JPH0340898A - Processed article of base material - Google Patents

Abstract

PURPOSE:To obtain the title processed article reduced in a change of color with the passage of time, capable of providing sterilizing and deodorizing characteristics to the coated material and useful to retention of freshness by blending glyoxal of specific amount based on the total amount of iron compound and L-ascorbic acid with the iron compound and L-ascorbic acid. CONSTITUTION:A composition being a water based composition containing (A) at least one kind of iron (II) compound selected from iron (II) sulfate, iron (II) chloride and iron (II) nitrate, (B) L-ascorbic acid and (C) glyoxal and being 1-4000wt.% based on total amount of the components A and C in an used amount of the component C in the composition and being 0.01-30wt. based on the composition in total used amount of the components A and B in the composition is applied to or impregnated into a base material to provide the aimed processed article.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a processed support material which reduces discoloration over time and effectively imparts sterilizing and deodorizing properties to the coated object.

<Prior Art> It is generally known that a composition comprising L-ascorbic acid and an iron (II) compound has bactericidal and deodorizing properties. Examples of cases in which such properties are effectively utilized include the use of the former (sterilizing property) to sterilize processed foods and raw materials for salads that cannot be sterilized by heat, or to sterilize fresh foods and seafood products that tend to lose their freshness, for example. vegetables, fruits, meat,
It also sterilizes seafood, keeps it fresh, preserves it, and preserves it.

Further, as an example of the use of the latter (deodorizing property), there is a use as a deodorizing agent in which the composition is attached to an activated carbon-containing carrier, or the composition itself is contained in paper cloth.

Therefore, the characteristics and uses of the above-mentioned composition were quickly proposed by the present inventor as a result of his research, and related publications include JP-A-59-59604, JP-A-9-143576, and JP-A-9-143576. Kaisho 59-132937
No. 60-66753, etc.

<Problems to be Solved by the Invention> However, the composition containing the L-ascorbic acid and iron (■) compound cannot be coated on a support or (.

When impregnated, color change may occur over time, and depending on the usage, the product value may be significantly impaired.

Therefore, in order to overcome this drawback, it has been considered to mix the composition with a type of white pigment, but since the composition is strongly acidic, it has been difficult to cause aggregation or gelation.

Another possible method is to apply or impregnate the composition, dry it, and then apply a layer of white paint to hide the discoloration, but in this case, the surface coated with the composition and the top coat may This is not practical because the top coating layer tends to fall off due to insufficient adhesive strength. Furthermore, the above-mentioned publication regarding button compositions also states that discoloration over time can be reduced by incorporating an appropriate amount of thiosorbate or dithionite into the composition.
Depending on the type of support, you may not be able to expect much of an effect.

From this perspective, how to solve the above problem has become a particularly urgent issue.

The present invention has been made in view of the above points, and an object of the present invention is to provide a processed support that reduces discoloration over time and has good sterilization and deodorization properties.

Means for Solving the Problems> As a result of intensive research to solve the above problems in the most rational and effective manner, the present inventors have developed a conventional composition containing L-ascorbic acid and an iron (II) compound. The present invention was completed by conducting experiments using multiple methods, and found that an aqueous solution obtained by mixing glyoxal with a support can be expected to reduce discoloration over time when coated or impregnated onto a support.

That is, the present invention uses ferrous sulfate and ferrous chloride.

At least one type of iron (I) selected from ferrous nitrate
I) An aqueous composition containing a compound, L-ascorbic acid, and glyoxal, wherein the amount of glyoxal used in the aqueous composition is the total amount of the iron'(II) compound and L-ascorbic acid used. 1 to 4000% by weight based on the iron(II) compound and L in the aqueous composition.
- A processed support product obtained by coating or impregnating a support with an aqueous composition in which the total amount of ascorbic acid used is 0.1 to 30% by weight based on the aqueous composition.

Therefore, to prepare the aqueous composition required in the present invention, one of the following methods may be used: Q, p4t, etc.

Just do it.

(2) A mixed solid (including powder; the same applies hereinafter) containing L-ascorbic acid and an iron (II) compound and a solid glyoxal are simultaneously dissolved in water.

(2) Dissolve solid glyoxal in a mixed aqueous solution containing L-ascorbic acid and an iron (II) compound.

(2) A mixed aqueous solution containing L-ascorbic acid and an iron (II) compound and an aqueous glyoxal solution are mixed.

■ In the above aqueous composition in which a mixture containing L-ascorbic acid and an iron (II) compound (both solid substances) are dissolved separately or in a mixture in an aqueous solution of glyoxal, the content of glyoxal is equal to or less than that of L-ascorbic acid. Iron (■
) 1 to 4000% by weight based on the total amount used with the compound (
It is important that the amount is preferably 5 to 400% by weight (in terms of solid content; the same applies hereinafter). When the amount used is less than 1% by weight, the effect of reducing discoloration over time when a support is coated or impregnated with the obtained aqueous composition becomes insufficient. Also,
If the usage amount exceeds the upper limit of 4000% by weight, the above-mentioned disadvantages will be resolved, but if the Pi degree of the two-component composition (mixture containing L-ascorbic acid + iron (II) compound) is too low, the bactericidal and deodorizing properties will deteriorate. This makes it difficult to apply and is not practical.

At this time, the concentration of the water-based Mi precept liquid is 0.3 to 50.
The total content of L-ascorbic acid and iron (IT) compounds in the liquid is preferably 0.1 to 30% by weight, preferably 1 to 35% by weight, or 1.0 to 35% by weight. It is important to keep the content within the range of 20% by weight. This range is the best range for imparting the desired sterilizing and deodorizing properties to the support after coating or impregnation. When this content is less than 0.1% by weight, the desired sterilization and
It cannot be combined with deodorizing properties. In addition, if the content exceeds 30% by weight, the above-mentioned drawbacks will not be resolved or it will be difficult to maintain the specified concentration (0.3 to 50% by weight) of the aqueous composition, making it unsuitable for treatments such as coating. .

As described above, the present invention can most effectively achieve the desired object by mixing the components constituting the aqueous composition so as to have a certain mixing ratio (range) as described above.

The support for coating the aqueous composition is paper.

Non-woven fabric 9 Synthetic resin film type, paper for impregnation,
Optionally, non-woven fabrics may be used.

Effect> As described above, the present invention utilizes L-ascorbic acid and iron (II).
) By mixing a certain amount of glyoxal (solid content) with the total usage amount (solid content equivalent) of the composition containing the compound, the iron(II) compound forms a complex with the malodor source (component) and eliminates the malodor source. In addition to effectively removing superoxide radicals (02) and exhibiting bactericidal properties, the mixed use of glyoxal makes it possible to effectively remove superoxide radicals (02). Reduces the degree of discoloration over time.

<Effect of the invention> The present invention exhibits the following unique effects.

■ The present invention provides a composition comprising L-ascorbic acid and at least one type of iron (II) compound selected from ferrous sulfate, ferrous chloride, and ferrous nitrate. Since the composition is a mixture of a certain amount of glyoxal (solid content) with respect to the total usage amount (in terms of solid content) of L-ascorbic acid and the iron (II) compound, the aqueous solution is coated on a support or The degree of discoloration over time during impregnation is reduced, and the decline in commercial value due to discoloration can be minimized.

(2) Furthermore, as described above, this invention forms a complex with the iron (IF) compound or the malodor source (component) when it comes into contact with the malodor source, while by mixing L-ascorbic acid,
It generates superoxide radicals (OS-) and imparts bactericidal properties. Moreover, while the deodorizing properties of compositions containing L-ascorbic acid and iron (II) compounds have traditionally been excellent against nitrogen-based malodors (components) such as ammonia and oxidation, sulfur The deodorizing power against sulfur-based bad odors (components) such as hydrogen and mercaptan is as follows:
However, the aqueous composition of the present invention contains glyoxal, which itself has deodorizing properties. And its deodorizing effect is
Although the composition contains nitrogen-based malodors (components) such as ammonia and amines, it is not as good as the composition containing L-ascorbic acid and the iron (II) compound, but it does not have sulfur-based malodors (components) such as hydrogen sulfide and mercaptan. is the above L
- Has superior efficacy to compositions containing ascorbic acid and the iron(II) compound.

Therefore, if glyoxal is used, the deodorizing effect against sulfur-based malodors (components) such as hydrogen sulfide and mercapta will be enhanced, and the imbalance in deodorizing effectiveness against nitrogen-based malodors (components) and sulfur-based malodors (components) described above will be improved. It can be corrected, balanced, and impart stronger deodorizing properties.

Therefore, the present invention reduces the degree of discoloration over time when the coating liquid is applied to or impregnated on the support, and simultaneously imparts sterilization and deodorization properties to the support.
It is suitable for multipurpose uses such as deodorization (containing deodorization) and maintaining freshness, etc., and its application fields are wide-ranging, and its practical benefits are remarkable.

<Example> ■ Preparation of aqueous solution (a) A total amount of L-ascorbic acid and ferrous sulfate used is 100
10 g of the former and 90 g of the latter are 1 volume so that g
Weighed into a 1000 mβ flask, added 300 g of water and stirred to obtain the total amount of L-ascorbic acid and sulfur (b) (C) (d) ferrous acid used in the aqueous solution (in terms of solid content; (same below) is 2
A composition (aqueous solution) prepared to have a concentration of 5% by weight was obtained.

Solution B Dilute 100g of Solution A prepared in (a) above with 62.3g of water so that the total amount of L-ascorbic acid and ferrous sulfate in the aqueous solution is 15.4% by weight. A prepared composition (aqueous solution) was obtained.

Solution C 10Q.g of Solution A prepared in (a) above and 62.5g of glyoxal 40% by weight solution were mixed and stirred, and the total amount of L-ascorbic acid and ferrous sulfate in the aqueous solution was 1
A composition (aqueous solution) was obtained in which the amount of Cryoxal used was 15.4% by weight.

Add and stir 1.25 g of solid sodium thiosulfate to 100 g of B solution prepared in (a) above, dilute with 61.1 g of water, and add (e) L-ascorbic acid to the aqueous solution. The total usage amount with ferrous sulfate is 15
．． A composition (aqueous solution) was obtained in which the amount of sodium thiosulfate was 4% by weight and the amount of sodium thiosulfate was 5% by weight based on the total amount of L-ascorbic acid and ferrous sulfate.

Solution E To 100g of Solution A prepared in (a) above, 25g of an aqueous solution of locust bean gum with a concentration of 5% by weight was added and stirred to determine the total amount of L-ascorbic acid and ferrous sulfate used in the aqueous solution. A composition (aqueous solution) was obtained in which the amount of locust bean gum used was 5% by weight relative to the total amount of L-ascorbic acid and ferrous sulfate used.

E' Solution A prepared in above (a): Add 100 g of a 5% by weight aqueous solution of locust bean gum to 100 g and stir to determine the total amount of L-ascorbic acid and ferrous sulfate in the aqueous solution. A composition (aqueous solution) was obtained in which the amount of locust bean gum used was 201 fi % with respect to the total amount of L-ascorbic acid and ferrous sulfate used.

(f) Solution F Add glyoxal 4 to 100g of Solution A prepared in (a) above.
Add and stir 62.5 g of 0 wt % liquid and 31.3 g of 4 wt % liquid of locust bean gum to determine the L-
The total usage amount of ascorbic acid and ferrous sulfate is 12.9
Weight%, amount of Guwaoxal used is 12.9% by weight, L
- A composition (aqueous solution) was obtained in which the amount of locust bean gum used was 5% by weight relative to the total amount of ascorbic acid and ferrous sulfate used.

(f) Solution F' Add 40M glyoxal to 100 g of solution A prepared in (a) above. Add and stir 62.5 g of a 4% solution by weight and 125 g of a 4% solution of locust bean gum to determine the L occupied in the aqueous solution.
-The total amount of ascorbic acid and ferrous sulfate used is 8.7
% by weight, the amount of cryoxal used is 8.7% by weight, L-
A composition (aqueous solution) was obtained in which the amount of locust bean gum used was 20% by weight relative to the total amount of ascorbic acid and ferrous sulfate used.

■ Discoloration test over time (a) Test the above A on commercially available western paper. The liquid-containing coated paper and the liquid-C coated paper obtained by rod coating (conventional method) with liquids a and C were
The sample was stored in an environment controlled at 65% relative humidity at 1° C., and the change in hue over time was measured using a color difference meter, and the results shown in Table 1 and FIG. 1 were obtained. In addition, the coating amount of the liquid is the total solid content of L-ascorbic acid and ferrous sulfate, and the amount of liquid A is 6.
．． 1g/m2. The concentration of liquid B is 6.0 g/m2. Also,
The values in Table 1 are the color difference ΔE between the liquid coated paper and uncoated paper, and ΔE is ΔE= −+a−a +b−bL, a , b
: Measured values for the liquid-coated paper L', a, b'H are given by measured values for the uncoated paper.

(b) The above B liquid, C liquid, D liquid, E liquid and F liquid on commercially available paperboard.
Apply the liquid to the rod (regular method) and do the same as in (a) above.
When we measured the hue change of each liquid-coated paper over time, we found that
The results shown in the table and FIG. 2 were obtained. The amount of liquid applied is
B based on the total solid content of L-ascorbic acid and ferrous sulfate.
The liquid is 4.7g/m2. C liquid is 5゜2g/m2. D liquid is 5.5g/m2. E liquid is 4.0g/m2゜F liquid is 2
．． It is 0m2.

In addition, the values in Table 2 indicate the color difference △ between the liquid-coated paper and uncoated paper.
E, and ΔE is as shown in (a) above.

(hereinafter, blank) Table 1 (hereinafter, blank) Table 2 As is clear from Table 1, Table 2, Figures 1 and 2, an aqueous solution containing L-ascorbic acid and ferrous sulfate or When a composition (aqueous solution) containing glyoxal is mixed with an aqueous solution containing L-ascorbic acid, ferrous sulfate, and vegetable gum, the degree of discoloration over time when applied to western paper or paperboard is as follows: It can be seen that this is significantly reduced.

Deodorization test The following deodorization test was conducted on the A-coated paper, C-liquid coated paper, and F-liquid coated paper obtained in (a) of the above ① temporal discoloration test, and the results shown in Table 3 were obtained.

(Ammonia deodorization test) (a) Air is injected into a smell bag for environmental analysis (manufactured by Gascro Industries Co., Ltd., capacity 3ff), and after injecting an appropriate amount of ammonia vapor into it and dispersing it uniformly, the detection tube (Kitazawa Sangyo Co., Ltd. Ammonia concentration is measured via a

(b) Cut the specimen to a size of 5 mm x 30 mm to obtain a certain number (30 pieces) of the specimen.

After that, the entire amount of the test piece (B) was put into the ammonia-containing bag (A), and a silicone rubber stopper was applied.After an hour and several liters, the ammonia concentration in the bag was measured through a detection tube. Measure.

(Hydrogen sulfide deodorization test) (a) Air is injected into a scent bag for environmental analysis (manufactured by Gascro Kogyo Co., Ltd., capacity 3I, and an appropriate amount of hydrogen sulfide vapor is injected into it to disperse it uniformly, then the detection tube ( (manufactured by Kitazawa Sangyo Co., Ltd.) to measure hydrogen sulfide concentration.

(b) Cut the specimen to a size of 5a+m x 30mm to obtain a certain number (150 pieces) of the specimen.

After that, the test piece (b) is placed in the hydrogen sulfide-containing bag (a).
After putting in the entire amount of the bag and applying a silicone rubber stopper, the hydrogen sulfide concentration in the bag was measured through a detection tube after being left for 7 hours.

(Hereinafter, blank space) As is clear from Table 3 of Table f53, a composition (aqueous solution) in which an aqueous solution containing L-ascorbic acid and ferrous sulfate and glyoxal were mixed with this aqueous solution was applied in a coating amount (L-ascorbic acid). The deodorization rate when coated paper is coated on a support (paper) so that the total solid content of acid and ferrous sulfate is the same and is treated in an odor-containing atmosphere by a prescribed method, or about ammonia. Do both solutions show equally high deodorization rates?
Regarding hydrogen sulfide, the solution containing glyoxal has a significantly higher deodorization rate than the solution containing no glyoxal. That is, by using glyoxal in combination, the original bactericidal and deodorizing effects of L-ascorbic acid and iron (II) compounds are not inhibited in any way,
Furthermore, the imbalance in deodorizing power with respect to the type of malodorous components is corrected.
It can be seen that the deodorizing properties are balanced and more powerful. Furthermore, even when a vegetable gum substance is mixed, the effect of glyoxal is not inhibited in any way.

■ Liquidity test Above, A liquid, E liquid, E° liquid, C liquid, F liquid, F.

When the liquid viscosity and water retention were measured, the fourth
The results listed in the table were obtained.

(Hereinafter, blank space) Table 4 shows that when a vegetable gum substance is mixed into an aqueous solution containing L-ascorbic acid and ferrous sulfate, the viscosity and water retention of the solution can be increased, but glyoxal Even when mixed with a vegetable gum substance, the desired liquid viscosity and water retention can be increased.

[Brief explanation of drawings]

FIGS. 1 and 2 are characteristic diagrams showing the relationship between color difference and number of days over time. Iroka E Basatsu JE recognition

Claims (1)

[Claims] An aqueous composition comprising at least one type of iron (II) compound selected from ferrous sulfate, ferrous chloride, and ferrous nitrate, L-ascorbic acid, and glyoxal,
The amount of glyoxal used in the aqueous composition is greater than the amount of iron (I) used in the aqueous composition.
I) 1 to 4000% by weight based on the total amount of the compound and L-ascorbic acid used, and the total amount of the iron (II) compound and L-ascorbic acid in the aqueous composition is 1. A processed support, characterized in that the support is coated or impregnated with an aqueous composition of 0.1 to 30% by weight based on the weight of the support.