JPH02211240A - Iron (ii) composition - Google Patents

Abstract

PURPOSE:To obtain a functional composition stable and active even when used along with various materials by combining an org. acid component and a polyaminocarboxylic acid component with a divalent iron compound. CONSTITUTION:As an active composition having deodorizing properties and freshness keeping properties, a divalent iron compound such as ferrous sulfate or ferrous chloride, an org. acid component such as citric acid or tartaric acid and a polyaminocarboxylic acid component such as ethylenediaminetetraacetic acid or transcyclohexanediaminetetraacetic acid are compounded. Since this divalent iron compound is excellent in stability in an aqueous solution and also excellent in stability under various processing conditions such as a temp. rise condition, said composition is easily formed into a powder and can be mixed with a plastic film or a fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a composition containing an iron (II) compound as a main ingredient, which has excellent stability and has high activities such as deodorizing properties and freshness retention properties.

(Prior Art) The present inventors have previously demonstrated a wide range of adsorption ability for malodorous substances, and developed a new deodorizing agent that combines an iron (II) compound and L-ascorbic acid as an inexpensive, safe, and stable deodorizing agent. (Japanese Patent Publication No. 61-43091), and the present inventors also proposed a composition having deodorizing properties in which an iron (II) compound contains ethylenediaminetetraacetic acid and alum without using L-ascorbic acid. (Unexamined Japanese Patent Publication No. 60-145
No. 143).

The field of application of these deodorizers has expanded further since then, and the forms of use for these deodorizers are not only in liquid form, but also in activated carbon, ceramics, etc., or in solid form, incorporated in resin base materials and used in plastic films, fibers, etc. It has become so.

(Problems to be Solved by the Invention) However, various molding processes under severe conditions are unavoidable before mixing such materials into a base material (for example, resin) and processing them into films, fibers, etc. In particular, processing under heating or elevated temperature conditions cannot be avoided. Therefore, if the stability of a composition containing an iron (II) compound is low, it may change color, change in quality, and in some cases lose its original activity (deodorizing effect, etc.). In the case of compositions using L-ascorbic acid mentioned above, this is not always sufficient. Therefore, when drying an aqueous solution and turning it into powder, L-ascorbic acid is added within a range that does not cause coloring of the powder. - The operation had to be carried out while controlling the concentration of ascorbic acid, which was a problem in terms of quality control. Furthermore, even when the above-mentioned ascorbic acid is not used, the same drawbacks arise, and ethylenediaminetetraacetic acid and alum had to be used in combination in order to exhibit activities such as deodorizing properties.

Therefore, its functions can be stably utilized by coexisting with materials such as aqueous solutions or solvents for long periods of time, and even with materials such as ceramics, activated carbon, and plastics, and the quality is stable during manufacturing. There has been a demand for the development of a functional composition that can be secured at low cost.

An object of the present invention is to provide a new iron (II) compound composition that meets these needs.

(Means for Solving the Problems) The above-mentioned object of the present invention is to provide an iron (If) compound containing an organic acid component and a polyaminocarboxylic acid component to an iron (II) compound.
) Achieved by a compound composition.

The present invention will be explained in detail below.

Examples of iron(II) compounds used in the present invention include ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous bromide, ferrous iodide, and ferrous ammonium sulfate (Mohr's salt). ), ferrous gallate, ferrous malate, etc.
Examples include iron (II) organic salts such as iron and ferrous fumarate. The iron (II) compound is not limited to those exemplified above, and any compound can be used as long as it dissolves in water and forms divalent iron ions.

In the present invention, the organic acid component has the effect of stabilizing the active divalent iron ion by coordinating with the divalent iron ion of the iron(II) compound. Examples of such organic acids include carboxylic acids, such as oxyacids such as citric acid, isocitric acid, citric acid, tartaric acid, malic acid, hydroxybutyric acid, monoethyl tartrate, monoethyl citrate, gluconic acid, and ketogluconic acid. Acid, aliphatic or aromatic compounds such as salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gallic acid, water-soluble salts thereof, etc. are used.

Examples of carboxylic acids include the above-mentioned bakaoxocarboxylic acids and polycarboxylic acids such as maleic acid.

The present invention is characterized in that a predetermined amount of polyaminocarboxylic acid is used in combination with such an organic carboxylic acid. Examples of such polyaminocarboxylic acids include ethylenediaminetetraacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, diethylenetriaminepentaacetic acid, and the like. Of course, these salts may be salts such as sodium salts, potassium salts, and ammonium salts.

This iron (If) composition contains an iron (II) compound as a main component. The ratio of iron (II) and organic acid component in the iron (Ill) compound is usually 1:0.01 to 0.80. Preferably 1:0.01-1:0.10, more preferably 1
: In the range of 0.01 to 1:0.04. Even if the organic acids are used in amounts exceeding the upper limit of the above range, no increase in effectiveness can be expected and it becomes uneconomical, while below the lower limit, the activity (freshness preservation, deodorizing function, etc.) will be insufficient.

In the present invention, the polyaminocarboxylic acid component used in combination with the organic acid component is usually 1 to 100% by weight based on the organic acid component.
However, preferably 10 to 75% is used. If the content of polyaminocarboxylic acid is too small, the stability (discoloration resistance) of the iron (II) composition will be insufficient, and if it is too large, the stability will be high but the activity (deodorization, freshness preservation, etc.) will be insufficient.
is damaged.

In the present invention, the organic acid components may be used alone or in combination of two or more.

It is preferable to add alum to the iron (II) compound of the present invention to stabilize its freshness-keeping and deodorizing functions. In this way, it can also function as a flame retardant. The amount of alum to be added varies depending on the purpose and form of use of the composition of the present invention, but iron (iron in the former compound (weight ratio to the former is in the range of 1:10 to 10:1, preferably 10:2) It is preferable to add the alum in the range of 10 to 10:5. Although there are no particular restrictions on the alum, potassium alum, ammonia alum, sodium alum, etc. are preferable, and calcined alum is particularly preferable.

In order for the iron (II) composition of the present invention to exhibit stability and activity, it is necessary that an organic acid component such as citric acid and a polyaminocarboxylic acid component be bound to the iron (JI) compound as the main component. It is. Such a composition can be prepared by mixing and dissolving the same components and powdering the resulting aqueous solution by spray-drying, freeze-drying, or the like.

The iron (II) composition of the present invention is not only extremely stable in an aqueous solution, but is also extremely advantageous in that it is stable and maintains its activity even during such drying and powdering processes.

The composition of the present invention is prepared by mixing the above-mentioned components in a predetermined ratio as an aqueous solution, but a major feature is that the composition can be changed into a wide variety of forms. This is based on the fact that in the present invention, stabilization of iron (II) by an organic acid such as oxycarboxylic acid is extremely facilitated by the coexistence of a polyaminocarboxylic acid (eg, EDTA), and stability is maintained permanently.

The iron (II) composition of the present invention can be used as it is as a solution or as a powder by being incorporated into a base material such as a carrier, resin, or fiber by methods such as impregnation, kneading, coating, and scattering.

More specifically, in order to use this composition, it can be used as it is as an aqueous solution, or it can be dried to form powder or granules, and the solid form can be used as it is, or zeolite, zeolite, etc. can be added to it as appropriate.
Clay minerals and activated carbon may be added and used as a support. Drying methods include spray drying and freeze drying, but iron (II) compounds can be easily dried in a stable form. I can do it.

The powder obtained by drying can also be dispersed in plastics, e.g.
% of the composition is used as a masterbatch, and this material is diluted with a dilutable plastic to obtain a new material containing a predetermined amount of the composition of the present invention. If the material can be made into a film, its uses can be expanded as a material for new functional materials.

In order to contain this composition as a fiber material, it is possible to prepare fibers from a masterbatch, but it is more preferable to use a method in which the composition is dispersed and injected within a very short period of time immediately before spinning. The composition of the present invention can be said to be revolutionary in that it has various physical properties that can withstand the various conditions at that time.

When using the present composition by mixing, dispersing, coating, or impregnating other materials, in particular, in the case of coating or impregnating methods, PVA or
Preferably, VA and dextrin or CMC are used.

This method is considered to be effective in finely dispersing the components that are precipitated and bonded during the formation of the coating film, and is an effective method for coating and impregnating paper, wood, nonwoven fabrics, etc.

The content of the iron (old composition) of the present invention when used with a base material varies depending on the use and type of the base material containing the iron (II) composition, but is usually 5 to 7 parts by weight per 100 parts by weight of the base material.
A range of 0 parts by weight is preferred.

(Effects of the Invention) The iron (II) composition of the present invention not only has excellent stability in an aqueous solution, but also has excellent stability under various processing conditions, such as elevated temperatures, so it can be easily powdered by spray drying etc. . Furthermore, since the powdered composition of the present invention has high stability, it can be mixed into plastic films, fibers, etc. without any problem even under various processing conditions. Therefore, the iron (II) composition of the present invention can stably exhibit deodorizing, freshness preservation, mold-proofing, flame-proofing functions, etc. for an extremely wide range of uses. Furthermore, the composition of the present invention is inexpensive, and by selecting appropriate combinations of iron (II) compounds, organic acids, polyaminocarboxylic acids, etc., it is said that it is possible to easily create a composition that is safe from a food hygiene perspective. It also has significant practical advantages.

(Example) Next, the present invention will be explained in more detail based on examples.

In addition, in the following examples, unless otherwise specified, % indicating the composition indicates weight %.

Example 1 Test system A: 0.014 citric acid per mole of ferrous sulfate
An aqueous solution containing 0.003 mole of ethylenediaminetetraacetic acid (hereinafter referred to as EDTA) at 1°C was prepared.

Control system B: An aqueous solution lβ was prepared by adding 0.014 mol of citric acid to 1 mol of ferrous sulfate.

Both systems A and B were placed in beakers open to the atmosphere and left at room temperature for one month, during which time changes in ferrous ion concentration and discoloration of the liquid were observed. The result is the first
Shown in the table.

Example 2 5% EDTAo and 3% citric acid for iron in ferrous sulfate
% and 10% alum were added, and this was spray-dried at 150° C. and powdered. This is called Powder A. This powdered iron (■) composition has a particle size of 65 mesh or less in 90% or more.

For comparison, a powder was obtained by spray drying in the same manner as above without using EDTA. This is called Powder B.

These dry powders were gradually heated in the air and the state of discoloration was observed. The results are shown in Table 2.

Table 2 Next, the following test was conducted to test the removal of ammonia odor using the above powder A, powder B, and activated carbon. 10% ammonia water in 3 approximately 212 volume polyethylene bags
After adding cc, add A powder, B powder and activated carbon respectively.
3 g was added, shaken well, and an odor sensory test was performed every 2 minutes to determine the elapsed time until no odor was felt. The results are shown in Table 3.

Table 3 Furthermore, filter paper was placed in a container with a lid of about 500 cc of polyethylene bag, and 10% ammonia water was added dropwise to the filter paper (1 drop of about 0.1 cc). At this time, 3 g of powder A was added, the lid was closed, and the container was allowed to stand for a certain period of time, and the ammonia odor inside was observed to disappear. Ordinary activated carbon 3 with the same powder particle size
The situation in which the ammonia odor disappears was compared by using g instead.

The results are shown in Table 4.

Example 3 Approximately 20% of powder composition (A powder) having the same composition as Example 2
Table 5 shows the results of a deodorization test using 150 g of granular (3 m / m + cylindrical) material made up of zeolite and clay, the remaining 80% of which was packed in a packed reaction tube.

Compared to normal activated carbon, where the wind speed in the reaction tower is 20 cm/sec and the contact time is 3 seconds, about 210 kg of activated carbon is required to completely deodorize the gas with the above-mentioned original odor concentration, but the product of the present invention When using 20 kg, equivalent exhaust gas was obtained.

Example 4 5% EDTAo, 5% citric acid for iron in ferrous sulfate
A fine powder obtained by spray-drying an aqueous solution to which 10% of acetic acid was added in an ambient temperature of 150° C. is dispersed in a polyolefin at a rate of 20% using a surfactant. The obtained plastic dispersed phase (referred to as a masterbatch) can be arbitrarily diffused and dispersed in polyethylene or polypropylene. In this way, by appropriately selecting the amount of the masterbatch, it is possible to obtain a plastic with a desired content of iron (II) composition dispersed therein. polyethylene blown film can be easily produced. This film can be laminated with another layer of polyethylene having a thickness of about 20 microns on its inner and outer layers to produce a packaging material consisting of a polyethylene sandwich plate containing polyethylene.

This material has gone through various temperature histories until it is completed, but iron(II) compounds cannot be stabilized even if they are attempted to be stabilized with organic acids alone. However, in the system of the present invention in which EDTA coexists with an organic acid, the iron (II) compound does not change at all even under the above temperature history, and 3% iron (
II) A film containing the composition is produced.

When the interlayer film of the sandwich plate is immersed in water, ferrous ions are eluted by diffusion from the surface.Furthermore, when the sandwich plate is immersed in water as described above, elution is almost suppressed. The situation is shown in Table 6 below.

Example 5 (Freshness-preserving anti-mold effect) Using an aqueous solution prepared by diluting the powder of Example 2 (Powder A) to a predetermined concentration, the antibacterial and anti-mold effect of the product of the present invention was tested. The concentrations that inhibit proliferation are shown below. The antibacterial and antifungal effect of the product of the present invention is demonstrated at a concentration of approximately 1. OOO~5. OO
It turns out that Oppm is good.

Bacteria body Escherichia coli Bacillus subtilis Pseudomonas aeruginosa Staphylococcus aureus Composition concentration (ppm) baker's yeast candida 5.000 5.000 blue mold black stag and Wallemia 5ebi i,oo.

1.000 3.000 The antibacterial effect of the freshness preservation bag containing the iron (II) composition of the present invention (3%) is shown below.

Invention product Invention product Conventional product Conventional product chicken breast Chicken thigh chicken breast Chicken thigh General bacterial count 5.2XlO' 4.9X10' 3.8X10' 3.6X10' coliform count 6.9XIO” 6.5X10" 4.0X10' 3.4XIO'

Claims (2)

[Claims] (1) An iron (II) composition comprising an iron (II) compound as a main component, to which an organic acid component and a polyaminocarboxylic acid component are combined. (2) The iron (II) composition according to claim 1, comprising alum.