JPH0662376B2 - Antibacterial paper - Google Patents

Description

TECHNICAL FIELD The present invention relates to antibacterial paper containing or adhering an addition salt of an acid having a lipophilic group having a total carbon number of 9 or more of a bactericidal guanidine compound. is there.

"Prior art" Conventionally, the antibacterial paper used for the fruit bag to prevent the disease of fruits has been often used as an organic mercury compound as a bactericide to be contained or attached, but it is not only highly toxic to humans and animals. As is well known, it is no longer used because it causes chemical damage to plants.

"Problems to be solved by the invention" However, in recent years, antibacterial papers containing or adhering various bactericides have been proposed as alternatives. Poorly effective,
Further, there are problems in terms of phytotoxicity to plants and toxicity to humans and animals. For example, 1,1'-iminodi (octamethylene) diguanidine (hereinafter referred to as iminoctadine)
Is generally put to practical use as a low molecular weight acid addition salt, and its examples include hydrochlorides, sulfates, carbonates, nitrates, phosphates and other mineral salts or formates, acetates, It is known as an acid addition salt such as lactate, succinate, maleate, citrate, salicylate and p-toluenesulfonate. However, iminoctadine which has formed these addition salts, such as iminoctadine. Although triacetate has an excellent control effect against diseases that occur in useful plants,
When attempting to put it into practical use as an antibacterial paper, it causes phytotoxicity to fruits and has high toxicity to humans and animals (a deleterious substance). Since the triacetate is water-soluble, it lacks rain resistance (water resistance) and has a drawback that a long-term bactericidal effect cannot be expected. (JP-A-50-105906
No.) Furthermore, when iminoctadine triacetate is added as an aqueous solution or powder in a method of dispersing or dissolving a bactericide in molten paraffin, which is the most general method for producing antibacterial paper, and immersing the paper in this solution, In either case, the dispersibility in molten paraffin was poor and a uniform dispersion solution was not obtained, so it was difficult to attach the active ingredient of the desired concentration to the paper.

"Means for Solving the Problem" The present inventors have earnestly studied and found that the use of a bactericidal guanidine compound as an addition salt of an acid having a specific lipophilic group increases the oil solubility and improves the phase with molten paraffin. It was found that the bactericidal effect can be maintained for a long period of time because the solubility is good, the dispersion and the dissolution are easy, and the rain resistance (water resistance) is obtained, and the present invention has been completed.

That is, the present invention provides a bactericidal guanidine compound having a total carbon number of 9
The present invention provides a bacteriostatic paper characterized by containing or adhering an acid addition salt having a lipophilic group as described above.

"Structure" As the bactericidal guanidine compound in the present invention, iminoctadine [1,1'-iminodi (octamethylene) diguanidine], 1,8-diguanidinooctane, 1,1-
Diguanidinododecane (JP-A-57-48902), bis (8-guanidinooctyl) ether, bis (8-guanidinooctyl) thioether, 8-guanidinooctyl-3-guanidinopropyl ether (above, JP-A-56) -95102), 4-guanidinomethyl-1,8-bisguanidinooctane (JP-B-57)
-61252 No.), guanidation aliphatic polyamines (JP-B-57-7605, for example, G (CH ₂₎ containing iminoctadine _{8 G, G (CH 2)} 8 NH (CH 2) 8 NH 2, H 2 N (CH ₂ ) ₈ G '(CH ₂ ) ₈ NH
₂ , G (CH ₂ ) ₈ G '(CH ₂ ) ₈ NH ₂ , G (CH ₂ ) ₈ G' (CH ₂ ) ₈ G, G (CH ₂ ) ₈
NH (CH ₂ ) ₈ NH (CH ₂ ) ₈ G and other iminoctadine compounds such as one or more guanidine compounds) can be mentioned, but not limited to the above compounds.

Preferred is iminoctadine.

The acid of the acid addition salt of the present invention has a lipophilic group having 9 or more carbon atoms in total, and the lipophilic group is preferably linear.
It is a branched or cyclic alkyl group or alkylaryl group having a total carbon number of 9 or more. Particularly preferred are carboxylic acids, lipophilic groups having a total carbon number of 9 or more, sulfuric acid monoesters, sulfonic acids or phosphoric acid.

The carboxylic acid of the present invention may be a carboxylic acid having a total carbon number of 9 or more, preferably 9 to 25, particularly preferably 11 to 20 and having a lipophilic group, and saturated and unsaturated fatty acids, straight chain, Examples thereof include a carboxylic acid having a branched or cyclic alkyl group and a carboxylic acid having another functional group in the alkyl group.

Examples of such carboxylic acids are capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Arachidic acid, behenic acid, oleic acid, erucic acid,
Examples thereof include linoleic acid, linolenic acid, eleostearic acid, sulfated fatty acids, sulfonated fatty acids, hydroxylated fatty acids, cyclic fatty acids, dimer acids, and the like. Pork fat, sheep fat, beef fat, butter fat containing these Obtained from plant oils such as palm oil, soybean oil, olive oil, castor oil, palm oil, sesame oil, bran oil, tall oil, cottonseed oil, poppy oil, linseed oil, perilla oil, tung oil, rapeseed oil, peanut oil, etc. Also included are higher fatty acids that are used alone or as various mixtures. Further, resin acids such as abietic acid, neoabietic acid and dehydroabietic acid, and carboxylic acids having a polycyclic lipophilic group such as naphthenic acid are also included.

The sulfuric acid monoester of the present invention is a sulfuric acid monoester having a total carbon number of 9 or more, preferably 9 to 25, particularly preferably 11 to 20 and includes decyl sulfuric acid monoester, lauryl sulfuric acid monoester, myristyl sulfuric acid. Monoesters, primary higher alcohol sulfuric acid monoesters such as cetyl sulfuric acid monoester, stearyl sulfuric acid monoester, oleyl sulfuric acid monoester, secondary higher alcohol sulfuric acid monoesters, higher fatty acid ester sulfuric acid monoesters, higher alcohol ether sulfuric acid Examples include monoesters, alkylolated sulfuric acid monoesters of higher fatty acid amides, and resin acid alcohol sulfuric acid monoesters.

The sulfonic acid of the present invention is a sulfonic acid having a total carbon number of 9 or more, preferably 9 to 25, particularly preferably 11 to 20 and having a lipophilic group, such as primary higher alkyl sulfonic acid, secondary
Higher alkyl sulfonic acid, higher fatty acid ester sulfonic acid, higher alcohol / ether sulfonic acid, higher fatty acid amide alkyl sulfonic acid, sulfosuccinic acid ester, alkylbenzene sulfonic acid, alkylphenol sulfonic acid, alkylnaphthalene sulfonic acid, alkyl diphenyl Examples thereof include sulfonic acid, alkyl allyl ether sulfonic acid, alkyl allyl ester sulfonic acid, alkyl allyl ketone sulfonic acid, alkyl benzimidazole sulfonic acid, and lignin sulfonic acid.

The phosphorus oxyacid of the phosphorus oxyacid addition salt of the present invention has a total carbon number of 9 or more, preferably 9 to 25, particularly preferably 11 to 2
It has 0 lipophilic group, and the lipophilic group is preferably a linear, branched or cyclic alkyl group having 9 or more carbon atoms or an aryl group. Preferably, phosphoric acid, ester of phosphorous acid, phosphonic acid, phosphonous acid and ester thereof having a lipophilic group having 9 or more carbon atoms in total;
Alternatively, it is phosphinic acid, phosphinous acid; or polyphosphoric acid and its ester.

The phosphoric acid and phosphorous acid esters are monoesters or diesters of phosphoric acid and phosphorous acid having a lipophilic group having 9 or more carbon atoms in total, and examples thereof include dodecyl phosphate, α-naphthyl phosphate, and phosphoric acid. Di (2-ethylhexyl),
Examples thereof include diphenyl phosphite, dodecyl phosphite, α-naphthyl phosphite, didodecyl phosphite, and diphenyl phosphite.

The phosphonic acid, phosphonous acid and esters thereof,
Phosphonic acid, phosphonous acid, and monoesters thereof having a lipophilic group having 9 or more carbon atoms, such as dodecylphosphonic acid, 4-butylbenzylphosphonic acid, dodecylphosphonous acid, triphenylmethylphosphonous acid, and phenylphosphon. Examples thereof include acid monobutyl ester and benzyl phosphonous acid monobutyl ester.

The osphinic acid and phosphinous acid are phosphinic acid and phosphinic acid having a lipophilic group having 9 or more carbon atoms in total, and examples thereof include dicyclohexylphosphinic acid, diphenylphosphinic acid, didodecylphosphinic acid, and diphenylphosphinic acid. Can be mentioned.

The polyphosphoric acid and its ester are polyphosphoric acid and its ester having a lipophilic group having 9 or more carbon atoms in total, for example, diphenylpyrophosphoric acid, pyrophosphoric acid diphenyl ester, pyrophosphoric acid tributyl ester, hexaphosphoric acid penta (2- Examples thereof include ethylhexyl) ester.

The ester means an alkyl group having 9 or more carbon atoms,
It is a compound obtained by reacting a compound having an aryl group and a hydroxyl group such as alcohols and phenols with the phosphoric acid.

The bactericidal guanidine compound of the present invention has an addition salt of an acid having a lipophilic group having 9 or more carbon atoms in total, particularly a carboxylic acid as an acid,
Addition salts of sulfuric acid monoester, sulfonic acid and phosphoric acid have no phytotoxicity to plants (Japanese Patent Application No. 59-33978),
Further dodecylbenzenesulfonate also example iminoctadine in toxicity surface for humans and animals is greatly secure acute oral toxicity in comparison with the LD ₅₀ 300 mg / kg of acetic acid salt of guazatine the LD ₅₀ 2099mg / kg in rats Female It is expensive. In addition, the total carbon number of the bactericidal guanidine compound is 9
As the base paper containing or adhering the above-mentioned addition salt of an acid having a lipophilic group (hereinafter referred to as the present addition salt), in addition to ordinary pulp paper, polypropylene, polyamide, polyester, synthetic fibers such as polyacrylonitrile, or
Any of woven or non-woven fabric obtained from natural fibers such as cotton and hemp, and synthetic paper obtained from polystyrene, polypropylene, polyethylene and the like can be used.

The antibacterial paper of the present invention is 0.01 to 10% with respect to such a base paper.
This addition salt is contained or adhered so that it will be in the range of (weight ratio), but if the amount is 10% by weight or more, the bactericidal effect does not particularly increase, it only increases the cost and is economical. If it is less than 0.01% by weight, the antibacterial effect against penetration of bacteria is insufficient and it is not suitable for practical use.

The antibacterial paper of the present invention can exert a sufficient antibacterial effect only by containing or attaching an addition salt of an acid having a lipophilic group having a total carbon number of 9 or more of a bactericidal guanidine compound to the base paper. When used under conditions such as exposure to wind and rain for a long time, molten paraffin, oils and fats such as linseed oil or synthetic resins such as vinyl chloride, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer. It is desirable that a polymer, vinyl chloride-vinyl acetate copolymer, chloroprene, natural rubber or the like is used in combination in a solvent form or an emulsion form to be attached or contained.

In order to obtain the antibacterial paper of the present invention, any known method can be applied. As an example, a case where pulp paper is used as the base paper will be described. This acid addition salt is added, papermaking is performed, and if necessary, it is immersed in any one of molten paraffin, oil and resin.

(B) The acid addition salt, molten paraffin, oil and fat,
It is manufactured by a method of immersing paper in a liquid mixed with a resin or the like.

In particular, the acid addition salt of the present invention has high oil solubility and excellent miscibility and compatibility with molten paraffin, oils and fats, resins and the like, and has practically preferable physical properties.

The antibacterial paper obtained in this manner has a very low toxicity even though it has an excellent antibacterial effect, and therefore has a fruit bag,
It can be applied to a wide range of applications such as horticultural paper pots, multi-cultivation paper, protective paper for fruit transportation, wallpaper, and paper towels.

“Effect” As described above, the antibacterial paper containing or adhering the addition salt of the acid having a lipophilic group having a total carbon number of 9 or more of the bactericidal guanidine compound of the present invention is 1) bactericidal in use Since the phytotoxicity of guanidine compounds to useful crops is reduced, the safety is improved. Therefore, it can be used for many crops.

2) The rain resistance (water resistance) of the antibacterial paper is improved and the bactericidal effect is maintained for a long time.

3) The use of a specific bactericidal guanidine compound addition salt having excellent solubility or dispersibility in molten paraffin, fats and oils, which is an auxiliary agent at the time of production, makes it easy to produce antibacterial paper.

4) It is safe with improved toxicity to humans and animals.

Such a water-soluble bactericidal guanidine compound has a usefulness not found in low-molecular-weight acid addition salts.

[Examples] Hereinafter, the usefulness of the present invention will be specifically described with reference to Examples and Test Examples. In the text, "part" and "%" are based on weight unless otherwise specified.

Example 1 2 parts of a 50% methanol solution of iminoctadine-3dodecylbenzenesulfonate (hereinafter referred to as iminoctadine-3DBS salt) was mixed with 1 part of white carbon and dried,
A powder containing 50% of iminoctadine / 3DBS salt was obtained. Next, 0.38 parts of the above-mentioned powder was added to 100 parts of paraffin melted at 100 ° C. and dispersed by stirring (concentration of iminoctadine in paraffin: 500 ppm). 60 g / m ² of foreign paper was dipped in this paraffin solution, and the excess solution was hung in a thermostatic chamber at 100 ° C. to remove it, and then cooled at room temperature to obtain antibacterial paper.

Example 2 10 parts of iminoctadine-3DBS salt, 50 parts of naphthenic acid,
A preparation was prepared by mixing and dissolving 5 parts of potassium octylate and 35 parts of butyl carbitol. Next, 1.88 parts of the above preparation was added to 100 parts of paraffin melted at 100 ° C. and melted (concentration of iminoctadine in paraffin: 500 ppm)
). The antibacterial paper was obtained according to Example 1 below.

Example 3 1 part of iminoctadine / tall oil and fat proofing salt was added to linseed oil 9 parts.
It is dissolved in 9 parts, and Western paper is immersed in this solution to remove excess liquid and then dried to obtain antibacterial paper.

Example 4 40 parts of 1,12-diguanidinodecane dioleate, 5 parts of potassium oleate and 55 parts of butyl carbitol were mixed and dissolved to prepare a preparation. Next, 0.125 parts of the above-mentioned preparation was added and dissolved in 100 parts of paraffin melted at 100 ° C. (concentration of 1,12-guanidinododecane dioleate in paraffin of 500 ppm). The antibacterial paper was obtained according to Example 1 below.

Example 5 A preparation is prepared by mixing and dissolving 20 parts of iminoctadine-3 oleate, 5 parts of potassium oleate and 75 parts of butyl carbitol. Next, paraffin 100 melted at 100 ° C.
0.84 parts of the above-mentioned preparation was added to and dissolved therein (concentration of guazatine in paraffin: 500 ppm). The antibacterial paper was obtained according to Example 1 below.

Control Example 1 2 parts of a 50% aqueous solution of iminoctadine triacetate was mixed with 1 part of white carbon and then dried to obtain a powder containing 50% of iminoctadine triacetate. Next, 0.15 parts of the above powder was added to 100 parts of paraffin melted at 100 ° C. and stirred and dispersed (concentration of iminoctadine in paraffin 5
00 ppm). Immediately after the stirring was stopped, the active ingredient was separated and settled. Therefore, the paper was immersed in the paraffin solution while heating and stirring, and the antibacterial paper was obtained in the same manner as in Example 1 below.

Control Example 2 For 100 parts of paraffin melted at 100 ° C., N-
A wettable powder (commercially available product) containing 80% of (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide (diforman) as an active ingredient was added to 0.06.
Twenty-five parts were added and dispersed by stirring (concentration of difortan in paraffin: 500 ppm). Immediately after the stirring was stopped, the active ingredient was separated and settled. Therefore, the paper was immersed in the paraffin solution while stirring and heating, and the antibacterial paper was obtained in the same manner as in Example 1 below.

Comparative Example 3 Using a wettable powder (commercially available product) containing 75% of tetrachloroisophthalonitrile (daconyl) as an active ingredient,
Antibacterial paper having a Daconyl concentration of 500 ppm in paraffin was obtained in the same manner as in Control Example 2.

Test Example 1 Antibacterial effect test against pear black spot fungus 50, 100, 25 by the method shown in Examples and Controls
Paraffin containing 0,500ppm active ingredient
A test antibacterial paper was obtained by treating the paper with g / m ² of paper. The concentration of the iminoctadine compound was adjusted not as the acid addition salt of iminoctadine but as iminoctadine.

The test antibacterial paper prepared by the above method was cut into a square of 4 cm on each side, and this piece of paper was attached to the surface of a potato decoction agar plate medium. In the center of this pear black spot fungus (Alternaria
One drop of spore suspension of kikuchiana) was added dropwise, and the suspension was kept at 25 ° C for 4 days. The presence or absence of penetration of the bacteria was confirmed by removing a piece of paper on the medium and observing the medium with a microscope. The results are shown in Table 1. In addition, the observation results of dispersion stability of each drug are also shown.

In a preliminary test, the degree of penetration of bacteria and the extent of elongation of hyphae after penetration were correlated with the diameter of the flora grown on the test piece, so by measuring the diameter of the flora on the test piece, The degree of penetration (antibacterial effect) was evaluated.

The results are shown in Table 2.

From the above results, iminoctadine 3DBS salt and iminoctadine 3 oleate of the present invention are
It was found that it is equivalent to triacetate, has a superior antibacterial effect than difortan and daconyl, and can completely prevent bacterial penetration at a concentration of 250 ppm in paraffin.

Test Example 2 <Water resistance test> The test antibacterial paper prepared in Test Example 1 was immersed in sterilized water for 24 hours and then air-dried. Table 3 shows the results of confirming the penetration of the bacteria in the same manner as in Test Example 1 using the test antibacterial paper subjected to the water immersion treatment, and Table 4 shows the results of evaluating the penetration level.
Shown in the table.

From the above results, the iminoctadine / 3DBS salt and iminoctadine / 3oleate treated antibacterial paper after soaking in water was 25
There was no penetration at 0 ppm, which was exactly the same as the no penetration density obtained in the result of Test Example 1. On the other hand, in the difortan treated antibacterial paper, the concentration of no penetration of bacteria is 500ppm or more,
It was found that the sterilization effect was diminished by immersion in water. The non-penetrating concentration of iminoctadine triacetate-treated antibacterial paper after immersion in water was 500 ppm. The result obtained in Test Example 1 was 250.
It was found that the antibacterial effect was lower than that of ppm.

From the above Experimental Examples 1 and 2, it is estimated that the antibacterial paper of the present invention has an excellent effect of preventing penetration of bacteria, and is also excellent in rain resistance and water resistance, considering the actual use situation of the fruit antibacterial bag. To be done.

Test Example 3 <Dispersibility test of active ingredient in paraffin> The dispersibility of the fungicide of the present invention in molten paraffin was tested. 50% of iminoctadine / 3DBS salt of Example 1
Powder, preparation of iminoctadine / 3DBS salt of Example 2, preparation of 1,12-diguanidinododecane / 2-oleic acid of Example 4, Control Example 1 iminoctadine triacetate 50% powder, iminoctadine Sesquisulfate, iminoctadine sesquicarbonate, 1,12-diguanidinododecane
A comparative test was conducted using diacetate and difortan wettable powder (80% active ingredient, commercial product). Put 10 g of paraffin in a test tube with a plug having a diameter of 1.2 cm, and heat to 100 ° C. to melt.
The above drug was added to the test tube so that the active ingredient was 1000 ppm, shaken vigorously, and allowed to stand in a thermostat at 100 ° C. After 15 minutes, the paraffin was taken out from the thermostat and allowed to cool to solidify the paraffin, and about 1 g of the upper layer was scraped off, and the concentration of the active ingredient contained therein was measured.

The dispersibility of each bactericide is shown in Table 5 by the dispersion ratio of the following formula.

From the results shown in Table 5, the acid addition salt of the guanidine compound of the present invention group has much better dispersibility than the conventional guanidine compound of the control group, and especially those prepared by using a surfactant, a solvent, etc. It was confirmed that it was uniformly dissolved in paraffin and a high dispersion rate was obtained. Generally, guanidine compounds are
Since it has a strong polarity and no lipophilicity, it is insoluble in nonpolar solvents such as paraffin, and its dispersibility is poor. However, the specific guanidine compound of the present invention has solubility or good dispersibility in a solvent such as paraffin, which is an extremely useful property.

Claims (1)

[Claims] 1. A bactericidal paper containing or adhering an addition salt of an acid having a lipophilic group having a total carbon number of 9 or more of a bactericidal guanidine compound.