JPS6134459B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-dispersible composite consisting of a combination of microcrystalline cellulose and saccharides. More specifically, it is a complex that is easily dispersible in water and has functions such as suspension stability, emulsion stability, ice crystal prevention ability, foam stability, and thermal stability, and is suitable for use in, for example, ice creams and frozen confections. , dressings, puddings, topping creams, and foods to be sterilized at high temperatures, which can be used as natural stabilizers without restriction. Conventionally, synthetic or natural water-soluble polymers have been used for food stability. These water-soluble polymer stabilizers exhibit viscosity behavior close to Newtonian flow at the commonly used water-soluble concentration (often about 0.2 to 2%), and the viscosity of the liquid depends on the liquid temperature. It has the characteristic that the viscosity decreases dramatically as the liquid temperature increases. Therefore, when applied to soft-serve ice cream, for example, it increases the stability of the mix, allows the soft-serve ice cream served in a cone to form a well-shaped mound (stand-up property), and allows it to melt and drip even when exposed to high temperatures outside. In order to maintain its shape (shape retention), it is necessary to add a considerable amount of water-soluble polymer.
However, when increasing the amount of water-soluble polymer added,
A sticky, so-called pasty taste appears, resulting in a taste that is disliked by consumers. Here, there was a desire for a stabilizer that was crisp and had a shape-retaining effect or stand-up properties. Also, emulsions that undergo high temperature sterilization,
For suspension or paste foods, the stabilization mechanism of conventional water-soluble polymer stabilizers relies on the thickening effect of the liquid, so even if stability is achieved before the sterilization process, high-temperature sterilization is not possible. In the process, the viscosity decreases as the liquid temperature increases, resulting in coalescence of oil droplets and agglomeration and sedimentation of suspended substances. Here, thermal stability was required in addition to emulsion stability and suspension stability. Salad dressings require not only emulsion stability but also good flow out from storage containers. It is true that conventional polymer stabilizers give a sloppy feel, but because of their viscosity, it is difficult to shake them out of narrow-mouthed glass containers, for example, and there is a need for stabilizers that exhibit thixotropic flow. Ta. As mentioned above, in order to achieve emulsion stability and foam stability, it is necessary to add a large amount of conventional polymer stabilizers, which can adversely affect texture, etc. It had insufficient functionality to maintain stability. The present invention relates to a complex that provides desirable effects such as suspension stability, emulsion stability, and ice crystal prevention ability without adversely affecting food texture. The composite referred to in the present invention is a composite that is easily dispersed in water and is composed of microcrystalline cellulose and a dispersion disintegrant, and has a composition of 50 to 95 microcrystalline cellulose.
% by weight, the dispersion disintegrant should be 50-5% by weight. Further, in order to fully exhibit the effects of the present invention, it is necessary to use microcrystalline cellulose having an average degree of polymerization of 375 or less and an average particle size of 15 microns or less. A more detailed description of each component of the present invention is as follows. The microcrystalline cellulose referred to in the present invention is defined by a paper by Mr. O. A. Batista in Industrial and Engineering Chemistry, Vol. 42, pp. 502 to 507 (1950). It is a cellulose crystallite aggregate having a substantially constant degree of polymerization obtained by acid hydrolysis or alkali oxidative decomposition of cellulose. For example, when hydrolyzed with 2.5 N hydrochloric acid at 105° C. for 15 minutes, an acid-insoluble residue having a constant level-off degree of polymerization is produced, and when this is washed and filtered, microcrystalline cellulose is obtained. In order to enhance the function as a stabilizer as intended by the present invention, the particle size of the microcrystalline cellulose is preferably as small as possible, and the microcrystalline cellulose is such that particles of 1 micron or less account for at least 5% by weight. It is preferable to use It is necessary that the average particle size of the microcrystalline cellulose does not exceed 15 microns, preferably the average particle size is 10 microns or less,
Microcrystalline cellulose containing 10% by weight or more of particles smaller than 1 micron is preferred. Measurement of these particle size distributions is performed by sedimentation method or centrifugation method. Microcrystalline cellulose containing less than 5% by weight of particles of 1 micron or less does not exhibit sufficient colloidal dispersibility even when combined with a dispersion disintegrant, has weak thixotropy, and causes flocculation and sedimentation, making it ineffective. The average particle diameter measured by the centrifugal sedimentation method exceeds 15 microns, and when applied to ice creams, for example, it causes graininess and is not desirable in terms of texture. Such fine microcrystalline cellulose can be obtained by chemical decomposition treatment or by mechanical grinding treatment following chemical decomposition treatment, but whether the grinding process is dry or wet, It may also be carried out at cryogenic temperatures using refrigerants. The average degree of polymerization of the microcrystalline cellulose aggregate must be 375 or less, and microcrystalline cellulose exceeding 375 is difficult to make into fine particles in the kneading and grinding process, and does not colloidally disperse but aggregates and settles. easy to clean and has weak thixotropy. It is difficult to determine the lower limit of the average degree of polymerization. This is because it depends on the chemical decomposition treatment conditions and the type of raw material cellulose, but in the case of the present invention, in order to facilitate the purification and filtration operation after the chemical decomposition treatment, the It is better to use things. If the average degree of polymerization is less than 60, it becomes muddy and difficult to perform purification operations such as filtration and washing, but if it is acceptable to sacrifice production efficiency, product yield, etc., use a polymerization degree of less than 60. You can also use. Next, the dispersion disintegrant as used in the present invention refers to water-swellable and/or water-soluble saccharides that are naturally occurring or obtained by fermentation methods, etc., as described below. Namely, locust bean gum, guar gum, tamarind seed gum, and cleanseed gum extracted from legumes; gum arabic, gum taragant, gum karaya, gum gatuti, and arabinogalactan extracted from tree sap; agar, gum extracted from seaweed, Alginic acid and its salts, carrageenan, furcelleran, laminarin; Vectin extracted from fruit, quince; Xanthan gum, curdlan, pullulan, dextran produced by microorganisms; Soluble starch and starch decomposition products, such as alpha starch, dextrins, Low-viscosity modified starch, cyclodextrin, etc.; monosaccharides such as sucrose, glucose, fructose, lactose, and disaccharides. These dispersion disintegrants are characterized by high swelling power or rapid dissolution in water, and are also characterized by good compatibility with microcrystalline cellulose in water. Among these dispersion disintegrants, particularly effective dispersion disintegrants are:
These are guar gum, karaya gum, carrageenan, alginate, xanthan gum, and starch degradation products. As an essential requirement for a stabilizer, it must first be easily dispersed in water, and the composite of the present invention, when subjected to a moderate shearing force in water, has microcrystalline cellulose with a fine particle size that is uniformly dispersed in water. and can be stabilized. Addition of a dispersion disintegrant facilitates the dispersion of microcrystalline cellulose in water. Some dispersion disintegrants slightly increase the viscosity of the entire system, increasing the dispersion stability of microcrystalline cellulose, and also function as a protective colloid. Additionally, some dispersion disintegrants improve only the dispersibility of microcrystalline cellulose without increasing the viscosity of the system. Which of these natural polymers should be selected may be determined in consideration of the intended use of the stabilizer to be ultimately used. In order to provide water dispersibility or water dispersibility to the composite, it is necessary that the amount of dispersing agent in the composite composition be at least 5% by weight.
If the amount of dispersion disintegrant is less than 5% by weight, water dispersibility of the composite cannot be achieved. Aqueous solutions of sugars mentioned as dispersion disintegrants exhibit behavior similar to Newtonian fluids when used alone, with a few exceptions such as xanthan gum and carrageenan. However, when combined with microcrystalline cellulose, it exhibits a much more pronounced thixotropic flow than an aqueous solution of microcrystalline cellulose or sugar alone. It is this thixotropic property that improves the smooth texture and stand-up properties of soft serve ice creams, and improves the ease with which dressings can be shaken out from narrow container mouths.
In order to enhance this effect, it is necessary that the amount of dispersion disintegrant added to the microcrystalline cellulose is less than 50% by weight, particularly preferably 10 to 20% by weight of the composite composition. Addition of too much dispersion disintegrant reduces thixotropy. The combination of microcrystalline cellulose and dispersion disintegrant can be obtained by grinding, kneading, and drying the two in the presence of moisture. Prior to the grinding and kneading of these two materials, it is free to grind and use only the microcrystalline cellulose. The machine used for grinding and mixing is
It is freely selected depending on the amount of water present in the system. For example, to grind and knead slurry-like materials, a colloid mill, continuous ball mill, homogenizer,
A kneading and grinding machine such as a three-roll machine can be used, and a kneader, a laikai machine, an extruder, etc. can be used to grind and knead dry materials with less moisture. In the case of a thick material, a kneader, extruder, triple roll, etc. can be used. In this grinding process, in order to grind microcrystalline cellulose efficiently and reduce drying energy costs in the next process, it is better to grind microcrystalline cellulose in a dry state or rice cake-like state rather than grinding and kneading a slurry-like product. It is better to grind and knead in a viscous state, and for slurry-like products, it is better to grind and knead in the presence of moisture not exceeding 90% by weight on a wet basis. In this grinding and kneading step, it is necessary that the microcrystalline cellulose is refined so that its average particle size is 5 microns or less. The surface of this finely divided microcrystalline cellulose is covered with the coexisting dispersion disintegrant and separated from each other, thereby making the entire system homogenized. For this purpose, during kneading and grinding, the moisture content must be at least 25% by weight and not more than 90% by weight on a wet basis. If the water content is less than 25% by weight, the surface of the microcrystalline cellulose particles will not be tightly covered by the dispersing agent, and the microcrystalline cellulose will not be finely divided, so the kneaded and ground product is dried. When dispersed in water, sedimentation of coarse particles is observed.
If the water content exceeds 90% by weight, the grinding efficiency will not increase even though the drying energy cost for the next step will increase. This is due to the fact that when grinding with a thin slurry system,
This is thought to be because even if mechanically intense grinding conditions are selected, the grinding effect due to collisions between dispersed particles becomes poor. The kneading and grinding process may be completed in one step or may be carried out in several stages. For example, microcrystalline cellulose and a dispersing agent may be weighed, an appropriate amount of water may be added, and the mixture may be kneaded and ground at the same time, or the microcrystalline cellulose may be kneaded and ground in the presence of water in advance, and then dispersion may be disintegrated. The kneading and grinding treatment may be carried out again by adding the agent. Moreover, the addition of water can be replaced by using microcrystalline cellulose in a wet state. It is not necessarily necessary to form an aqueous colloid dispersion by adding a liquid such as water and applying mechanical shearing force to the material after the completion of the grinding and kneading process before transferring it to the drying step. Of course, if a slurry-like material is ground and kneaded, an aqueous colloid dispersion will be formed at the same time, but it is also possible to add a dry or mochi-like material to a liquid and apply mechanical shearing action. This is because, if an aqueous colloid dispersion is formed, the drying method will be limited, and of course the cost of drying energy will be high in order to dissipate the excess water added. According to the present invention, a composite with good water dispersibility can be obtained without forming an aqueous colloid dispersion. The most appropriate method for drying to be carried out after kneading and grinding should be selected depending on the moisture content or condition of the object to be dried. for example,
Spray drying can be used to dry slurry-like kneaded and ground materials, and for slurry-like and mochi-like materials, tray dryers, belt dryers, fluidized fluid dryers, and hot air drying pulverizers can be used. , vacuum freeze dryer, etc. What is important in the drying process is controlling the moisture content of the product after drying, and the moisture content must be 2.5% or more on a wet basis. If the water content is less than this, the redispersibility of the dried product in water will deteriorate. On the other hand, the upper limit of the moisture content should be determined taking into account ease of handling, commercial value, stability over time, etc. Although there is no restriction, it is convenient to handle the product as a powder if it is between 15 and 18%. It is. In addition, products dried in a tray dryer or fluidized bed dryer should be pulverized into a powder using an appropriate pulverizer if commercial value, easy dispersibility in water, etc. are taken into consideration. If the powder particle size after grinding is fine enough to pass through a 40 mesh sieve, rapid dispersion in water is achieved. An example of the method for producing the composite of the present invention is as follows. 1 kg of purified linter (average degree of polymerization 1500-1600)
After hydrolyzing in a 2.5N hydrochloric acid solution at 105°C for 15 minutes (15 times the bath ratio), the mixture was washed and filtered with warm pure water, and 2.3 kg of wet cake with a moisture content of 70% was recovered. A small amount of sample was taken from this and the particle size distribution was measured using a centrifugal sedimentation particle size distribution analyzer CP-50 manufactured by Shimadzu Corporation.The average particle size was 4.2 microns, and particles of 1 micron or less accounted for 5% by weight. Ta.
2.0kg of this wet cake and 0.4kg of guar gum (medium viscosity) were placed in a 10 kneader, kneaded and ground for 90 minutes, and then passed through an extruder with an extrusion fitting with a hole diameter of 2.5mmφ and an open area of 40% to form noodles. extrude into a shape and air dry this material to a moisture content of 4.3%.
A dried product was obtained. This was then passed through a hammer mill to obtain 700 g of powder that would pass through a 50 mesh sieve. The results of measurement using a rotational viscometer revealed that the composite thus obtained had good dispersibility in water, and a 2% aqueous solution thereof had thixotropic properties. The complex of the present invention can be applied as a stabilizer for foods alone or in combination with other natural polymers as necessary. It is suitable for use in dairy products, pasty foods, pastry products, frozen products, baked goods, beverages, and dressings, and contributes to improving emulsion stability, suspension stability, ice crystal prevention ability, and foam stability. Example 1 DP pulp (average degree of polymerization 750) was selected as a cellulose raw material and treated in a 1-2% sulfuric acid solution at 99°C for 30 minutes.
Hydrolysis treatment was performed for 90 minutes, and the mixture was filtered and washed with pure water to obtain a wet cake.

[Table] Crushed and reduced particle size The particle size distribution of this wet cake was as shown in Table 1. Using these wet cakes, the formulations shown in Table 2 with various ratios of microcrystalline cellulose/dispersing disintegrant were passed through a continuous kneader 5 times to complete kneading and grinding. The amount of water during kneading was adjusted to 50% by weight, including the water brought in with the microcrystalline cellulose.
The obtained wet mass was finely loosened and the moisture content was 8.
The powder was dried with hot air at 80°C until it became % by weight, coarsely pulverized with a crusher, finely pulverized with a hammer mill, and further sieved with a 100-mesh sieve to obtain the desired product powder. The moisture content of the final product is
It was 7.2-8%. Table 3 shows the product characteristics of the obtained composite. However, the evaluation method is as follows. Particle size distribution measurement method: First, the particle size distribution of the raw material microcrystalline cellulose itself was measured as follows. A 15% by weight dispersion of microcrystalline cellulose is dispersed in a household mixer for 10 minutes, then diluted to 1% by weight and stirred for an additional 5 minutes. This was further diluted to about 4 times to make a dispersion with a solid content concentration of about 0.25% by weight.
For example, it is measured using a centrifugal sedimentation type particle size distribution analyzer CP-50 manufactured by Shimadzu Corporation. Next, the particle size distribution of the microcrystalline cellulose after the microcrystalline cellulose and the dispersion disintegrant were ground and kneaded was as follows. Add pure water to the desired kneaded material so that the solid content concentration is 1.0 to 2.0% by weight, and mix with a universal homogenizer manufactured by Nippon Seiki Seisakusho Co., Ltd.
Stirring was performed at 12,000 rpm for 3 minutes, and the resulting uniform dispersion was diluted to a solid content concentration of 0.2 to 0.5% by weight.
Stir and shake until the mixture is sufficiently homogeneous, and then measure using Shimadzu's CP-50 model.

【table】

【table】

[Table] Redispersibility test: Add 99 parts of pure water to 1 part of the composite, and after dispersing for 3 minutes with a household mixer,
After passing through a small homogenizer once at a pressure of 250 Kg/cm ² , the sample is transferred to a 100 c.c. sedimentation tube and left for 20 hours to observe the presence or absence of synergic sedimentation. Viscosity measurement: The 1% dispersion obtained in the redispersibility test was kept in constant temperature water baths at 20°C and 80°C, and measured using a B-type viscometer.
Measure viscosity with No. 2 rotor at 30 rpm. Thixotropy: A 2% dispersion was prepared according to the redispersion test procedure.
12rpm and 30rpm using No. 2 rotor with type viscometer
The viscosity of the dispersion at two rotational speeds is measured, and the thixotropic index is calculated using the following formula. Thixotropy = η ₃₀ −η ₁₂ /30−12 where η is the subscript viscosity and hydration rate of the dispersion measured under rotational speed conditions: Each sample was sieved through a 60-mesh sieve and a 100-mesh sieve; One of the coarse particles remaining on the top is placed on a slide glass, covered with a cover glass, and 1 to 2 drops of water are poured from the side of the cover glass, and observation is performed using a microscope (40 to 100 times magnification). The time for the composite particles to absorb water and swell to maximum volume is recorded. As is clear from the results in Table 3, a composite with satisfactory properties has an average degree of polymerization of 375 or less, an average particle size of 10 microns or less, and 5% by weight or more of particles of 1 micron or less. 50-95% by weight of microcrystalline cellulose, 50-5% of dispersing agent
It was a dry powder obtained by blending in a proportion of % by weight, kneading and grinding. Example 2 Ice milk was produced according to the recipe shown in Table 4.
The raw materials were melted at 30℃ for 30 minutes, and 100Kg/
After passing the mixture through a homogenizer once at a pressure of 130 Kg/cm ² and 130 Kg/cm ² and rapidly cooling it to +5°C, 1.2 Kg was placed in a Mitsubishi Sunnyserve SF-3A5 type freezer for freezing, and the mixture was taken out at an overrun of 75%. After that, fill the cup and store it in the freezer at -40℃ for 1 hour.
Freeze overnight. Table 5 shows the type of stabilizer used and the product characteristics of the iced milk.

【table】

【table】

[Table] As is clear from the results in Table 5, the stabilizer formulations with excellent emulsion stability, foam stability, and ice crystal prevention ability are K-3 to K-5, K-7 to X-1, and No.6
It was hot. Compared to Nos. 1 to 5, which used only water-soluble polymers as stabilizers, it was found that the iced milk using the composite of the present invention as a stabilizer had a smoother and crispier taste. Example 3 A thiokolate drink was prepared according to a conventional method according to the formulation shown in Table 6. Although it is said that it is difficult to obtain the suspension stability of cocoa after the high-temperature sterilization process in the tyokolate drink, it was confirmed that the composite of the present invention has improved thermal stability and suspension stability. Table-6 Water 85.95% by weight Crushed sugar 7.50 Skimmed milk powder 5.80 Cocoa 0.50 Stabilizer 0.25 100.00

[Table] Example 4 A whipped topping cream was prepared using the formulation shown in Table 8. The composites of the present invention have been found to have improved foam stability and body and texture. Table-8 Whipped and topping formulation Hydrogenated coconut oil (mp98℃) 30.0% by weight Sugar 7.0 Corn syrup (DE65) 4.0 Sodium caseinate 2.0 Emulsifier* 0.4 Stabilizer 0.3 43.7% (Note) Stabilizer composition; X-1 Emulsifier Agent: Kao Atlas Atmos 150

【table】

[Table] Note that the system to which X-1 was added had a smooth and light texture, but the system containing only carrageenan had a heavy texture. Example 5 A French type dressing was prepared according to the recipe shown in Table 10. Using the complex of the present invention,
It was found to be creamy and have excellent long-term emulsion stability. Furthermore, the composition using the composite of the present invention had good shake-out properties from a narrow-neck bottle.

【table】

[Table] Comparative example; Guar gum alone (Comparative example 1) 288 mg of crystalline cellulose (“Avicel” PH-101 manufactured by Asahi Kasei Corporation) and 32 mg of guar gum were added to 25
It was added to 75 ml of water at ~30°C and stirred for 5 minutes using a laboratory emulsifier (“Waring Blender”; manufactured by Waring Co., USA) to obtain an aqueous dispersion of crystalline cellulose/guar gum (abbreviated as MCC/G). . The aqueous dispersion contains about 0.42% of crystalline cellulose/guar gum in a weight ratio of 9/1. According to Example 3, a thiokolate drink was prepared with the formulation shown in Table 12, and the suspension stability was observed under heat sterilization conditions of 116° C. for 20 minutes. The evaluation results are shown in Table 13.

【table】

[Table] G-1 in Table 13 is obtained by grinding and kneading a crystalline cellulose to guar gum ratio (weight ratio) of 9/1 in the presence of moisture and drying. From this, it is clear that the effects of the present invention cannot be obtained by simply dispersing crystalline cellulose and guar gum in water.

Claims (1)

[Claims] 1. 50 to 95% by weight of microcrystalline cellulose having an average degree of polymerization of 375 or less and an average particle size of 15 microns or less,
A water-dispersible product containing a dispersing agent at a ratio of 50 to 5% by weight, grinding, kneading, drying, and pulverizing in the presence of moisture of 25% to 90% by weight on a wet basis. complex. 2. The composite according to claim 1, characterized in that microcrystalline cellulose having an average particle size of 15 microns or less and containing 5% by weight or more of particles of 1 micron or less is used. 3. The composite according to claim 1, characterized in that microcrystalline cellulose having an average particle size of 10 microns or less and containing 10% by weight or more of particles of 1 micron or less is used. 4. The composite according to claim 1, characterized in that one type selected from guar gum, karaya gum, carrageenan, xanthan gum, and starch decomposition products is used as a dispersion disintegrant. 5. The composite according to claims 1 and 4, characterized in that a dispersion disintegrant is blended in a proportion of 10 to 20% by weight. 6. The composite according to claim 1, wherein the composite is ground and kneaded so that the average particle size of the microcrystalline cellulose is 5 microns or less. 7. The composite according to claim 1, wherein the moisture content after drying is 2.5 to 15% by weight. 8. Mix 50 to 95% by weight of microcrystalline cellulose with an average degree of polymerization of 375 or less and an average particle size of 15 microns or less, and a dispersion disintegrant of 50 to 5% by weight, to give a total weight of 25% by weight on a wet basis. A stabilizer consisting of a water-dispersible composite that is ground, kneaded, and dried in the presence of moisture of at least 90% by weight. 9. The stabilizer according to claim 8, characterized in that microcrystalline cellulose having an average particle diameter of 15 microns or less and containing 5% by weight or more of particles of 1 micron or less is used. 10. The stabilizer according to claim 8, characterized in that microcrystalline cellulose having an average particle diameter of 10 microns or less and containing 10% by weight or more of particles of 1 micron or less is used.