JP2017209086A - Hydrous chocolates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide hydrous chocolates that are excellent in shape retention at ordinary temperature and offer a good eat-texture.SOLUTION: Provided is hydrous chocolates that are characterized by containing cellulose nanofibers. More specifically, by using a chemically modified cellulose nanofiber (in particular, an oxidized cellulose nanofiber or a carboxymethylated cellulose nanofiber), hydrous chocolates having both shape retention and eat-texture at ordinary temperature can be provided and the hydrous chocolates are suitable for use in bread and confectionery.SELECTED DRAWING: None

Description

  The present invention relates to water-containing chocolates and bread and confectionery using the same. More specifically, water-containing chocolates containing cellulose nanofibers and breads and confectionery using the same, no stickiness at room temperature, excellent shape retention, smoothness and mouthfeel without stickiness The present invention relates to a hydrated chocolate having a ganache-like body feeling, and bread and confectionery using the same.

  Water-containing chocolate such as raw chocolate and ganache is manufactured by blending water-based raw materials such as fresh cream into chocolate dough, and has a softer and better mouthfeel than ordinary chocolate. ing. Bread and confectionery using a combination of these ganache-like water-containing chocolate-based foods are manufactured, and many of them are filled and coated with these ganache-like water-containing chocolate-based foods after baking.

  Such a water-containing chocolate has a problem that the melted chocolate easily adheres to hands and packaging containers. In particular, there is a demand for foods that are not sticky and easy to eat even in high temperatures such as summer.

  Furthermore, since such a water-containing chocolate is too soft at room temperature, a simple shape causes difficulty in shape retention, and it is often used as a center for truffles or the like coated with ordinary chocolate. However, since it is coated with ordinary chocolate, there is a drawback that the outer coated chocolate is obstructed by the smooth and smooth touch of the water-containing chocolate.

  In order to solve such drawbacks, for example, in Patent Document 1 below, hydrophilic ingredients such as fresh cream, milk and liquor and chocolates, chicken eggs such as whole eggs, egg yolks and egg whites, and non-fat milk are used. A method of containing whey protein as a solid is disclosed. As another method, various methods for maintaining shape retention at room temperature have been proposed. Patent Document 2 proposes a method of adding microcrystalline cellulose, thickening polysaccharide, or the like.

JP 2001-54355 A Japanese Patent Application No. 2013-527989

However, in the method of Patent Document 1, there is a problem that the flavor of chocolate is impaired by the inclusion of the egg component, and the mouthfeel and other textures are unsatisfactory. Moreover, in the method of patent document 2, there existed a problem that a neva remains in a water-containing chocolate. Therefore, in order to achieve the above object, the present inventors have conducted intensive research and found the following means.

The present invention provides the following.
(1) Water-containing chocolates containing cellulose nanofibers.
(2) The water-containing chocolate according to (1), wherein the cellulose nanofiber is a chemically modified cellulose nanofiber.
(3) The chemically modified cellulose nanofiber is an oxidized cellulose nanofiber having an amount of carboxyl groups of 0.5 mmol / g to 3.0 mmol / g with respect to the absolutely dry weight of the chemically modified cellulose nanofiber. The water-containing chocolate according to (2), characterized in that it is characterized.
(4) The chemically modified cellulose nanofiber is a carboxymethylated cellulose nanofiber having a degree of carboxymethyl substitution per glucose unit of the chemically modified cellulose nanofiber of 0.01 to 0.50, The water-containing chocolate according to (2).
(5) A bread using the water-containing chocolate according to any one of (1) to (4).
(6) A confectionery using the water-containing chocolate according to any one of (1) to (4).

According to the present invention, by blending cellulose nanofibers into a water-containing chocolate composed of hydrophilic components such as fresh cream, milk, and liquor and chocolates, etc., there is no stickiness even at room temperature, and there is a neatness. Water-containing chocolates having a ganache-like body feeling, and bread and confectionery using the same can be obtained.

  The present invention is described in detail below.

<Water-containing chocolates>
The chocolates in the present invention are not only chocolates defined in the so-called laws and regulations, in which the oil and fat component consists only of cocoa butter, but usually hard butter as cocoa butter substitute oil used in place of cocoa butter It also includes various chocolates using Therefore, it can be rolled as usual using one or more kinds of cocoa mass, cocoa powder, cocoa butter or hard butter as well as sweet chocolate or milk chocolate known in the art. Chocolate dough obtained by conching treatment can be used. Further, in the present invention, it is also possible to use white chocolate obtained by using a solid component such as cocoa butter or hard butter and sugar, whole milk powder or skim milk powder without using cocoa or cacao mass, Color chocolates with various flavors and colors can be used in combination with flavoring materials such as coffee and fruit.

  In addition to water, liquid sugar, natural fresh creams and milk, etc. as hydrophilic components, creams using animal and vegetable oils and fats that have been developed in the past, concentrated milk or various fruits, fruit juices, natural honey Western liquors can be exemplified, and one or more of these can be used.

<Bread, confectionery>
In the present invention, bread and confectionery are mainly flour such as wheat flour (including starch and gluten), yeast, salt and water, and added with auxiliary materials such as sugars, dairy products, egg products and edible fats and oils. , Refers to those produced by fermentation, molding, baking, steaming, frying, etc. of chaotic dough, French bread such as pullman, French bread such as table roll, baguette, batar, sweet roll, table roll, etc. Baked goods such as rolls, croissants, Danish pastries, yeast donuts, baked goods such as cakes, cookies, rusks, scones, crackers, short breads, custard cream, flower pastes, sponge cakes, butter Examples include cakes such as cakes, donuts and biscuits.

<Cellulose nanofiber>
The water-containing chocolates of the present invention are characterized by containing cellulose nanofibers. Cellulose nanofiber is a material produced by loosening plant fibers to the nano level, and is generally a fine fiber having an average fiber diameter of about 3 to 500 nm and an average aspect ratio of 50 or more. The average fiber diameter and average fiber length of cellulose nanofibers can be obtained by averaging the fiber diameter and fiber length obtained from the results of observing each fiber using a field emission scanning electron microscope (FE-SEM). it can. The aspect ratio can be calculated by the following formula: aspect ratio = average fiber length / average fiber diameter

  Cellulose nanofibers can be produced by applying a strong shearing force after the cellulose raw material is left unmodified or chemically modified. In the present invention, the cellulose raw material may be unmodified or chemically modified, but is more preferably chemically modified. Cellulose nanofibers manufactured using chemically modified cellulose raw materials have a uniform fiber length and fiber diameter compared to cellulose nanofibers manufactured using unmodified cellulose raw materials. It is assumed that it is stable and exhibits a superior effect. Although the method of chemical modification is not particularly limited, for example, oxidation, etherification, phosphorylation, esterification, phosphate esterification, silane coupling, fluorination, cationization and the like can be performed. Among these, any of oxidation, carboxymethylation, and cationization using an N-oxyl compound is preferable, and carboxymethylation or ozone oxidation is particularly preferable because of food use.

<Cellulose raw material>
In the present invention, cellulose raw materials for producing cellulose nanofibers include plants (for example, wood, bamboo, hemp, jute, kenaf, farmland residue, cloth, pulp (conifer unbleached kraft pulp (NUKP), conifer bleach). Kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP) thermomechanical pulp (TMP), regenerated pulp , Waste paper, etc.), animals (for example, ascidians), algae, microorganisms (for example, acetic acid bacteria (Acetobacter)), microbial products and the like are known, and any of them can be used in the present invention. Is a cellulose fiber derived from a plant or a microorganism, more preferably a plant Is a cellulose fiber of come.

  The fiber diameter of the cellulose fiber raw material used in the present invention is not particularly limited, and the number average fiber diameter is 1 μm to 1 mm. What has undergone general purification is about 50 μm. For example, when a chip or the like having a size of several centimeters is refined, it is preferable to perform a mechanical treatment with a disintegrator such as a refiner or a beater to make it about 50 μm.

<Oxidation>
In the present invention, the oxidation of the cellulose raw material can be performed using a known method, and is not particularly limited, but the amount of carboxyl groups is 0.5 mmol / g with respect to the absolute dry weight of the cellulose nanofiber. It is preferable to adjust so that it may be -3.0 mmol / g.

  For example, cellulose can be obtained by oxidizing cellulose in water in the presence of an N-oxyl compound and a compound selected from the group consisting of bromide, iodide or a mixture thereof. By this oxidation reaction, the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, and a cellulose fiber having an aldehyde group and a carboxyl group or a carboxylate group on the surface can be obtained. The concentration of cellulose during the reaction is not particularly limited, but is preferably 5% by mass or less. The N-oxyl compound refers to a compound that can generate a nitroxy radical. As the N-oxyl compound, any compound can be used as long as it promotes the target oxidation reaction.

  The amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount that can oxidize cellulose as a raw material. For example, 0.01 to 10 mmol is preferable, 0.02 to 1 mmol is more preferable, and 0.05 to 0.5 mmol is more preferable with respect to 1 g of absolutely dry cellulose. Moreover, about 0.1-4 mmol / L with respect to a reaction system is good.

  Bromide is a compound containing bromine, examples of which include alkali metal bromides that can dissociate and ionize in water. Further, an iodide is a compound containing iodine, and examples thereof include alkali metal iodide. The amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted. The total amount of bromide and iodide is, for example, preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, and still more preferably 0.5 to 5 mmol with respect to 1 g of absolutely dry cellulose.

  As the oxidizing agent, known ones can be used, and for example, halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, peroxide and the like can be used. Of these, sodium hypochlorite is preferable because it is inexpensive and has a low environmental impact. The appropriate amount of the oxidizing agent used is, for example, preferably 0.5 to 500 mmol, more preferably 0.7 to 50 mmol, further preferably 1 to 25 mmol, and most preferably 3 to 10 mmol with respect to 1 g of absolutely dry cellulose. . For example, 1-40 mol is preferable with respect to 1 mol of N-oxyl compounds.

  The cellulose oxidation process allows the reaction to proceed efficiently even under relatively mild conditions. Therefore, the reaction temperature is preferably 4 to 40 ° C, and may be room temperature of about 15 to 30 ° C. As the reaction proceeds, a carboxyl group is generated in the cellulose, so that the pH of the reaction solution is reduced. In order to advance the oxidation reaction efficiently, an alkaline solution such as an aqueous sodium hydroxide solution is added to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11. The reaction medium is preferably water because it is easy to handle and hardly causes side reactions.

The reaction time in the oxidation reaction can be appropriately set according to the progress of oxidation, and is usually 0.5 to 6 hours, for example, about 1 to 4 hours.
The oxidation reaction may be performed in two stages. For example, by oxidizing the oxidized cellulose obtained by filtration after the completion of the first-stage reaction again under the same or different reaction conditions, the efficiency is not affected by the reaction inhibition by the salt generated as a by-product in the first-stage reaction. Can be oxidized well.

  Another example of the carboxylation (oxidation) method is a method of oxidizing by contacting a gas containing ozone and a cellulose raw material. By this oxidation reaction, at least the hydroxyl groups at the 2nd and 6th positions of the glucopyranose ring are oxidized and the cellulose chain is decomposed. The ozone concentration in the gas containing ozone is preferably 50 to 250 g / m3, and more preferably 70 to 220 g / m3. The amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by mass, and more preferably 5 to 30 parts by mass when the solid content of the cellulose raw material is 100 parts by mass. The ozone treatment temperature is preferably 0 to 50 ° C, and more preferably 20 to 50 ° C. The ozone treatment time is not particularly limited, but is about 1 to 360 minutes, and preferably about 30 to 300 minutes. When the conditions for the ozone treatment are within these ranges, the cellulose can be prevented from being excessively oxidized and decomposed, and the yield of oxidized cellulose is improved. After the ozone treatment, an additional oxidation treatment may be performed using an oxidizing agent. The oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid. For example, these oxidizing agents can be dissolved in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and a cellulose raw material can be immersed in the solution for additional oxidation treatment.

The amount of the carboxyl group, carboxylate group, and aldehyde group of the cellulose fiber can be adjusted by controlling the amount of the oxidizing agent added and the reaction time. The method for measuring the amount of carboxyl groups is, for example, preparing 60 ml of a 0.5 mass% slurry (aqueous dispersion) of oxidized cellulose, adding 0.1 M hydrochloric acid aqueous solution to pH 2.5, and then adding 0.05 N sodium hydroxide. The electrical conductivity was measured by dropping the aqueous solution until the pH reached 11, and the amount was calculated from the amount of sodium hydroxide (a) consumed in the neutralization step of the weak acid where the change in electrical conductivity was slow, using the following formula: can do:
Carboxyl group amount [mmol / g oxidized cellulose or cellulose nanofiber] = a [ml] × 0.05 / oxidized cellulose mass [g].

<Carboxymethylation>
In the present invention, the carboxymethylation of the cellulose raw material can be carried out using a known method and is not particularly limited. However, the degree of carboxymethyl group substitution per anhydroglucose unit of cellulose is 0.01-0. It is preferable to adjust to 50. As an example, the following production method can be mentioned, but it may be synthesized by a conventionally known method or a commercially available product may be used. Cellulose is used as the starting material, and water and / or lower alcohol 3 to 20 times by weight in the solvent, specifically methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, tertiary butanol, etc. Or a mixed medium of two or more. The mixing ratio of the lower alcohol is 60 to 95% by weight. As the mercerizing agent, 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per anhydroglucose residue of the bottoming material. A bottoming raw material, a solvent, and a mercerizing agent are mixed and subjected to mercerization treatment at a reaction temperature of 0 to 70 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Thereafter, a carboxymethylating agent is added in an amount of 0.05 to 10.0 times mol per glucose residue, a reaction temperature of 30 to 90 ° C., preferably 40 to 80 ° C., and a reaction time of 30 minutes to 10 hours, preferably 1 hour. Perform etherification reaction for ~ 4 hours.

As a measuring method of the carboxymethyl substitution degree per glucose unit, it can obtain by the following method, for example. That is, 1) About 2.0 g of carboxymethylated cellulose fiber (absolutely dry) is precisely weighed and put into a 300 mL conical stoppered Erlenmeyer flask. 2) Add 100 mL of a solution of 100 mL of special concentrated nitric acid to 1000 mL of nitric acid methanol and shake for 3 hours to convert the carboxymethyl cellulose salt (CM cellulose) into hydrogenated CM cellulose. 3) Weigh accurately 1.5 to 2.0 g of hydrogenated CM-modified cellulose (absolutely dry) and put into a 300 mL conical flask with a stopper. 4) Wet the hydrogenated CM cellulose with 15 mL of 80% methanol, add 100 mL of 0.1N NaOH, and shake at room temperature for 3 hours. 5) Back titrate excess NaOH with 0.1 N H2SO4 using phenolphthalein as indicator. 6) The degree of carboxymethyl substitution (DS) is calculated by the following formula:
A = [(100 × F ′ − (0.1N H 2 SO 4) (mL) × F) × 0.1] / (absolute dry mass of hydrogenated CM-modified cellulose (g))
DS = 0.162 × A / (1−0.058 × A)
A: 1N NaOH amount (mL) required for neutralizing 1 g of hydrogenated CM-modified cellulose
F ′: 0.1N H 2 SO 4 factor F: 0.1 N NaOH factor

<Cationization>
In the present invention, the cationization of the cellulose raw material can be performed using a known method, and for example, ammonium, phosphonium, sulfonium, or a group having ammonium, phosphonium or sulfonium can be contained in the cellulose molecule by cationization. A group containing ammonium is preferred, and a group containing quaternary ammonium is particularly preferred. The specific cationization method is not particularly limited, but as an example, cationization of cellulose raw material such as glycidyltrimethylammonium chloride, 3-chloro-2hydroxypropyltrialkylammonium hydride or its halohydrin type Cation having group containing quaternary ammonium by reacting agent and catalyst alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) in the presence of water and / or alcohol having 1 to 4 carbon atoms Modified cellulose can be obtained. In this method, the cation substitution degree per glucose unit of the cation-modified cellulose obtained is controlled by the amount of the cationizing agent to be reacted, the composition ratio of water and / or alcohol having 1 to 4 carbon atoms. Can be adjusted. The degree of substitution herein refers to the number of substituents introduced per unit structure (glucopyranose ring) constituting cellulose. In other words, it is defined as “a value obtained by dividing the number of moles of the introduced substituent by the total number of moles of hydroxyl groups of the glucopyranose ring”. Since pure cellulose has three substitutable hydroxyl groups per unit structure (glucopyranose ring), the theoretical maximum value of the degree of substitution of the cellulose fiber of the present invention is 3 (minimum value is 0).

In the present invention, the degree of cation substitution per glucose unit of the cationized cellulose is preferably 0.01 to 0.40. By introducing a cationic substituent into cellulose, the celluloses repel each other electrically. For this reason, the cellulose which introduce | transduced the cation substituent can be nano-defibrated easily. In addition, when the cation substitution degree per glucose unit is smaller than 0.01, nano-defibration cannot be sufficiently performed. On the other hand, if the degree of cation substitution per glucose unit is larger than 0.40, the fiber form cannot be maintained because it swells or dissolves and may not be obtained as nanofibers.
The degree of cation substitution per glucose unit can be calculated from the following equation by measuring the nitrogen content with a total nitrogen analyzer TN-10 (Mitsubishi Chemical) after drying the sample (cation-modified cellulose). . The degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.
Degree of cation substitution = (162 × N) / (1-151.6 × N)
N: Nitrogen content

<Esterification>
A method for obtaining an esterified cellulose fiber or an esterified cellulose nanofiber by esterifying a cellulose raw material or a defibrated cellulose fiber is not particularly limited, and examples thereof include a method of reacting compound A with a cellulose raw material or a defibrated cellulose fiber. It is done. Compound A will be described later.

  Examples of the method of reacting compound A with cellulose raw material or defibrated cellulose fiber include a method of mixing a powder or aqueous solution of compound A with cellulose raw material or defibrated cellulose fiber, and compound A into a slurry of cellulose raw material or defibrated cellulose fiber. The method of adding the aqueous solution of this is mentioned. Among these, since the uniformity of the reaction is enhanced and the esterification efficiency is increased, a method in which an aqueous solution of Compound A is mixed with a cellulose raw material, a defibrated cellulose fiber or a slurry thereof is preferable.

  Examples of compound A include phosphoric acid compounds (eg, phosphoric acid, polyphosphoric acid), phosphorous acid, phosphonic acid, polyphosphonic acid, and esters thereof. Compound A may be in the form of a salt. Among them, a phosphoric acid compound is preferable because it is low in cost, easy to handle, and can improve the fibrillation efficiency by introducing a phosphate group into cellulose of a cellulose raw material (eg, pulp fiber). . The phosphate compound may be any compound having a phosphate group. For example, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, diphosphate Examples include potassium hydrogen, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium metaphosphate. . The phosphoric acid compound used may be one type or a combination of two or more types. Among these, phosphoric acid, phosphoric acid sodium salt, phosphoric acid potassium salt, phosphoric acid, from the viewpoint that phosphoric acid group introduction efficiency is high, is easy to be defibrated in the following defibrating process and is industrially applicable. Ammonium salt is preferable, sodium salt of phosphoric acid is more preferable, and sodium dihydrogen phosphate and disodium hydrogen phosphate are more preferable. In addition, it is preferable to use an aqueous solution of a phosphoric acid compound in the esterification because the uniformity of the reaction is enhanced and the efficiency of introduction of phosphoric acid groups is increased. The pH of the aqueous solution of the phosphoric acid compound is preferably 7 or less because the efficiency of introduction of phosphate groups is increased. From the viewpoint of suppressing hydrolysis of pulp fibers, pH 3 to 7 is more preferable.

  Examples of the esterification method include the following methods. Compound A is added to a cellulose raw material or a suspension of defibrated cellulose fibers (for example, a solid content concentration of 0.1 to 10% by weight) with stirring to introduce phosphate groups into the cellulose. When the cellulose raw material or defibrated cellulose fiber is 100 parts by weight, when compound A is a phosphoric acid compound, the amount of compound A added is preferably 0.2 parts by weight or more, and preferably 1 part by weight or more as the amount of phosphorus element. Is more preferable. Thereby, the yield of esterified cellulose fiber or esterified cellulose nanofiber can be further improved. The upper limit is preferably 500 parts by weight or less, and more preferably 400 parts by weight or less. Thereby, the yield corresponding to the usage-amount of the compound A can be obtained efficiently. Therefore, 0.2 to 500 parts by weight is preferable, and 1 to 400 parts by weight is more preferable.

  When the compound A is reacted with the cellulose raw material or the defibrated cellulose fiber, the compound B may be further added to the reaction system. Examples of the method of adding Compound B to the reaction system include a method of adding Compound B to a slurry of cellulose raw material or defibrated cellulose fiber, an aqueous solution of Compound A, or a slurry of cellulose raw material or defibrated cellulose fiber and Compound A. It is done.

  The compound B is not particularly limited, but preferably exhibits basicity, and more preferably a nitrogen-containing compound exhibiting basicity. “Show basic” usually means that the aqueous solution of Compound B is pink to red in the presence of a phenolphthalein indicator, or / and the pH of the aqueous solution of Compound B is greater than 7. The nitrogen-containing compound showing basicity is not particularly limited as long as the effects of the present invention are exhibited, but a compound having an amino group is preferable. Examples of the compound having an amino group include urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine and the like. Of these, urea is preferable because it is easy to handle at low cost. The amount of compound B added is preferably 2 to 1000 parts by weight, and more preferably 100 to 700 parts by weight. The reaction temperature is preferably 0 to 95 ° C, more preferably 30 to 90 ° C. Although reaction time is not specifically limited, Usually, it is about 1 to 600 minutes, and 30 to 480 minutes are preferable. If the conditions for the esterification reaction are in any of these ranges, cellulose can be prevented from being excessively esterified and easily dissolved, and the yield of phosphorylated esterified cellulose can be improved. it can.

  After reacting compound A with the cellulose raw material or defibrated cellulose fiber, a suspension of esterified cellulose fiber or esterified cellulose nanofiber is usually obtained. The suspension of esterified cellulose fiber or esterified cellulose nanofiber is dehydrated as necessary. Heat treatment is preferably performed after dehydration. Thereby, hydrolysis of a cellulose raw material or a defibrated cellulose fiber can be suppressed. The heating temperature is preferably 100 to 170 ° C., and is heated at 130 ° C. or less (more preferably 110 ° C. or less) while water is contained in the heat treatment, and after removing water, it is heated at 100 to 170 ° C. More preferably, it is processed.

  In phosphate esterified cellulose, a phosphate group substituent is introduced into the cellulose, and the cellulose repels electrically. Therefore, the phosphate esterified cellulose fiber can be easily defibrated up to cellulose nanofibers (the defibration performed until the cellulose nanofibers are thus formed is also referred to as nano-defibration). The phosphate group substitution degree per glucose unit of the phosphate esterified cellulose fiber is preferably 0.001 or more. Thereby, sufficient defibration (for example, nano defibration) can be implemented. The upper limit is preferably 0.40 or less. Thereby, swelling or melt | dissolution of phosphate esterified cellulose fiber can be suppressed, and generation | occurrence | production of the situation where a cellulose nanofiber cannot be obtained can be suppressed. Therefore, it is preferably 0.001 to 0.40. Further, the degree of phosphate group substitution per glucose unit of cellulose nanofibers (phosphate esterified cellulose nanofibers) modified by phosphoric esterification is preferably 0.001 or more. The upper limit is preferably 0.40 or less. Therefore, it is preferable that the phosphate group substitution degree per glucose unit of phosphate esterified cellulose nanofiber is 0.001 to 0.40. It is preferable that the phosphorylated cellulose fiber is subjected to a washing treatment such as washing with cold water after boiling. Thereby, defibration can be performed efficiently.

<Defibration>
In the present invention, an apparatus for defibrating is not particularly limited, but a strong shearing force is applied to the aqueous dispersion using an apparatus such as a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, or an ultrasonic type. Is preferred. In particular, for efficient defibration, it is preferable to use a wet high-pressure or ultrahigh-pressure homogenizer that can apply a pressure of 50 MPa or more to the aqueous dispersion and can apply a strong shearing force. The pressure is more preferably 100 MPa or more, and further preferably 140 MPa or more. In addition, prior to defibration / dispersion treatment with a high-pressure homogenizer, the cellulose nanofibers may be pretreated using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer as necessary. Is also possible.

  In the case of defibration by the above treatment, the solid content concentration as the cellulose fiber raw material is 0.1% by weight or more, preferably 0.2% by weight or more, particularly 0.3% by weight or more, and 10% by weight or less, particularly 6%. It is preferable that it is below wt%. When the solid content concentration is too low, the amount of liquid is too large with respect to the amount of the cellulose fiber raw material to be processed, resulting in poor efficiency, and when the solid content concentration is too high, the fluidity is deteriorated.

In the present invention, the mode of the cellulose nanofibers to be contained in the water-containing chocolate is not particularly limited, and may be a dispersion of cellulose nanofibers, a dry solid of cellulose nanofibers, or a wet solid that is an intermediate state thereof. There may be. In addition, in this invention, the dry solid substance of a cellulose nanofiber means what dehydrated and dried the dispersion liquid containing a cellulose nanofiber to 12% or less of moisture content.
Examples of dry solids of cellulose nanofibers include those obtained by drying a dispersion of cellulose nanofibers, or those obtained by drying a mixed liquid of cellulose nanofibers and a water-soluble polymer. The latter is preferable in terms of redispersibility. Examples of the water-soluble polymer include cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose), xanthan gum, xyloglucan, dextrin, dextran, carrageenan, locust bean gum, alginic acid, alginate, pullulan, starch, and hard starch. , Scrap flour, Positive starch, Phosphorylated starch, Corn starch, Gum arabic, Locust bean gum, Gellan gum, Gellan gum, Polydextrose, Pectin, Chitin, Water-soluble chitin, Chitosan, Casein, Albumin, Soy protein lysate, Peptone, Polyvinyl alcohol , Polyacrylamide, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl acetate, polyamino acid, polylactic acid, polymalic acid, polyglyce Latex, rosin sizing agent, petroleum resin sizing agent, urea resin, melamine resin, epoxy resin, polyamide resin, polyamide / polyamine resin, polyethyleneimine, polyamine, plant gum, polyethylene oxide, hydrophilic cross-linked polymer, polyacrylic Refers to acid salts, starch polyacrylic acid copolymers, tamarind gum, gellan gum, pectin, guar gum and colloidal silica and mixtures of one or more thereof. Among these, it is preferable from a compatible point to use carboxymethylcellulose and its salt.

  The dry solid of the cellulose nanofiber is dehydrated and dried after adjusting the pH of the cellulose nanofiber aqueous dispersion or the mixture containing the cellulose nanofiber dispersion and the water-soluble polymer to 9-11. It is preferable from the viewpoint of redispersibility. When the water-soluble polymer is blended in the cellulose nanofiber dispersion, the amount of the water-soluble polymer is preferably 5 to 50% by weight based on the absolutely dry solid content of the cellulose nanofiber. If it is less than 5% by weight, the effect of sufficient redispersibility is not exhibited. On the other hand, when it exceeds 50% by weight, problems such as viscosity characteristics and dispersion stability, which are characteristic of cellulose nanofiber, occur.

  As the dehydration / drying method of the cellulose nanofiber dispersion or the mixture containing the cellulose nanofiber dispersion and the water-soluble polymer, any conventionally known method may be used, for example, spray drying, pressing, air drying, hot air drying, And vacuum drying. Examples of the drying apparatus specifically used in the method of the present invention are as follows. That is, continuous tunnel dryer, band dryer, vertical dryer, vertical turbo dryer, multi-stage disk dryer, aeration dryer, rotary dryer, air dryer, spray dryer dryer, spray dryer , Cylindrical dryers, drum dryers, screw conveyor dryers, rotary dryers with heating tubes, vibration transport dryers, batch-type box dryers, aeration dryers, vacuum box dryers, stirring dryers, etc. These drying apparatuses can be used alone or in combination of two or more. Among these, it is preferable to use a drum drying apparatus from the viewpoint of energy efficiency because the heat energy is uniformly supplied directly to an object to be dried. The drum drying apparatus is also preferable in that it can immediately collect a dried product without applying heat more than necessary.

  The dried solid matter can be crushed and classified to obtain the water-containing chocolate of the present invention. In particular, dry pulverization or wet pulverization is preferable because a more refined additive can be obtained. Examples of the apparatus used in the dry pulverization include impact mills such as a hammer mill and a pin mill, medium mills such as a ball mill and a tower mill, and jet mills. Examples of the apparatus used in the wet pulverization include apparatuses such as a homogenizer, a mass collider, and a pearl mill.

<Addition to hydrated chocolate>
In the present invention, the amount of cellulose nanofibers added to the water-containing chocolate is such that the absolute dry weight of the cellulose nanofibers in the water-containing chocolate is 0.08% by weight or more, preferably 0.15%, based on the total absolute dry weight of the water-containing chocolate. It is preferable that it is weight% or more. If the content is less than 0.05%, sufficient effects are not exhibited. On the other hand, if the absolute dry weight of the cellulose nanofibers is more than 1.0 weight with respect to the total absolute dry weight of the hydrated chocolate, it is preferably 1.0 part or less because there is an effect of an increase in the nevaness.

  Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these.

<Manufacture of oxidized cellulose nanofiber>
Add 500 g of bleached unbeaten kraft pulp (whiteness 85%) derived from coniferous tree (absolutely dry) to 500 ml of an aqueous solution in which 780 mg of TEMPO (Sigma Aldrich) and 75.5 g of sodium bromide are dissolved, until the pulp is uniformly dispersed Stir. An aqueous sodium hypochlorite solution was added to the reaction system to 6.0 mmol / g to initiate the oxidation reaction. During the reaction, the pH in the system was lowered, but a 3M sodium hydroxide aqueous solution was sequentially added to adjust the pH to 10. The reaction was terminated when sodium hypochlorite was consumed and the pH in the system no longer changed. The reaction mixture was filtered through a glass filter to separate the pulp, and the pulp was sufficiently washed with water to obtain oxidized pulp (carboxylated cellulose). The pulp yield at this time was 90%, the time required for the oxidation reaction was 90 minutes, and the amount of carboxyl groups was 1.6 mmol / g.

  The oxidized pulp obtained in the above step was adjusted to 1.0% (w / v) with water and treated three times with an ultrahigh pressure homogenizer (20 ° C., 150 MPa) to obtain a cellulose nanofiber dispersion. The obtained fiber had an average fiber diameter of 3 nm and an aspect ratio of 250.

<Production of carboxymethylated cellulose nanofiber>
In a stirrer capable of mixing pulp, 200 g dry pulp (NBKP (conifer bleached kraft pulp), manufactured by Nippon Paper Industries Co., Ltd.) and 111 g sodium hydroxide dry mass are added, and the pulp solid content is 20% (w / V) was added water. Thereafter, after stirring at 30 ° C. for 30 minutes, 216 g of sodium monochloroacetate (in terms of active ingredient) was added. After stirring for 30 minutes, the temperature was raised to 70 ° C. and stirred for 1 hour. Thereafter, the reaction product was taken out, neutralized and washed to obtain a carboxymethylated pulp having a carboxymethyl substitution degree of 0.25 per glucose unit. Thereafter, the carboxymethylated pulp was made 1% solids with water, and fibrillated by treating it with a high-pressure homogenizer 5 times at 20 ° C. and 150 MPa to obtain carboxymethylated cellulose fibers. The obtained fiber had an average fiber diameter of 15 nm and an aspect ratio of 50.

<Manufacture of cationized cellulose nanofiber>
Add pulp (NBKP, manufactured by Nippon Paper Industries Co., Ltd.) in dry weight of 200g and sodium hydroxide in dry weight of 24g to pulper that can stir the pulp, and add water so that the pulp solid concentration is 15%. It was. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 200 g (in terms of active ingredient) of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added as a cationizing agent. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain cation-modified cellulose having a cation substitution degree of 0.05 per glucose unit. Thereafter, the cation-modified pulp was treated at a solid concentration of 1% and treated twice with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa. The obtained fiber had an average fiber diameter of 25 nm and an aspect ratio of 50.

<Example 1>
Carboxymethylcellulose (trade name: F350HC-4, manufactured by Nippon Paper Industries Co., Ltd.) is added to 0.7% by weight aqueous suspension of the above oxidized cellulose nanofibers with respect to the cellulose nanofibers, and a TK homomixer is added. The mixture was stirred at (12,000 rpm) for 60 minutes. To this aqueous suspension, 0.5% aqueous sodium hydroxide solution was added to adjust the pH to 9, and then the vapor pressure was 0.5 MPa. G, and dried with a drum dryer D0405 (manufactured by Katsuragi Industry Co., Ltd.) with a drum rotation speed of 2 rpm, to obtain a mixed dry solid of cellulose nanofibers and carboxymethylcellulose having a water content of 5 wt%. The dried solid was pulverized by a dry mill to obtain cellulose nanofiber for addition in the present invention.

  Subsequently, 100 g of fresh cream and 0.5 g of the above cellulose nanofiber for addition were mixed and stirred while warming until there was no granular lump of cellulose nanofiber. After stirring, 200 g of crushed chocolate was added and melted. This dough was refrigerated and hardened to obtain water-containing chocolate. The content of the cellulose nanofiber for addition of the present invention in the water-containing chocolate is 0.17% by weight with respect to the weight of the water-containing chocolate, and the absolute dry weight of the cellulose nanofiber in the cellulose nanofiber for addition is the water-containing chocolate. It was 0.16 weight% with respect to the weight of. About the obtained water-containing chocolate, the test regarding shape retention property, stickiness, and food texture was done by the following method.

<Example 2>
The same procedure as in Example 1 was performed except that the cellulose nanofiber in the cellulose nanofiber for addition in Example 1 was changed to the carboxymethylated cellulose nanofiber produced by the above method.

<Comparative Example 1>
The same operation as in Example 1 was performed except that the cellulose nanofiber for addition was not used in Example 1.

<Comparative example 2>
The same procedure as in Example 1 was performed except that carboxymethylated cellulose (trade name: F350HC-4, manufactured by Nippon Paper Industries Co., Ltd.) was used instead of the cellulose nanofiber for addition in Example 1.

<Shape retention and stickiness>
The hydrated chocolate after cooling was picked up and subjected to sensory evaluation according to the following criteria.
○: The chocolate hardly adheres to the hand and keeps the shape for a long time even at room temperature. Δ: The chocolate adheres to the hand for a while, and after a few hours, the shape collapses at the room temperature. The prototype will soon collapse.

<Food texture>
Ten panelists sampled and evaluated the texture (feeling of mouthfeel) by the following five-point method, and the average score was taken as the evaluation score.
5 points: Smooth and refreshing mouth 3 points: No stickiness, smooth mouth opening 1 point: There is stickiness and lacks smoothness

  As is clear from the results in Table 1, in Example 1 and Example 2 containing cellulose nanofibers, the shape retention was good compared to Comparative Example 1 not containing cellulose nanofibers. In addition, it can be seen that the shape retention and mouthfeel are better than Comparative Example 2 using carboxymethylcellulose which is microcrystalline cellulose.

Claims (6)

  Water-containing chocolates characterized by containing cellulose nanofibers.   The water-containing chocolate according to claim 1, wherein the cellulose nanofibers are chemically modified cellulose nanofibers.   The chemically modified cellulose nanofiber is an oxidized cellulose nanofiber having an amount of carboxyl groups of 0.5 mmol / g to 3.0 mmol / g with respect to the absolutely dry weight of the chemically modified cellulose nanofiber. The water-containing chocolate according to claim 2.   The water-containing chocolate according to claim 2, wherein the chemically modified cellulose nanofiber has a degree of carboxymethyl substitution per glucose unit of the modified cellulose nanofiber of 0.01 to 0.50.   Bread using the hydrated chocolate according to any one of claims 1 to 4.   Confectionery using the hydrated chocolate according to any one of claims 1 to 4.