JPS59207976A - Starch paste composition - Google Patents

Abstract

PURPOSE:To provide a starch paste composition resistant to the viscosity decrease caused by amylase, by adding a trivalent metal compound, etc. to a starch suspension, treating the suspension with a mineral acid in the presence of a benzenecarboxylic acid (salt), and dispersing the product in water, etc. CONSTITUTION:The objective starch liquid compositon can be prepared by treating a starch suspension containing (A) a trivalent metal compound (preferably aluminum sulfate, etc.) or its mixture with (B) a zinc compound (preferably zinc borate, etc.) as active components with a mineral acid in the presence of (C) a benzene-carboxylic acid (preferably benzoic acid) or its salt, and dispersing or dissolving the treated product in water. The pH of the starch paste is preferably adjusted to 3.7-6.0 when the active components are the components (B) and (C), or 3.7-9.0 when the acitve components are the components (A), (B) and (C). The concentrations of the components (A), (B) and (C) are preferably 0.2-0.4wt%, 0.2-0.8wt%, and 0.8-2.0wt%, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a starch paste composition, and more particularly to an improved starch paste composition containing an amylase (starch degrading enzyme) inhibitor that prevents viscosity reduction of the natural starch paste.

Various types of starch glues, each of which uses starch as its main raw material, are used in large quantities over a wide range of applications, including household, office, and industrial applications, particularly as adhesives for paper. For these uses, consistency stability is particularly important due to conditions such as distribution and the variety of environments in which it is handled, such as the workability of the paste and practical aspects such as storage. be done. Microorganisms that decompose starch glue are widely distributed in the natural world, and in fact, viscosity decreases due to amylase produced by microorganisms or contamination by digestive medicines and saliva during use of starch glue due to bacteria attached to containers and airborne bacteria. This results in a marked decline in adhesive performance as a glue, making it unusable. This phenomenon occurs when the pH of the glue is below 37 or 9.0 when on shore.
1? It is known that in the pH range of 37 to 90, viscosity reduction due to amylase is likely to occur. For these reasons, poor viscosity, especially a decrease in viscosity, after adjusting the starch paste poses a major problem in terms of marketability and workability.

Conventionally, in order to prevent such a decrease in viscosity, for example, formaldehyde was used as an amylase inhibitor for starch in the pH range of 3.7 to 90, which is susceptible to viscosity decrease by amylase. Inhibition41], preservatives, and fungicides were required to be used together (Note: JIS-3602
However, despite the addition of these high concentrations, the effect of preventing viscosity reduction is sustained for a short period of time, and the quality is maintained for a short period of time. did not fully satisfy the requirements of For this reason, it is almost essential to use a preservative or bactericide instead of a formaldehyde donor. Also, according to this pond, amylase i! 11 Harmful substances include mild oxidizing agents such as ferricyanide, cisdesi, and iodine, alkyl reagents such as iodoacetamide and iodoacetate, mercaptide-forming gold ions, acetylation agents such as ketene and acetic anhydride, and picrin. acid, good organic acids such as cucinic acid, and f which is structurally similar to glucose.
f1li glycosuria is known. Due to distribution and usage habits, starch glue must be able to withstand storage and use for more than one year.6 However, the effectiveness of conventional starch pastes is long, despite the fact that many of them have excellent initial formulation effects.1 In terms of action and effect, the second one lacks sustainability and is not sufficient, and tends to require a large amount of added food, so toxicity and medicinal properties tend to be ignored.

An object of the present invention is to provide a starch paste composition that is effective in preventing the viscosity of starch paste from decreasing due to microorganisms, particularly amylase.

That is, as a result of intensive research in search of an excellent amylase inhibitor to achieve the above object, the present inventors found that when starch is gelatinized using a normal method, after neutralizing the gelatinized product with a neutralizing agent, 3. A starch paste composition containing a valence metal compound, benzenecarboxylic acid or its salt, and a zincite compound as an active ingredient in a combination of predetermined additions has a pH range of 37 to 9.
What is the outstanding effect on preventing the viscosity reduction caused by amylase at 0.0 and long-term (right)? This is based on the discovery of facts that have excellent effects, and the following measures are taken.

That is, the present invention provides a starch paste composition in which a trivalent metal compound or a mixture of a trivalent metal compound and a zinc compound is added to the active ingredient in the presence of benzenecarposis acid or a salt thereof. The purpose is to

The present invention (r:i) Further, natural starch and water are mixed together in one yarn to produce starch paste, and benzenecarboxylic acid is added to 3,
1 and then adding a trivalent metal compound alone or a mixture of a trivalent metal compound and a zinc compound to produce a starch paste composition which has the effect of preventing viscosity reduction due to amylase in starch paste as an active ingredient. This is the way to do it.

To explain Starch 81-1 in more detail, the starch of the present invention]? Composition No. 11 can be applied in accordance with normal working methods and can be expected to have many effects. In other words, glue shaving, neutralizing agent (t-1) Any conventionally used neutralizing agent may be used, and there is no particular restriction. For example, caustic soda may be used as the gelatinizing agent, and the concentration of the neutralizing agent may be adjusted to the starch concentration. 5~6.5 layers 1B
%, as the intermediate phase 1'FIJ (d) Acid expansion such as sulfuric acid, nitric acid, salt 1, etc. is used, and its addition concentration is required, and the neutralization concentration should be 1 to 3. The natural starch used for J is not particularly limited, and any starch that falls within the scope of Keamy Cornstarch such as wheat starch, potato starch, cornstarch, cupioca starch, etc. can be used.Also, if necessary, starch can be used. Starch inducer 4
Can be used for mixed use with type 1 or type 2 ball-L.

These starch raw materials are starch I41
In order to obtain a viscosity state of 15 to 3
It is used at an additive concentration of 0% by weight, but preferably 18-2
It is 2% by weight.

゛The starch II of the present invention has a significantly superior effect in preventing viscosity reduction caused by beamylase compared to conventional starch pastes to which 1.0% by weight of formaldehyde has been added, and can satisfy market demands. It is something. Furthermore, compared to conventional starch pastes using formaldehyde, there is no odor, no irritating gas, and no emission of irritating gases, so the working environment is significantly improved. This remarkable effect of the present invention is due to the active ingredient 3Ill! of the starch paste composition. It can only be obtained by mixing a compound, a benzenecarboxylic acid or its salt, and a zinc compound in combination as shown in the examples below, and when each is used alone, it has no viscosity reduction prevention property. I can't get it.

In the present invention, typical examples of trivalent gold and teso compounds that are effective in the present invention include aluminum sulfate, aluminum chloride, aluminum oxide, aluminum nitrate,
Potassium aluminum sulfate, aluminum sulfate, ferric ammonium sulfate, ferric chloride, ferric fluoride, ferric sulfate, r) ferric phosphate, ferric sulfate, chromium ammonium sulfate, chromium nitrate, Potassium chromium sulfate, chromium sulfate, etc., and benzenecarboxylic acids include benzoic acid, P-hydroxybenzoic acid, P-inpropylbenzoic acid (cumic acid), and phthalic acid as monobasic acids and O/polybasic acids. , isophthalic acid, benzenepencarboxylic acid, fluorobenzoic acid, chlorobenzoic acid, anisic acid, vanillic acid,
iso/< diphosphoric acid and its salts, and zinc compounds include zinc chloride, zinc nitrate, zinc borate, zinc hydroxide, zinc meborate, etc.; Eleven types or one or more of these can be used. For example, in the present invention, particularly preferred 3fllIi metallized materials include aluminum sulfate, aluminum nitrate, and ferric sulfate. The addition concentration is determined by the type of starch used and the viscosity of the sizing agent required for 0.0%, and it is used at 0.05 to 1.0% by weight, but it is preferably 0.2 to 0.0%. .quadruple If1
% will be added. In this case, the starch paste solution has a P HJt of 3.7 to 6.0 in the presence of the benzene carboxylic acid described below, and the system containing metal salts exhibits extremely excellent dispersibility. By increasing the synergistic effect of the salt, the W-active ingredient of the trivalent metal compound can be effectively utilized, and good results can be obtained overall. And if the PHV exceeds 6.0 in odor, 3
Regardless of the presence of @fi compounds, it basically does not exhibit viscosity reduction prevention properties. Also, if the pH is below 3.7, it will be hydrolyzed at high temperatures and will be spoiled. However, one of the above trivalent metal compounds
Rice 11 with 0.05% by weight of rice: When used in rice bran, viscosity reduction is not noticeable and young fruit is not noticeable, and resistance to amylase is weak. The decrease in viscosity caused by strained amylase cannot be sufficiently suppressed, and if it exceeds 1.0% by weight, it will have an adverse effect on the adhesive's viscoelasticity, which is not preferable. Among the free benzenecarboxylic acids and salts thereof, particularly preferred are monobenzoic acid and salts thereof. Its concentration is 0.5 to 8.0% by weight, preferably 0.8 to 2.0% by weight. 0.5
Lri viscous anti-viscosity prevention effect at less than 8.0% weight
Exceeding this is undesirable as it adversely affects the viscosity of the resulting glue. Further, as the zinc compound, zinc oxide, zinc phosphate, zinc nitrate, etc. are effectively used.

In particular, the addition of zinc oxide, which is said to have almost no effect on the human body, provides anti-mold properties and prevents viscosity reduction without affecting the physical properties of the starchy polymer. It generates things, and its stabilizing effect is also great. The applied concentration of vines is preferably 0.05 to 5.0% by weight, but can be 0.2 to 0.8% by weight.

and the zinc compound has a pH of 3.7 with the benzenecarboxylic acid or its salt and the trivalent metal compound as the main component.
It works like a 1J to a glue of ~6.0 and is extremely small 1i''
Demonstrates sufficient viscosity prevention effect. If it is less than 0.05% by weight, the effect is sufficient, and if it is more than 5.0% by weight, the effect will not change, but the solubility in the size liquid and the fractional stability of the zinc compound tend to decrease. Undesirable. f
In addition to using the iQ trivalent metal (compound e) alone, the combined addition of a 11j lead compound exhibits an effect as a facilitator that increases sensitivity to microorganisms such as mold and amylase.

In order to achieve the object of the present invention, when benzenecarboxylic acid or its salt is used within the above-mentioned allowable range and a nearly valent metal compound is used alone, the OPH value must be adjusted to a sizing agent of 3.5' to 6.0. It is effective in preventing viscosity reduction caused by amylase, but it cannot exhibit surface viscosity prevention effect outside this pH range, and if benzenecarboxylic acid or trivalent metal compound is used respectively in China or Germany, viscosity reduction prevention effect cannot be achieved. However, when both are used together and contain less than the active ingredient, the starch suspension is treated with an alkali and then treated with a mineral acid to give a pH of 3.7 to 6.0. The essential condition is that the product has been treated as a chemical agent. The use of crushed zinc compounds is tjffie PH3,7~6.0)
By adjusting the processed sizing agent'(II') to have a PHJt of 3.7-g, 0, it can be applied to a wider range of applications and can be used as a practical starch. In other words, in the case of using a trivalent metal compound, the starch suspension after the alkali treatment is treated with a mineral acid, and a zinc compound is usually added as a sizing agent with a pH of 3.7 to 9.0. In this case, the product glue may be selected as appropriate depending on the required properties, but preferably P
H4.5 to 7.0 is good.

The paste making according to the present invention is carried out by a generally known method as described above, and is not particularly limited. By dispersing or dissolving these formulations, it is possible to obtain a uniform starch paste 1] with the essential condition of forming a sizing agent with a pH of 6.0 or a sizing agent with a pH of 3.7 to 9.0 to which a zinc compound has been added. I can do it. In addition, if necessary, anti-foaming agents and anti-mold agents may be added to an extent that does not contradict the idea of the present invention, and it is also possible to add fragrance surfactants and the like.

As described above, the starch paste composition obtained by the present invention is easy to manufacture and can be distributed and supplied in stock. In particular, it has been confirmed through experiments that the viscosity reduction prevention period can be extended to a length of 150 days, and a strong effect can be maintained over a long period of time, for example, one and a half years or more. Compared to the conventional starch fWI WIJ, which is made by adding formalin to maintain long-term stability, it is particularly effective against amylase, which causes a decrease in the viscosity of starch.
It also improves the ease of contact during practical use, and is suitable for its use.
Q] has excellent performance as L'1, and is very advantageous in terms of use and economy. Thus, glue composition 9 of the present invention
All of the drawbacks of the conventional r/II O have been eliminated or significantly improved.

Furthermore, the present invention adds only a small amount of active ingredient I to achieve the effect of preventing a decrease in viscosity. It is not clear why this unexpectedly remarkable effect is exhibited against a wide range of amylases, but the reaction products of metal ions and benzenecarboxylic acid or its salts may be antagonistic or non-antagonistic to amylases. It is presumed that it acts as a type 9 inhibitor or acts on the C'(-1,47" glucosidic bond, α-1,6 glucosidic bond) of starch, weakening its affinity with the active group of amylase. It is thought that this provides an effective effect of preventing viscosity reduction.

Next, Examples and Comparative Examples will be given to show the test results of the present invention. Fl is not limited to these examples.

Note that parts and percentages in the examples indicate parts by weight and percentages by weight.

1. Comparative Example 1 Basic Starch Glue Composition Natural starches shown in Table 1 below were suspended in water and then transferred to a reaction tank for 30'
While stirring, 10% caustic soda aqueous solution was gradually added at step c, and stirring was continued for 20 minutes, followed by gradual addition of diffusion to neutralize the mixture to obtain a white translucent basic starch paste composition.

(2) Comparative Example 2 A formaldehyde-triple composition is obtained in the basic starch paste composition.

(3) Production of Examples 1 to 8 After suspending the natural starch shown in Table 1 in water, it was transferred to a reaction tank, and benzenecarboxylic acid or its soda salt was added thereto at 30'C. Gradually pour in the 10% caustic soda aqueous solution while stirring. After stirring for 20 minutes, gradually pour in the p+++ and i acids. When the glue becomes neutral, add the trivalent metal compound or After adding the chemical compound and the zinc compound, the pH is adjusted to obtain a white and transparent Tengo. ・Rice 2 Test conditions - f1 product 200
g into a suitable container, add 0.4 ml of VCo, 25% air-amylase (bacterial, Kishida Kagaku KK's sip liquid (using Toyo J Paper KK, Qualitative Ito Paper No. 2), The mixture was stirred 100 times on the left and right sides to form an even -C ratio.Then, after storage at 30°C for 1611 hours, curling was measured to see the effect of preventing viscosity reduction.These results are shown in Table 1. It was shown.

As is clear from the comparative examples, examples, and test results in Table 1 above, starch pastes in which the effective components of benzenecarboxylic acid, trivalent metal compounds, and zinc compounds are not added in the present invention cause a significant decrease in viscosity or a tendency thereof. do.

On the other hand, when the uninvented active ingredient IJ['' is added at a predetermined concentration, it exhibits an effect of preventing viscosity reduction against amylase, as seen in Examples 5 to 8. This is because the decrease in the viscosity of B11 starch IWI is caused by amylase, and as seen in Kokada Comparative Example 2, it has become clear that even a 37% aqueous solution of polyaltehyde cannot sufficiently prevent the decrease in viscosity. ing.

Patent applicant Fuyukio? Representative of 11 Industries Co., Ltd.
Yoshiaki Ashitachi603

Claims (1)

[Claims] (1) In the presence of benzenecarboxylic acid or its salt, a trivalent gold compound alone or a mixture of a trivalent gold compound and a zinc compound is added to form a starch suspension as an active ingredient, which is finally made into a mineral acid suspension. A starch paste composition characterized by being treated and dispersed or dissolved in water to provide an effect of preventing viscosity reduction! 21 1Jjl Claim No. 1, wherein the mineral acid treated product of the starch suspension a containing the benzene carboxylic acid or its salt and the 31'1lII metal compound as active ingredients is a sizing agent with a pH of 3.7 to 6.0. The starch paste composition described in Section i31 fJfj is a starch suspension treated with mineral acid containing benzenecarboxylic acid or its salt, a trivalent metal compound, and a zinc compound as active ingredients, and is a glue having a pH of 3.7 to 9.0. A starch paste composition according to claim 1 or t/'i (2): 4) A patent comprising a starch paste composition with a pH that is less than any one of the claims set forth in tjft. Starch composition according to claim 1 or 3 (5) Natural starch and water are mixed together, benzenecarboxylic acid or a salt thereof is added, and then a trivalent phenolic compound alone or 3 1i characterized in that a mixture of a valent metal compound and a zinc compound is added.
ij. A method for producing a starch paste composition according to any one of claims (1) to (3).