature of esterification reaction is 200 degreeC or more, it is preferable to neutralize after cooling liquid temperature to about 180-200 degreeC. Moreover, when reaction temperature is 200 degrees C or less, you may perform a neutralization process with the temperature as it is. For neutralization of the catalyst, for example, when sodium hydroxide is used as the catalyst and neutralized with phosphoric acid (85% by mass), the amount of phosphoric acid calculated by the neutralization reaction formula (1) shown below is used. The amount of phosphoric acid (85% by mass) divided by 0.85 ^* or more, preferably about 2-3 times the amount obtained by dividing the amount of phosphoric acid calculated by the neutralization reaction formula (1) by 0.85 Of phosphoric acid (85% by weight) is added to the reaction mixture and mixed well. After neutralization, it is allowed to stand at that temperature for about 0.5 hours or more, more preferably for about 1 to 10 hours. If unreacted triglycerin separates into the lower layer, it is removed.
* When the amount of sodium hydroxide used is 1.0 g, it is about 0.96 g.

  Next, the reaction mixture is cooled if necessary and maintained at about 60 ° C. or higher and lower than 180 ° C., preferably about 120 ° C. or higher and lower than 180 ° C., more preferably about 130 to 150 ° C. About 0.5 to 10 times, preferably about 0.5 to 5 times, the amount of glycerin is added relative to the total mass of fatty acids. After thoroughly mixing the reaction mixture and glycerin, leave at that temperature for about 0.5 hours or more, preferably about 1 to 10 hours, and remove the lower layer (glycerin phase containing unreacted triglycerin) separated into two phases. Or centrifuge to remove the glycerin phase containing unreacted triglycerin. When the amount of glycerin added to the reaction mixture is small, removal of unreacted triglycerin becomes insufficient. Moreover, when there is too much addition amount of glycerol, it will take time for isolation | separation and removal of a glycerol phase, and it will lead to the fall of productivity, and is unpreferable.

  The triglycerol fatty acid ester obtained by the above treatment is preferably further distilled under reduced pressure to distill off the remaining glycerol, and if necessary, treatment such as desalting, decolorization, filtration is performed, finally, The free polyol is reduced to less than 6% by mass, preferably about 3% by mass or less, and a triglycerin fatty acid ester containing a monoester product of about 35% by mass to less than 50% by mass is obtained. Since the triglycerin fatty acid ester has a small content of free polyol, it has an excellent effect as a surfactant per unit mass, and further, by making the monoester form about 35 mass% or more and less than 50 mass%. In particular, an excellent anti-toothing effect is exhibited as an emulsifier added to soft candy.

  Although content of A component and / or B component in the soft candy of this invention is not specifically limited, For example, it is about 0.01-5 mass%, Preferably it is about 0.05-1 mass%.

  Soft candy as used in the present invention refers to saccharides or saccharides such as dairy products, fats and oils, fruits, fruit juices or seeds (including processed products), starches, flours, gelatins, egg whites, albumins, acidulants, flavorings, colorings. It is a soft candy obtained by cooling and shaping a candy dough boiled in a candy shape with a water content of about 6 to 10% by weight, using a mixture of ingredients, water, etc. Specifically, for example, caramel, nougat Etc.

  Examples of sugars include xylose, glucose, fructose, honey, maple syrup, sugar, maltose, lactose, isomerized liquid sugar (such as glucose fructose liquid sugar, fructose glucose liquid sugar, and high fructose liquid sugar), and sugar mixed isomerized liquid sugar. , Starch syrup, powdered candy, xylooligosaccharide, fructooligosaccharide, galactooligosaccharide, palatinose, isomaltoligosaccharide, xylitol, sorbitol, mannitol, lactitol, maltitol, erythritol, reduced syrup and reduced palatinose. These saccharides may be used alone or in any combination of two or more.

  Examples of dairy products include milk, creams obtained by centrifuging milk, fermented milk such as yogurt, sweetened milk, sugar-free milk, concentrated milk, whole milk powder, skimmed milk powder, cream powder, whey powder and butter Examples include milk powder such as milk powder, natural cheese, processed cheese, whey cheese, concentrated whey, and sodium caseinate. These dairy products may be used alone or in any combination of two or more.

  Examples of oils and fats include olive oil, canola oil, rice bran oil, safflower oil, high oleic safflower oil, soybean oil, corn oil, rapeseed oil, palm oil, palm kernel oil, sunflower oil, high oleic sunflower oil, cottonseed oil, palm Vegetable oils such as oil and peanut oil, animal fats such as beef tallow, pork fat, fish oil and milk fat, those obtained by fractionating these animal and plant oils (eg palm olein, palm stearin, etc.) or hydrogenated, Examples include animal and vegetable oils and fats that have been subjected to transesterification by arbitrarily combining two or more kinds. These fats and oils may be used alone or in any combination of two or more.

  Examples of the fruit and fruit juice include fruit or fruit juice such as mango, pine, pear, peach, orange, mandarin orange, grape, apple, melon or cowberry. The fruit may be a dried fruit. Examples of seeds include almonds, cashew nuts, macadamia nuts, pistachios or peanuts. Examples of the starch include potato starch, corn starch, wheat starch, tapioca starch, and processed starch thereof. Examples of the acidulant include citric acid, sodium citrate, DL-malic acid, L-oxalic acid, and lactic acid. Examples of the coloring agent include Benikouji pigment, β-carotene, anthocyanin pigment, gardenia pigment, safflower red pigment, safflower yellow pigment, turmeric pigment, caramel pigment, and anato pigment. One of these may be used alone, or two or more of these may be used in combination.

In addition, the soft candy of the present invention includes coffee extracts, black tea extracts, tea extracts or extracts such as propolis, vitamins such as vitamin C or vitamin E, or minerals such as calcium, magnesium or iron. It may be included. One of these may be used alone, or two or more of these may be used in combination.
Furthermore, for the purpose of improving the texture of soft candy, gum arabic, carrageenan, caraya gum, xanthan gum, guar gum, gellan gum, tamarind seed gum, tara gum, tragacanth gum, pectin, locust bean gum, etc. A thickening stabilizer may be added. A thickening stabilizer may be used individually by 1 type, and may be used in combination of 2 or more types.

  Moreover, the soft candy of this invention can be made to contain various emulsifiers in the range which does not inhibit the effect of this invention other than said A component or B component. Examples of the emulsifier include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, and lecithin. Here, glycerin fatty acid ester includes glycerin and fatty acid ester, glycerin organic acid fatty acid ester (for example, glycerin acetic acid ester, glycerin acetic acid fatty acid ester, glycerin lactic acid fatty acid ester, glycerin citric acid fatty acid ester, glycerin succinic acid fatty acid ester). Glycerin diacetyl tartaric acid fatty acid ester, etc.), polyglycerin fatty acid ester (excluding the A component and B component) and polyglycerin condensed ricinoleic acid ester. Further, as lecithin, liquid lecithin containing oil such as soybean lecithin and egg yolk lecithin, powdered lecithin obtained by removing oil from liquid lecithin, fractionated lecithin obtained by separating and purifying liquid lecithin, and enzyme-decomposed lecithin obtained by treating lecithin with enzyme and enzyme-treated lecithin Etc.

There is no restriction | limiting in particular in the manufacturing method of the soft candy of this invention, The soft candy of this invention can be manufactured by a conventional method, for example using a conventional apparatus etc.
For example, the outline of the production method of caramel is as follows. For example, saccharides such as sugar and starch syrup are added and dissolved in water sufficient to dissolve the saccharide, and if desired, dairy products, fats and oils, starch or flour are added, preferably heated to about 60 to 80 ° C. and mixed, Use raw material mixture. The obtained raw material mixture is preferably heated to about 120 to 125 ° C. under normal pressure or reduced pressure, and boiled until the desired water content (preferably about 6 to 10% by mass) is obtained to obtain a concentrated solution. The obtained concentrated liquid is cooled (preferably about 100 ° C.), and according to the type of caramel to be produced, fruit or seeds, acidulant, fragrance, pigment, etc. are added and kneaded uniformly to obtain a caramel dough. Is preferred.

  The component A and / or component B used in the present invention may be added to either the raw material mixture or the concentrated solution. In addition, the A component and / or the B component may be added directly as a solid or a liquid, or a dispersion in which the A component and / or the B component are dispersed in water may be prepared in advance.

  Next, the caramel dough is preferably cooled to a product temperature, preferably about 40 to 50 ° C., and then shaped with a molding machine, or shaped into a sheet with a roll or the like and then cut with a cutter or the like. The caramel dough which has been shaped or cut is more preferably cooled to about 20 to 25 ° C. to obtain caramel. The obtained caramel is preferably individually packaged, for example, with paraffin paper or synthetic resin sheets or sachets.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto.

[Production Example 1]
Into a reaction kettle equipped with a stirrer, thermometer, gas blowing pipe and water separator, 20 kg of glycerin was added, 100 mL of a 20 w / v% sodium hydroxide aqueous solution was added as a catalyst, and a glycerin condensation reaction was performed at 250 ° C. for 4 hours in a nitrogen gas stream. went.

  The obtained reaction product was cooled to about 90 ° C., neutralized by adding about 20 g of phosphoric acid (85% by mass) and filtered, and the filtrate was distilled under reduced pressure at 160 ° C. and 250 Pa under reduced pressure for glycerin. Next, molecular distillation was performed under high vacuum conditions of 200 ° C. and 20 Pa to obtain about 3.0 kg of a fraction containing 3% by mass of glycerin, 92% by mass of diglycerin and 5% by mass of triglycerin (diglycerin mixture). It was.

  Further, the distillation residue was subjected to molecular distillation under high vacuum conditions of 240 ° C. and 20 Pa, glycerin 0.2% by mass, diglycerin 5% by mass, triglycerin 88% by mass, tetraglycerin 6% by mass, cyclic glycerin 0.8%. About 1.5 kg of a fraction containing mass% (triglycerin mixture) was obtained.

  Next, 1% by mass of activated carbon was added to each fraction, followed by decolorization treatment under reduced pressure and filtration. The obtained diglycerin mixture had a hydroxyl value of about 1359, an average degree of polymerization of about 2.0, a triglycerin mixture having a hydroxyl value of about 1170, and an average degree of polymerization of about 3.0.

[Production Example 2]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 166 g (about 1.0 mol) of the diglycerin mixture obtained in Production Example 1 and palmitic acid (trade name: palmitic acid) acid 98; Miyoshi Yushi Co.) 100 g, stearic acid (trade name: NAA-180; manufactured by NOF Corporation) were charged 230 g _{(corresponding} to about 1.2 mol of _C 16 · _{C 18} mixed fatty acids), hydroxide as a catalyst 10 mL of a 10 w / v% aqueous solution of sodium was added, and an esterification reaction was performed for about 2 hours at 240 ° C. in a nitrogen gas stream until the acid value became 3 or less. The obtained reaction mixture was cooled to about 180 ° C., 2.3 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and the mixture was left at that temperature for about 1 hour, and the separated unreacted diglycerin was removed. About 5 g of the contained polyol was removed. Next, the reaction mixture was cooled to about 150 ° C., 335 g of glycerin was added and mixed uniformly, and then left at that temperature for about 1 hour to remove about 270 g of the separated glycerin phase. The obtained diglycerin fatty acid ester was distilled under reduced pressure at about 150 ° C. and about 400 Pa to distill away the remaining glycerin, thereby obtaining about 435 g of a diglycerin fatty acid ester (prototype 1). The acid value of this product was about 0.8.

[Production Example 3]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 166 g (about 1.0 mol) of the diglycerin mixture obtained in Production Example 1 and palmitic acid (trade name: palmitic acid) acid 98; Miyoshi Yushi Co.) 100 g, stearic acid (trade name: NAA-180; manufactured by NOF Corporation) were charged 230 g _{(corresponding} to about 1.2 mol of _C 16 · _{C 18} mixed fatty acids), hydroxide as a catalyst 10 mL of a 10 w / v% aqueous solution of sodium was added, and an esterification reaction was performed for about 2 hours at 240 ° C. in a nitrogen gas stream until the acid value became 3 or less. The resulting reaction mixture was cooled to about 180 ° C., 2.3 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, left at that temperature for about 1 hour, and separated unreacted diglycerin about 5 g was removed to obtain about 460 g of diglycerin fatty acid ester (prototype 2). The acid value of this product was about 1.0.

[Production Example 4]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 166 g (about 1.0 mol) of the diglycerin mixture obtained in Production Example 1 and palmitic acid (trade name: palmitic acid) acid 98; Miyoshi Yushi Co.) 133 g, stearic acid (trade name: NAA-180; manufactured by NOF Corporation) were charged 307 g _{(corresponding} to about 1.6 mol of _C 16 · _{C 18} mixed fatty acids), hydroxide as a catalyst 10 mL of a 10 w / v% aqueous solution of sodium was added, and an esterification reaction was performed for about 2 hours at 240 ° C. in a nitrogen gas stream until the acid value became 3 or less. The obtained reaction mixture was cooled to about 180 ° C., 2.3 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and the mixture was left at that temperature for about 1 hour to separate unreacted diglycerin. After confirming that it was hardly recognized, about 570 g of diglycerin fatty acid ester (prototype 3) was obtained. The acid value of this product was about 2.0.

[Production Example 5]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 240 g (about 1.0 mol) of the triglycerin mixture obtained in Production Example 1 and palmitic acid (trade name: palmitic acid) 120 g of acid 98; manufactured by Miyoshi Oil & Fats Co., Ltd. and 120 g of stearic acid (trade name: NAA-180; manufactured by Nippon Oil & Fats Co., Ltd.) (corresponding to about 0.89 moles as a C ₁₆ · C ₁₈ mixed fatty acid) were used and hydroxylated as a catalyst 10 mL of a 10 w / v% aqueous solution of sodium was added, and an esterification reaction was performed for about 2 hours at 240 ° C. in a nitrogen gas stream until the acid value became 12 or less. The obtained reaction mixture was cooled to about 180 ° C., 2.3 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and the mixture was left at that temperature for about 1 hour. About 40 g of the contained polyol was removed. Next, the reaction mixture was cooled to about 150 ° C., 400 g of glycerin was added and mixed uniformly, and then left at that temperature for about 1 hour to remove about 320 g of the separated glycerin phase. The obtained triglycerin fatty acid ester was distilled under reduced pressure at about 150 ° C. and about 400 Pa to distill off the remaining glycerin, thereby obtaining about 390 g of a triglycerin fatty acid ester (prototype 4). The acid value of this product was about 1.6.

[Production Example 6]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 240 g (about 1.0 mol) of the triglycerin mixture obtained in Production Example 1 and palmitic acid (trade name: palmitic acid) 120 g of acid 98; manufactured by Miyoshi Oil & Fats Co., Ltd. and 120 g of stearic acid (trade name: NAA-180; manufactured by Nippon Oil & Fats Co., Ltd.) (corresponding to about 0.89 moles as a C ₁₆ · C ₁₈ mixed fatty acid) were used and hydroxylated as a catalyst 10 mL of a 10 w / v% aqueous solution of sodium was added, and an esterification reaction was performed for about 2 hours at 240 ° C. in a nitrogen gas stream until the acid value became 12 or less. The obtained reaction mixture was cooled to about 180 ° C., 2.3 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and after neutralization, the liquid temperature was cooled to about 150 ° C. After leaving for 1 hour, about 40 g of the polyol containing unreacted triglycerin separated was removed to obtain about 410 g of triglycerin fatty acid ester (prototype 5). The acid value of this product was about 1.6.

[Production Example 7]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 240 g (about 1.0 mol) of the triglycerin mixture obtained in Production Example 1 and palmitic acid (trade name: palmitic acid) 216 g of acid 98; manufactured by Miyoshi Oil & Fats Co., Ltd., and 216 g of stearic acid (trade name: NAA-180; manufactured by Nippon Oil & Fats Co., Ltd.) (corresponding to about 1.6 mol as a C ₁₆ · C ₁₈ mixed fatty acid) were charged and hydroxylated as a catalyst. An aqueous 10 w / v% sodium solution (10 mL) was added, and an esterification reaction was performed for about 2 hours at 240 ° C. in a nitrogen gas stream until the acid value became 5 or less. The obtained reaction mixture was cooled to about 180 ° C., 2.3 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and after neutralization, the liquid temperature was cooled to about 150 ° C. After standing for 1 hour, it was confirmed that almost no separation of polyol containing unreacted triglycerin was observed, and about 640 g of triglycerin fatty acid ester (prototype 6) was obtained. The acid value of this product was about 2.0.

[Test Example 1]
The contents of free polyol and monoester in the diglycerin fatty acid ester and the triglycerin fatty acid ester (prototypes 1 to 6) obtained in Production Examples 2 to 7 were measured. The results are shown in Table 1.

[Method for measuring free polyol content]
A glass column (length: 21 cm, diameter: 2 cm) was packed with about 30 g of reverse phase silica gel (trade name: Inertsil ODS-3; GL Sciences) by a dry method. About 10 g of a sample was accurately weighed and dissolved in 50 mL of a 25% by volume aqueous methanol solution and poured into the upper layer of the column. Subsequently, 200 mL of a 25% by volume aqueous methanol solution was passed at a flow rate of 1 mL / 1 minute to collect the effluent. This effluent was washed into a concentration flask of known weight, concentrated using a rotary evaporator at about 90 ° C. and about 4 kPa, and then allowed to cool in a desiccator. The polyol content (mass%) was determined.

[Monoester content measurement method]
The ester composition analysis was performed using HPLC, and the quantitative analysis was performed by the absolute calibration curve method. That is, the peak area corresponding to the monoester form of the test sample recorded on the chromatogram by the data processor is measured, and the diglycerin monostearate or triglycerin monostearate purified by normal phase column chromatography The monoester content (% by mass) of the test sample was determined from a calibration curve prepared using ester as a standard sample.

The HPLC analysis conditions are shown below.
<HPLC analysis conditions>
Equipment Shimadzu high performance liquid chromatograph
Pump (Model: LC-10A; manufactured by Shimadzu Corporation)
Column oven (model: CTO-10A; manufactured by Shimadzu Corporation)
Data processing device (model: C-R7A; manufactured by Shimadzu Corporation)
Column GPC column (Model: SHODEX KF-802; Showa Denko)
Two-linked mobile phase THF
Flow rate 1.0mL / min
Detector RI detector (model: RID-6A; manufactured by Shimadzu Corporation)
Column temperature 40 ° C
Test solution injection volume 15μL (in THF)

[Example 1]
<Production of caramel>
Mix and dissolve 57 g of super white sugar, 90 g of starch syrup, 0.3 g of sodium chloride and 50 g of water, add 120 g of sweetened milk and 1.2 g of emulsifier (Prototype 1 or 4) listed in Table 3, mix and stir. The mixture was heated to about 80 ° C. Next, 27 g of butter and 4.5 g of palm kernel extremely hardened oil were added, mixed and emulsified. The obtained emulsified liquid (caramel dough stock solution) is heated and boiled with stirring in a conventional manner, and when the liquid temperature reaches about 120 ° C, the heating is stopped and poured into a metal vat, until the temperature reaches about 50 ° C. Cooled down. The obtained caramel dough was formed into a sheet through a 15 mm thick roller and further cut into 18 × 18 mm with a cutter to obtain a caramel sample (No. 1 or 4). The water content of the obtained caramel was about 7.0% by mass.

[Comparative Example 1]
<Production of caramel>
Example 1 except that 1.2 g of the emulsifier described in Table 3 (prototype 2, 3, 5 or 6) was used instead of 1.2 g of the emulsifier described in Table 3 (prototype 1 or 4). A caramel sample (No. 2, 3, 5 or 6) was obtained in the same manner as described above. The water content of the obtained caramel was about 7.0% by mass.

<Evaluation of caramel>
(1) Wrapping caramel samples (No. 1-6) with paraffin paper, placing them in aluminum laminate bags and keeping them at 25 ° C. for 7 days, and then softening bite and adhesion to teeth according to the evaluation criteria shown in Table 2 below Sex was evaluated.

The sensory test was conducted with 10 panelists, and the result was obtained as an average value of the scores of 10 people and was symbolized according to the following criteria. The results are shown in Table 3.
○ Average score is 2.5 or more △ Average score is 1.5 or more and less than 2.5 × Average score is less than 1.5

  It is clear that the caramel samples (Nos. 1 and 4) of the examples are soft to bite, have good adhesion to teeth, and have excellent texture. On the other hand, the caramel samples of comparative examples (Nos. 2, 3, 5 and 6) were inferior to the caramel of the examples because of low evaluation of the softness of biting and adhesion to teeth.

  (2) Caramel samples (No. 1 to 6) are wrapped in paraffin paper, placed in an aluminum laminate bag and kept at 25 ° C for 7 days, then a caramel chewing test is conducted with a physical property evaluation / testing machine to determine hardness and adhesion. Sex was measured.

[Method for measuring physical properties of caramel]
Apparatus: Shimadzu Texture Analyzer EZ Test (manufactured by Shimadzu Corporation)
Method: A caramel sample was placed on the lower platen, and the tooth-shaped push rod B probe was pressed at a speed of 20 mm / min, entered to a depth of 7 mm, and the applied maximum load (N) was made hard. Next, the rod B probe was pulled up at a speed of 20 mm / min, and the total amount of stress (N · mm) at that time was regarded as adhesive. The smaller the hardness value, the softer the caramel, and the lower the tackiness, the harder it adheres to the teeth and the better the tooth separation. The results are shown in Table 4.

  The caramel samples of Examples (Nos. 1 and 4) were soft and had low tackiness. On the other hand, the caramel samples of comparative examples (No. 2, 3, 5 and 6) were relatively hard and had high tackiness. The physical property evaluation / measurement results were in good agreement with the sensory test results.

[Example 2]
<Production of caramel>
Mix and dissolve 90g of super white sugar, 123g of syrup, and 75g of water, add 60g of sweetened milk and 1.5g of emulsifier (Prototype 1 or 4) listed in Table 5 and mix. Warmed up. Next, 25.5 g of extremely hardened palm oil was added and mixed and emulsified. The obtained emulsified liquid (caramel dough stock solution) is heated and boiled with stirring in a conventional manner, and when the liquid temperature reaches about 120 ° C, the heating is stopped and poured into a metal vat, until the temperature reaches about 50 ° C. Cooled down. The obtained caramel dough was formed into a sheet through a 15 mm thick roller and further cut into 18 × 18 mm with a cutter to obtain a caramel sample (No. 7 or 8). The water content of the obtained caramel was about 8.0% by mass.

[Comparative Example 2]
<Production of caramel>
Operation similar to Example 2 except having used 1.5 g of emulsifiers (commercial item AF) of Table 5 instead of 1.5 g of emulsifiers of Table 5 (prototype 1 or 4). And caramel samples (Nos. 9 to 14) were obtained. The water content of the obtained caramel was about 8.0% by mass. In addition, the following were used for the commercial items A to F.
Commercial product A: glycerol monobehenate (trade name: Poem B-100; manufactured by Riken Vitamin Co., Ltd.)
Commercial product B: tetraglycerin monostearate (trade name: Poem J-4081; manufactured by Riken Vitamin Co., Ltd.)
Commercial product C: hexaglycerin monostearate (trade name: SY-Glyster MS-5S; manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)
Commercial product D: polyglycerin polyricinoleate (trade name: Poem PR-300; manufactured by Riken Vitamin Co., Ltd.)
Commercial product E: sorbitan tristearate (trade name: Poem S-65V; manufactured by Riken Vitamin Co., Ltd.)
Commercial product F: Lecithin (trade name: SLP paste; manufactured by Sakai Oil Co., Ltd.)

<Evaluation of caramel>
Caramel samples (Nos. 7 to 14) are wrapped in paraffin paper, placed in an aluminum laminate bag and kept at 25 ° C. for 7 days, and then the softness of biting and adhesion to teeth are evaluated according to the evaluation criteria shown in Table 2 above. did. The sensory test was conducted with 10 panelists, and the result was obtained as an average value of the scores of 10 people and was symbolized according to the following criteria. The results are shown in Table 5.
○ Average score is 2.5 or more △ Average score is 1.5 or more and less than 2.5 × Average score is less than 1.5

It is clear that the caramel samples (Nos. 7 and 8) in the examples are soft to bite, have good adhesion to teeth, and have excellent texture. On the other hand, although the caramel sample (No. 9) of the comparative example had good tooth separation, it was quite hard, and the caramel sample (No. 10-14) had a low evaluation of adhesion to the teeth. It was inferior compared.

Claims (1)

Soft candy characterized by containing the following A component or B component;
A component: In 100 mass% of diglycerin fatty acid ester, the content of free polyol is 6 mass% or less, and the content of monoester is 35 mass% or more and less than 50 mass%,
Component B: Triglycerin fatty acid ester in which the content of free polyol is 6% by mass or less and the content of monoester is 35% by mass or more and less than 50% by mass in 100% by mass of triglycerin fatty acid ester.