JPH03236749A - Tubular formed composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having improved dimensional stability, strength, touch, feeling to the tongue and toughness by using a specific polysaccharide (derivative), a metal capable of forming bivalent or trivalent metal ion and water as essential components. CONSTITUTION:The objective tubular formed composition having a ratio (R/r) of 1.2-36 (R is maximum outer diameter and r is minimum inner diameter) can be produced by compounding (A) 0.08-12wt.% of a polysaccharide (derivative) (e.g. galactomannan) bonded with a hexose (derivative) (e.g. D-glucose), (B) 0.3-16wt.% (>=71wt.% based on the total mineral substances) of a metal capable of forming bivalent or trivalent metal ion (e.g. Mg), (C)>=40wt.% of water and (D)<=16 pts. (based on 1pt. of the component A) of a polymeric material originated from natural substance (e.g. cellulose), an inorganic filler (e.g. CaCO3), a colorant, a synthetic preservative, a reinforcing material, etc., and pouring the mixture into a closed mold containing a cylindrical core at the center.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to hydrogel compositions shaped into tubular shapes. More particularly, the present invention relates to compositions of hydrogels based on polyamide or its derivatives, metal salts, and water and having a tubular shaped formation.

[Conventional technology]

Among polysaccharides and their derivatives, many hexoses and hexose-substituted substances have an affinity for water, and under certain conditions, substances that form swollen bodies when they come into contact with water and coexist with water. There is.

This phenomenon is observed in some hexoses or hexose direct converters, and is a behavior that cannot be achieved with substances such as trisaccharides. However, the structure of such a swollen body is fragile or dimensionally unstable due to hydrogen bonds associated with water, intramolecular or intermolecular entanglements, etc. In other words, such a swollen body has a unique non-Newtonian flow or thixotropic behavior, so it only maintains a certain shape when stored in a certain container, or If the interlocking is particularly tight, you may be able to barely maintain its shape by gently removing it and placing it on a plate without losing its shape. Taking advantage of these properties, such swollen substances are often used in food additives as thickeners and to impart a so-called melty taste, or as unique and unique substances such as agar and pectin. Taking advantage of its texture, it is used in jelly sweets, yogurt, jam, etc., increasing its value as a food product. However, even if they are formed to have a three-dimensional effect, they still have fragile properties that can barely be maintained.

It is said that chicory milk has a stabilizing effect when a moderate amount of carrageenan gum is added, but in this case carrageenan gum as a polysaccharide derivative only has an effect as a food additive. alone forms a swollen body with water, but it cannot be said that the swollen body can be formed and maintained in a three-dimensional shape by its own cutting edge.

Some of the substances that have alkyl groups introduced into cellulose,
It is used for medicinal capsules because it is possible to prepare hollow excipients that do not collapse even when pinched with fingers, but the capsules themselves do not have appropriate flexure or bending strength, and these capsules are in the range of hydrogels. I can't say that.

In order to impart dimensional stability and strength to hydrogels, there are products in which the above-mentioned swollen structure is three-dimensionally crosslinked by shaping in the presence of metal salts. Foods shaped into lumps such as commercially available food products, impression material powders, membranes, and spun products based on polyuronide all require this method. However, the reality is that their formation is amorphous or too simple, and therefore their uses are limited.

[Problem to be solved by the invention]

The present invention solves all the drawbacks of the above-mentioned conventional article compositions and commercially available articles, and also provides a new
An object of the present invention is to provide a tubular shaped hydrogel composition containing I or a derivative thereof, a metal salt, and water as essential components. The present invention provides a specific excipient composition for hydrogels that are useful in a wide range of industries, such as independent dimensional stability of the hydrogel itself, imparting appropriate strength, and improving texture, texture, and chewiness. be.

((Means for solving one problem) One of the present inventions is a hexose or a hexose substituted product (1), a metal that forms a divalent or trivalent metal ion (
II), and a tubular excipient composition made of a hydrogel having a specific composition and water (III) as an essential component, the tubular excipient & 11. The ratio between the modulus minimum width and the length is specified.

Another aspect of the invention is that the outer and/or inner surfaces of such a tubular shaped m-acid have a specified structure.

Furthermore, a tubular excipient composition containing substances other than the essential components of such a tubular excipient composition in a specific ratio is also part of the present invention.

As a result of intensive investigation, the inventor found that the contents of the invention identified above are of great value for industrial use. The means for solving the problem will be explained in detail below.

Examples of hexose or hexose substituted substances include D-glucose, L-glucose, L-mannose, D-galactose, L-galactose, D-xylose, L-xylose and other carbonyl group or amino group substituted substances; These are carboxylic acids, sulfonic acids, or salts and alkyl esters of carboxylic acids and sulfonic acids. The multi-I! according to this invention is constructed by condensing these! Examples or derivatives thereof (r) include galactomannan,
glucomannan, polyxylose, aldehyde starch, poly D-glucosamine, polyuronic acid, polyuronide, K-carrageenan, etc., and these may be obtained by extraction and fractionation from natural products, as well as cellulose and starches. It may also be obtained by reacting chemical substances compatible with the above and separating the products.

Such said substance (1) accounts for 0.08 to 12% of the total weight of the tubular excipient composition of the present invention. Such substances (
If 1) is less than 0.08% in the above proportion, the hydrogel will not be able to maintain its own formation and structure, so it is not suitable for this invention, and if such substance (1) exceeds 12% in the above proportion In order to achieve this, it is extremely difficult to prepare a swollen body with water, which is a precursor of the composition, and therefore it is difficult to obtain the desired composition.The preferable range of the above ratio is 1.2 to 9%.

The substance [01) according to the present invention includes alkaline earth metals such as magnesium and calcium, amphoteric substances such as aluminum and zinc, iron group substances such as iron, nickel, and cobalt, and these may be used alone or They can be combined with each other to form &l11'Ii of the present invention. Other substances other than the above-mentioned substance (II) can also be used in the present invention, but if they cause environmental pollution or are toxic to humans and animals, it is better to refrain from using them.

The substance (II) according to the present invention has a total solid weight of 0.
It accounts for 3-16%. When the above ratio of the substance (If) is less than 0.3%, the hydrogel cannot be maintained in a constant formation by itself, and when the ratio exceeds 16%, the metal compound will phase separate. constitute the composition system.

Therefore, it is not only meaningless for the substance (I[) to exist more than that, but also disturbs the structure of the m* substance, which is undesirable.The above-mentioned preferred ratio range is 0.4 to 1
1%, but it is the most suitable one in consideration of the proportion of substances (1) and (III) and/or the amount of other additives, and the properties of the excipient and 11 precepts. Just choose the appropriate ratio.

Furthermore, the said substance 'It (It) must not be present in a proportion less than 71% of the total mineral substances present in the treasure.6 If it is less than this proportion, the said substance (II
This is because the formation of a strong hydrogel structure accompanying the ionization of ) is inhibited. However, since a moderate amount of impurities may be present, the proportion cannot necessarily reach 100%, and in some cases, the presence of mineral substances that are not within the scope of this invention can be approved from the composition properties. It is not necessarily necessary that the ratio reaches 100% because it will be obtained.
Mineral substances mainly refer to elements that originate from mineral products.

The substance (■) according to the invention, ie water, accounts for at least 40% of the total weight of the composition. When this ratio is less than 40%, it is difficult to form a swollen body, which is a precursor of a hydrogel. In order to solve this problem, when forming a hydrogel, a large amount of water is added in advance to create a swollen body, and then some means, such as natural laws such as phase transition or demixing of water, are used to complete the invention. Although there are methods such as adjusting the proportion of water to , even if such measures are taken, it is extremely difficult to form a hydrogel if the water content does not satisfy the above proportion. The preferred proportion of water is at least 73%, and the upper limit does not reach 100% since it depends on the amount of each substance constituting this invention.

The tubular excipient composition according to the present invention may have any form as long as it has a tubular structure, and its structure and formation are illustrated in FIGS. 1 to 5. tubular shaping,
The I acid always has an outer length (R) and a minimum inner length (r), but in the tubular excipient composition according to the present invention, the ratio of these, that is, R/ r is 1.2 to 3
6. When the R/r ratio is less than 1.2, the tubular excipient composition has a small wall thickness and becomes a hydrogel, so it cannot maintain its tubular shape; on the other hand, when the R/r ratio is less than 3.
If it exceeds 6, it no longer has the characteristics provided by the tubular structure, that is, in this case there is no need to have any tubular structure,
A lump or stick shape is sufficient for the purpose.

Among them, a preferable ratio of R/r is 1.3 to 33.

Further, one aspect of the present invention is a tubular shaped product having pleats on the outer and/or inner curved surfaces. The folds are formed continuously on the outer and/or inner surfaces of the tubular excipient compound, but they may also be discontinuously formed in the form of protrusions or islands. It is useful because it gives a unique feel, expands the surface area, and imparts strength.

In addition, in the tubular excipient composition according to the present invention, as mentioned above, R and "must be determined, but when it has pleats, it is natural to take the highest peaks of the pleats protruding from each surface as the measurement position. This is because the lowest point of the folds may create a depression, making the length measurement inaccurate.If the folds are intermittent, or there is a fluctuation in R, there is a possibility that r is fluctuating. If it seems that there is, it can be easily distinguished by preparing several tubular excipient compositions according to the present invention, randomly selecting a certain number of them, cutting them, and actually measuring them.

Another feature of the invention is that the objects f(1), (II
), (II[) is a tubular excipient composition containing not more than twice the weight ratio of additive (1) other than (II[). The additive mentioned here may be an organic substance or an inorganic substance, but in most cases it is a substance that does not cause a chemical reaction with the above-mentioned ATC component, but it is preferably a substance that is compatible with the above three components. Compatibility refers to the phenomenon of compatibility or association, or behavior such as inclusion, adhesion, and good adsorption and dispersion, but when carrying out this invention, extreme phase separation, precipitation, and aggregation (mamako-like) may occur. There is no problem as long as the additives do not cause special problems.Additives include cellulose, starch, derivatives and substituted products thereof, PVAL, polyhydric alcohols such as polyethylene glycol, glycerin, pentaerythritol, ethylene glycol, and butanediol. and its esters, natural gums that are insensitive to gelation even in the presence of salts such as gum karaya and gum tragacanth, polymeric materials derived from natural products such as cotton linters, pulp, paper and fabrics, and fine silica powder. Represented by inorganic fillers such as calcium carbonate, talc, barium sulfate, antimony Q oxide, colorants and their intermediates such as crystal violet lactone, phthalocyanine blue, titanium white, red iron, sorbic acid, benzoic acid, and their compounds. Synthetic preservatives, reinforcing materials such as cotton thread, silk thread, urethane thread, nylon thread, Tetoron thread, rayon thread, flavoring agents that are more or less compatible with water and each of the above substances, spreading agents, water retention agents, softeners, plasticizers agents, antioxidants, etc., but are not limited to these and can be used alone or in combination.

These additives may be uniformly dispersed in the tubular shaped rat material of this invention, or may be embedded, bonded or laminated so as to constitute a part of the tubular shaped rat material of this invention. However, the above-mentioned magnification should be 16 times or less, and even if this magnification exceeds 22 times, there is no difference in the composition, but it does mean that it is a hydrogel composition shaped into a tubular shape. Then, as mentioned above, extreme phase separation, precipitation,
It is better to avoid problems such as agglomeration (makoko-like) when implementing this invention, and the above magnification should be taken into consideration within the range of dangerous oxides that is in harmony with the content of the essential components of this invention. Needless to say, there is.

〔Example〕

Aspects of the present invention will be explained below with reference to Examples, but the present invention is not limited in any way by these Examples.

Production Example 1 300 g of water was weighed and 20 g of it was transferred to another container. A total of 20 g of the transferred water was placed in a bottle containing 0.15 g of calcium hydroxide and 0.05 g of magnesium hydroxide to prepare an emulsion, and the bottle was sealed and stored in a cool, dark place.

10 g of glucomannan powder was weighed out, and the remaining 280 g of water was added thereto to form a swollen body while stirring. 3
After a period of time had elapsed, the entire amount of the emulsion was added thereto and quickly kneaded to homogenize the whole. Inner dimension length 5.4 c
m x width 3.7 C11
This kneaded material was pushed without any gaps into a sealable stainless steel split mold having a core of 8 cm, the mold was tightened, and the mixture was left standing for 1 hour. The mold was then immersed in boiling water in a large pan and boiled for 1 hour. The filled mold was taken out and cooled to room temperature, then opened and the contents were taken out and boiled in boiling water for 40 minutes, then transferred to a stainless steel vat and cooled to room temperature. In this way, a hydrogel composition shaped into a tubular shape was obtained, which was then placed in 1 liter of cold water and allowed to stand until use.

Production Example 2 11 In Example 1, 0 potassium sorbate was added to glucomannan powder.
．． 03 g was added, the entire amount of calcium hydroxide was replaced with magnesium hydroxide, the inner slope had six folds of height 4cm, the other inner slope had a smooth cylindrical shape, and the outer slope A hydrogel composition shaped into a tubular shape as shown in Figure 2 was prepared using the method of Production Example 1, except that a mold that could be assembled and sealed so that the cylindrical core with a smooth surface fit in the center was used. This was placed in cold water together with the composition obtained in Production Example 1 and left until use.

Production Example 3 3 g of sodium polyuronic acid salt was stirred with 90 g of water in a container to prepare a uniform swollen body. Separately, make an emulsion by adding 1 otn of water to 1 g of calcium sulfate O. 0.5 OIM sodium metaphosphate solution
Add d. The liquid was added to the above-mentioned swelling body and mixed uniformly.

A male mold (inner mold) and a female mold (outer mold) for making a tubular square funnel-shaped object are prepared, and the female mold is sprayed with an O, 5M phosphoric acid solution. When the mixture had become elastic after being left for 2 hours, it was transferred into a female mold using a spatula, and a male mold was inserted and tightened for 10 minutes. When the mold was pulled out in step 8, the portion of the mixture that came into contact with the surface of the female mold proceeded to harden and was easily removed from the mold. The mixture thus temporarily shaped was immersed in a 20% calcium chloride solution while being attached to the male mold. When the mold was pulled out of the liquid after 3 minutes, the mixture easily came off the surface of the male mold, and a composition shaped into a tube as shown in Figure 3 was obtained. It was placed in a container and left under running water. These operations were repeated in the same manner to obtain four tubular excipient compositions.

Production Example 4 To a swollen body similar to Production Example 3, 4 g of a 1O overlay solution of polyvinyl alcohol (saponification degree 98%) was added to prepare a homogeneous mixture. This is continuously extruded through a nozzle with a protruding core, and first 130 g/f of calcium chloride is added.
fi, magnesium acetate L Og#! 100 g/ffi of aluminum chloride and 0.5 g of polyoxyethylene sorbitan laurate #!
The solution was passed through a solution containing 60 g/l of calcium chloride, and further washed with water to obtain a water-containing hollow system.

Production Example 5 92 g of water was weighed out, and 16 g of water and Log were placed in separate containers. In 16 g of water, 3 g of anhydrous calcium chloride and 1 g of ferrous chloride were dissolved and sealed tightly (hereinafter referred to as liquid A), and in 10 g of water, 0.0 g of ferrous chloride was dissolved.
Add 2g of β-phenylethyl alcohol to make a homogeneous liquid (hereinafter referred to as liquid B), and the remaining 66g of water and 112g
of glycerin and 8 g of kappa carrageenan to prepare a uniformly swollen product. After leaving it for 3 hours, add solution A to it, mix quickly and uniformly, and heat in a water bath at 80°C for 20 minutes. did.

Thereafter, the mixture was cooled to 60'C, and liquid B was added thereto, mixed uniformly, and poured into a mold with a core. After carefully cooling the injected material, it is released from the mold and shaped into a tubular shape as shown in Figure 4.
lI was a paraboloid. Such operations were repeated in the same manner to obtain three tubular shaped &Il hydric acid compounds.

Example 1 The various properties of the composition obtained in Production Example 1 were measured and the results were as shown in Table 1. This composition was cut under the layer as shown in Figure 5, and then cut by hand! Compared to ordinary lump-like cocoons prepared as lil for school lunches, it was possible to save the trouble of making cuts and holes on the inside, and it was possible to cook a large quantity of cocoons of the same shape.

Example 2 The various properties of the composition obtained in Production Example 2 were measured and the results were as shown in Table 1. This composition was formed in the form of bamboo shoots, and this was cut to the same thickness under the layer. The conventional bulk baking soda of Example 1 was also cut to the same thickness. 10
Each person cooked the food using a pot containing the same number of tmm ingredients using two monitors, and measured the time it took for the flavor of the seasonings to infuse and the food to finish cooking. Table 1 shows the difference (P-Q) between the cooking finishing time P of the tubular excipient composition cut product according to the present invention and the cooking finishing time Q of the conventional block-shaped cut product. It was as described. In addition, 10 monitors sampled both cooked products, and compared the taste based on the texture, spoilage, etc., and the degree of flavor secretion. The results are as shown in Table 1, where the number of participants was expressed as A/B, with A indicating the case where the food was acceptable and B indicating the case where the traditional cooking of lumpy rice was acceptable.

Example 3 The properties of &ll paraboloid obtained in Production Example 3 were measured and the results were as shown in Table 1. This &11 precepts 18
I applied it to the mouth of a liter can and used it as a refill funnel for mineral oil that was to be discarded. When this used composition with waste oil adhering to it was poured into a hot 20% sodium carbonate solution and the liquid was stirred, the composition swelled and dissolved in just over two hours, and the adhering substances disappeared. Waste oil was also saponified.

This liquid was poured into refilled waste oil, the can was capped, and the can was sent to a centralized disposal site.

As described above, the composition obtained in Production Example 3 was dissolved away as a disposable article without any trouble such as washing, and could be easily used.

Example 4 The results of measuring various properties of the &11 precept obtained in Production Example 4 were as shown in Table 1. Protein diffusion was measured using fibers with the same outer diameter manufactured in the same manner as the &[l paraboloid. Bovine serum globulin (molecules 15.8 x 10'
) was added in advance, and each fiber of a predetermined size was immersed in it in its entirety and left at 25°C for 3 minutes. Thereafter, the fibers were quickly pulled out of the solution to measure the amount of bovine serum globulin remaining in the solution. Concentration of bovine serum globulin added in advance per each fiber and per unit length (C3)
and bovine serum globulin concentration in the liquid after pulling up the fibers (C
The results of calculating the ratio CI/cs in 7) are shown in Table 1, and it is clear that the fiber according to the present invention has a higher ability to incorporate bovine serum globulin.

Example 5 The results of measuring the various properties of the &Il acid product obtained in Production Example 5 are shown in Table 1. Separately, a cylindrical composition was obtained in the same manner as in Production Example 5. 2 pieces each &ll
They were placed in airtight containers of the same volume with individual stopcocks, opened for 10 seconds at fixed times every day, and then immediately closed, with 10 monitors to test the activity and persistence of the fragrance. According to this invention, the results of tracking the ratio A/B of the number of people (A) who said that the parabolic object had a higher aroma and the number of people who said that the cylindrical m1Itc object had a higher aroma (B) over time. were as shown in Table 1.

〔Effect of the invention〕

In view of the above-mentioned Examples and their corresponding comparative examples, the tubular excipient composition of the present invention is different from conventional article compositions and formations in all industrial fields! It has much superior features compared to the 11-bottom model. Moreover, it can be seen that these characteristics are effectively exhibited in each case, and according to Table 1, the effects of the tubular excipient composition according to the present invention are obvious.

Figure 4 is a conceptual diagram of the tubular excipient composition obtained in Production Example 5 according to the present invention described in Example 5 of the present invention,
FIG. 5 is a schematic diagram illustrating a fifth embodiment of the present invention.

In these figures, when there is a plurality of R1's, decimal numbers are written together with R1, 'rl, etc. based on the corresponding parts. The shredded piece is a spore blade.

Claims (2)

[Claims] (1) Polysaccharides or derivatives thereof bound to hexoses or hexose substitutes (I); metals (II) forming divalent or trivalent metal ions; and water (III) made from hydrogels as essential components. , their composition is (I) 0.08 to 12% of the total weight, (II) 0.3 to 16% of the total solid weight, and 71% or more of the total mineral substance amount (III) at least the total weight A tubular excipient composition having a ratio R/r of the outer maximum length (R) to the inner minimum length (r) of 1.2 to 36. (2) The tubular excipient composition according to claim (1), which has folds on the outer and/or inner curved surfaces.