JPH10120414A - Antimicrobial lamellar silicate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial lamellar silicate improved in water resistance, chemical resistance, heat resistance, weather resistance and antimicrobial effect durability by carrying an antimicrobial organic compound between the lamellae of a hydrogen type lamellar silicate. SOLUTION: This antimicrobial lamellar silicate is obtained by immersing 100 pts.wt. of a lamellar silicate having an average particle diameter of <=10μm and a cation exchange capacity of >=0.1meq/g and containing a hydrogen ion as an ion-exchangeable ion in an antimicrobial organic compound solution having a pH of 0.1-13, stirring the mixture at 40-60 deg.C for 0.5-72hr at a rotation rate of 10-1000 turns/min, and subsequently drying the treated silicate. >=0.1 pt.wt. of the antimicrobial organic compound is carried between the lamellae of the lamellar silicate. Conditions for producing the antimicrobial silicate are especially not limited, and may suitably be changed in dependence on the kind of the used antimicrobial organic compound, the kind and carrying capacity of the hydrogen type lamellar silicate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to water resistance, chemical resistance,
The present invention relates to a mold-resistant layered silicate excellent in heat resistance, durability of a mold-proofing effect and weather resistance. The silicate of the present invention is compounded with a material such as rubber, plastic or the like and molded or molded. Is useful as an antifungal agent capable of imparting antifungal properties to a material or a molded product by coating the surface of the material.

[0002]

2. Description of the Related Art Conventionally, various fungicides have been developed for imparting fungicidal properties to desired materials, and organic and inorganic fungicides are known. As an organic antibacterial and fungicide,
Quaternary ammonium salt compounds such as benzalkonium chloride, sulfur-containing benzimidazole compounds such as 2,4-thiazolylbenzimidazole, bisthiocyanate compounds such as methylenebisthiocyanate, quinolinol compounds such as 8-quinolinol, Alcohol compounds such as ethanol, aldehyde compounds such as formalin,
Fungicides such as phenolic compounds such as cresol and carboxylic compounds such as sorbic acid are known. On the other hand, as an antibacterial and antifungal agent of an inorganic type, a metal ion exhibiting antibacterial properties such as silver, copper, and zinc supported on activated carbon, apatite, zeolite and the like is known.

[0003]

However, the conventional fungicides have advantages and disadvantages in both organic and inorganic systems, and have a problem to be improved. That is, since an organic fungicide generally has poor heat resistance, if it is used for kneading into plastics or fibers, it may cause problems such as discoloration and foaming, and may cause sufficient volatilization and decomposition during processing, resulting in sufficient fungicide resistance. The effect could not be demonstrated. Furthermore, organic compounds are inferior in chemical resistance and have relatively high solubility in various solvents, so they are eluted when used, and the antifungal effect is reduced, or there is a concern that they may adversely affect the human body. There is a problem that the possible uses are limited. Further, although the inorganic fungicide is excellent in heat resistance and chemical resistance, it has a problem that it is inferior in fungicide effect to fungi as compared with antibacterial effect against bacteria. As a technique for solving the above-mentioned problem, an antibacterial antifungal silicate obtained by replacing at least a part of the ion-exchangeable metal ion of a layered silicate with an antibacterial antifungal organic coordination compound is known (Japanese Patent Application Laid-Open (JP-A) No) 4-292410). However, we have:
In the layered silicate obtained by this improved technique, there is a problem that the discoloration easily occurs and the weather resistance is poor, and it has been found that the cause is the ion exchange metal in the layered silicate. An object of the present invention is to provide a fungicidal layered silicate which is less likely to be discolored and has excellent weather resistance.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to solve the above problems, the present inventors have found that it is extremely effective to use a layered silicate in which ion-exchangeable metal ions are hydrogen ions, and have completed the present invention. That is, the present invention is a fungicidal phyllosilicate characterized in that a fungicidal organic compound is carried between layers of a phyllosilicate in which the ion-exchangeable ions are hydrogen ions.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ Layered silicate The layered silicate in the present invention is a layered silicate having a hydrogen ion as an ion-exchangeable ion (hereinafter, simply abbreviated as a hydrogen-type layered silicate), and usually has a metal ion as an ion-exchangeable ion (hereinafter, referred to as a metal ion). Can be easily obtained by performing a treatment for replacing hydrogen ions with ion-exchangeable metal ions of metal-type layered silicate).

[0006] The metal-type layered silicate can be used without any particular limitation as long as the crystal layer units are stacked on each other to form a layered structure, and may be either a natural product or a synthetic product. Preferred metal-type layered silicates include clay minerals, and specific examples thereof include the following. That is, montmorillonite, beidellite, hectorite,
Smectites such as saponite, balm curite,
Mica groups such as illite, muscovite, phlogopite and biotite, brittle mica groups such as margarite and clintite, chlorite groups such as sudoite, kaolinites such as kaolinite and halloysite, and serpentine groups such as antigorite And so on. Other preferred metal-type layered silicates include the following. That is, there are layered sodium silicates such as magadiite, kenyaite, kanemite, macatite, and ironerite, layered calcium silicates such as tobermorite, and synthetic mica in which anions such as hydroxyl ions are substituted with fluorine ions.

The method of replacing the ion-exchangeable metal ions of the metal-type layered silicate with hydrogen ions is not particularly limited, and any conventionally known method can be employed. For example, the metal-type layered silicate is brought into contact with an acid. Then, a method by an acid treatment to replace the ion-exchangeable metal ion and the hydrogen ion, or a metal-type layered silicate in which the ion-exchangeable metal ion in the metal-type layered silicate is once replaced with ammonium or an amine, There is a method of decomposing the ammonium or amine to produce hydrogen ions. When replacing the ion-exchangeable metal ions of the metal-type layered silicate with hydrogen ions, it is preferable to treat with an amount exceeding the ion-exchange capacity of the metal-type layered silicate. After the treatment, a solvent such as pure water or ethanol is sufficient. More preferably, it is washed. If the treatment and washing are not sufficient, the ion-exchangeable metal ions may remain between the layers of the hydrogen-type layered silicate, and the effect of the present invention of exhibiting excellent weather resistance may not be sufficiently exhibited. The hydrogen-type layered silicate suitable in the present invention is one in which at least 90% of the number of ion-exchangeable metal ions in the metal-type layered silicate is replaced by hydrogen ions.

The particle size of the hydrogen-type layered silicate according to the present invention,
The water content, cation exchange capacity, color and the like are not particularly limited.
When used for kneading into plastics, rubber or fibers, powder having an average particle size of 10 μm or less is preferable, more preferably a powder having an average particle size of 0.1 to 7 μm, and further, the particle size distribution is narrow, More preferably, the particles have a uniform particle size. In order to exhibit a sufficient fungicidal effect when a fungicidal layered silicate is used, the cation exchange capacity is preferably 0.1 meq / g or more. One of these hydrogen-type layered silicates may be used alone, or two or more of them may be used in combination for controlling the sustained release.

The fungicidal organic compound of the present invention is conventionally known and is not particularly limited, but is soluble in water or a polar organic solvent or soluble in an acid or alkali. Are preferred. As a preferred specific example, α- [2- (4-
Chlorophenyl) ethyl] -α- (1,1-dimethyl-
Triazole compounds such as 1H-1,2,4-triazol-1-yl-ethanol, 2- (4-thiazolyl)
Benzimidazole, methyl 2-benzimidazolecarbamate, 1- [ortho-chloro-β-[(para-chlorobenzyl) oxy] phenethyl] -imidazole 1
Imidazole compounds such as nitrates, haloalkylthio compounds such as N-fluorodichloromethylthiophthalimide, pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 1,2-benzisothiazoline Thiazole compounds such as -3-one and 2- (4-thiocyanomethylthio) benzthiazole;
There are quaternary ammonium compounds such as benzalkonium chloride. The antifungal organic compound in the present invention may have antibacterial properties in addition to antifungal properties, or may be one kind or two or more kinds.

The lower limit of the preferred amount of the fungicidal organic compound to be supported in the hydrogen-type layered silicate is as follows per 100 parts by weight (hereinafter simply referred to as "parts") of the fungicidal layered silicate in the present invention.
0.1 part, more preferably 1 part, particularly preferably 5 parts. If the amount is too small, the antifungal effect is reduced. The upper limit of the supported amount is determined by the type of the hydrogen-type layered silicate and the antifungal organic compound, but the antifungal layered silicate unnecessarily supported in a large amount is kneaded into a plastic or the like. Since there is a risk of causing discoloration and difficulty in controlling the sustained release property, it is preferable to set a suitable upper limit of the amount supported by a preliminary test.

The method of supporting the fungicide-resistant organic compound on the hydrogen-type layered silicate is not particularly limited. Basically, the fungicide-resistant organic compound and the hydrogen-type layered silicate may be brought into contact with each other. It can be introduced regardless of whether the moldy organic compound is in a solid phase, a liquid phase, or a gas phase. For example, in the loading by the ion exchange method in the liquid phase, the fungicidal organic compound is dissolved in a highly soluble solvent, a hydrogenated layered silicate is added to the solution, and the mixture is stirred, followed by filtration, washing, drying, By crushing,
A fungicidal layered silicate in which an antifungal organic compound is supported on a hydrogen-type layered silicate can be obtained. Further, drying and pulverization may be performed without washing.

The conditions for preparing the above-mentioned mildew-resistant layered silicate are not particularly limited, and may be appropriately changed depending on the kind of the mildewproof organic compound and the hydrogen-type layered silicate to be used, the amount of the mildewproof organic compound to be carried, and the like. Can be. Specifically, for example, the pH of the solvent is 0.1 to 13, the stirring time is 0.5 to 72 hours,
The stirring temperature may be from room temperature to, for example, about 40 ° C. to 60 ° C., and the stirring speed may be 10 to 1000 times / minute.

Use The antifungal layered silicate of the present invention is useful as an antifungal agent imparting an excellent antifungal effect by being blended with various materials. Examples of materials that can be blended include rubbers such as silicone and acrylic; and plastics such as vinyl chloride, polyolefin, polyurethane, ABS, polystyrene, vinyl acetate, and polycarbonate.

The fungicidal layered silicate of the present invention is prepared by suspending a suspension in a liquid medium such as water or an organic solvent in the presence or absence of a binder by spray coating, coater coating, dipping, or the like. It can also be applied on the surface of various metals, plastics, ceramics, etc. to form a film by ordinary application means such as brush coating, roll coating, etc., thus inhibiting the growth of mold on articles of various materials can do. Furthermore,
The mold-resistant layered silicate of the present invention can be mixed with a material and molded.
It can be in any of a variety of shapes, such as a film, sheet, plate or block. A preferable ratio when the composition of the present invention is blended with various materials is 0.1 to 30 parts, more preferably 0.5 to 10 parts, per 100 parts of the material for imparting antifungal properties. . Specific applications of the material or molded article containing the mold-resistant layered silicate of the present invention include textile products such as towels, carpets, curtains, and clothing; leather; refrigerators, washing machines, dish dryers, vacuum cleaners, and air conditioners. Appliances such as machines, televisions and telephones; building materials such as wallpaper, tiles, bricks, concrete, screws, joints; washbasins, toothbrushes,
Sundry goods such as brooms, hoses, slippers, recycle bins, scrubbers; kitchenware such as cutting boards, triangular corners, kitchen knives; toiletries; various coating materials, paints and adhesives.

[0015]

The present invention will be described below in more detail with reference to examples. (Reference Example 1) Preparation of Hydrogen-Type Layered Silicate To 0.04 mol of a 0.05 mol / l HCl aqueous solution, 100.0 g of Na-type fluorine-substituted synthetic moth, which is a metal-type layered silicate, was stirred at room temperature for 24 hours ( (400 rpm). After the suspension was filtered, the filtrate was washed with ion-exchanged water, and it was confirmed that the Na ion in the washing solution was 1 ppm or less, and the washing was completed. Then, it was dried at 100 ° C. and crushed lightly. A hydrogen-type layered silicate having an average particle size of 5 μm was obtained.

(Example 1) Preparation of antifungal layered silicate In a 500 ml solution of equal volume of methanol and water, α- [2- (4-chlorophenyl) was used as an antifungal organic compound.
Ethyl] -α- (1,1-dimethyl-1H-1,2,4
-Triazol-1-yl-ethanol (5.0 g) was added and completely dissolved. 45.0 g of the hydrogen-type layered silicate obtained in Reference Example 1 was added thereto, and the mixture was stirred at room temperature for 1 hour, dried in a degreasing furnace as it was, and crushed lightly to form a white fungicidal layer having an average particle size of 5 μm. Silicate A was obtained.

(Example 2) Preparation of a fungicidal layered silicate The same procedure as in Example 1 was carried out except that the fungicidal organic compound was changed to 2- (4-thiazolyl) benzimidazole, and the average particle size was 5 µm. Was obtained as a white mold-resistant layered silicate B.

Comparative Example 1 The procedure of Example 1 was repeated, except that the layered silicate supporting the fungicidal organic compound was changed to a Na-type fluorine-substituted synthetic plum without replacing hydrogen ions. Thus, a white mold-resistant layered silicate C having an average particle size of 5 μm was obtained.

Comparative Example 2 The procedure of Example 2 was repeated, except that the layered silicate supporting the fungicidal organic compound was changed to a Na-type fluorine-substituted synthetic plum without replacing hydrogen ions. Thus, a white mold-resistant layered silicate D having an average particle size of 5 μm was obtained.

(Use Example 1) 3.0 g of fungicidal layered silicate A was added to 147 g of the resin composition A shown in Table 1 below.
After uniformly kneading at 150 ° C. for 5 minutes with a heating roll, a press machine (170 ° C., 100 kg / cm ² ) has a thickness of 2 mm and length of
The test piece was formed into a plate having a size of 2 cm and a width of 10 cm, and cut into a size of 2 cm square.

(Use Example 2) A test piece was prepared in the same manner as in Use Example 1 except that the mold-resistant layered silicate A was replaced with the mold-resistant layered silicate B.

(Use Example 3) The same procedure as in Use Example 1 was carried out except that the object to which the fungicidal layered silicate was blended was changed to the resin composition B of Table 1 instead of the resin composition A of Table 1 below. Test pieces were prepared.

[0023]

[Table 1]

* 1: TS1100 (manufactured by Toagosei Co., Ltd.) * 2: manufactured by Toho Rika Kogyo Co., Ltd. * 3: 300K (manufactured by Daicel Chemical Industries Co., Ltd.) * 4: ADK STAB 37 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) * 5: ADK STAB 102 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) * 6: Novalon AG300 (trade name, manufactured by Toagosei Co., Ltd.)

(Use Example 4) In the same manner as in Use Example 2, except that the object to which the fungicidal layered silicate was blended was changed to the resin composition B of Table 1 instead of the resin composition A of Table 1 above. Test pieces were prepared.

(Comparative Use Example 1) α- [2- (4-Chlorophenyl) ethyl] -α- which is a fungicidal organic compound
(149.7 g of the resin composition A shown in Table 1 above, without supporting 1,1-dimethyl-1H-1,2,4-triazol-1-yl-ethanol on the hydrogen-type layered silicate.
A test piece was prepared in the same manner as in Use Example 1 except that 0.3 g was directly added to the test piece.

(Comparative Use Example 2) The 2- (4-thiazolyl) benzimidazole which is a fungicidal organic compound was not supported on the hydrogen-type layered silicate, and was added to 149.7 g of the resin composition A shown in Table 1. Use example 1 except that 0.3g was added directly
A test piece was prepared in the same manner.

(Comparative Use Example 3) α- [2- (4-Chlorophenyl) ethyl] -α- which is a fungicidal organic compound
(1.1-Dimethyl-1H-1,2,4-triazol-1-yl-ethanol was directly supported on 149.7 g of the resin composition B shown in Table 1 without being supported on the hydrogenated layered silicate. A test piece was prepared in the same manner as in Use Example 1 except that 3 g was added.

(Comparative Use Example 4) A 2- (4-thiazolyl) benzimidazole which is a fungicidal organic compound was not supported on a layered silicate, and the resin composition B shown in Table 1 was used.
A test piece was prepared in the same manner as in Use Example 1 except that 0.3 g was directly added to 9.7 g.

(Comparative Use Example 5) A test piece was prepared in the same manner as in Use Example 1 except that the mold-resistant layered silicate A was replaced with the mold-resistant layered silicate C.

(Comparative Use Example 6) A test piece was prepared in the same manner as in Use Example 1 except that the mold-resistant layered silicate A was replaced with the mold-resistant layered silicate D.

(Comparative Use Example 7) A test piece was prepared in the same manner as in Use Example 3 except that the fungicide-resistant layered silicate C was used instead of the fungicide-resistant layered silicate A.

(Comparative Use Example 8) A test piece was prepared in the same manner as in Use Example 3 except that the fungicide-resistant layered silicate A was replaced with the fungicide-resistant layered silicate D.

(Comparative Use Example 9) A hydrogen-type layered silicate in which no mold-proof organic compound is supported in place of the mold-resistant organic layered silicate in which the hydrogen-type layered silicate carries a fungicide-resistant organic compound A test piece was prepared in the same manner as in Use Example 1 except that was mixed.

(Comparative Use Example 10) Na-type fluorine-substituted synthesis in which a mold-resistant organic compound is not supported at all in place of the mold-resistant layered silicate obtained by supporting a mold-resistant organic compound on a hydrogen-type layered silicate A test piece was prepared in the same manner as in Use Example 1 except that plum was compounded.

Evaluation of antifungal property The test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 10 were allowed to stand in warm water at 50 ° C. for 7 days, and after 1 day and 7 days, the antifungal property was measured. To evaluate the antifungal effect over time. As a method for evaluating the antifungal property, the test piece was placed on a potato dextrol agar medium, and the antifungal property was evaluated by measuring the width of the formation of the inhibition zone after 14 days. Molds include black koji mold (Aspergil
ls niger) and black mold (Cladosporium cladosporioides)
Were used. The results of the antifungal test are shown in Tables 2 and 3 below.
Shown in

Evaluation of Weather Resistance The test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 10 were evaluated using a weather resistance tester (UVCON manufactured by ATLAS). The test conditions of the weather resistance tester are as follows: one cycle is 8 hours, a 4-hour process of irradiating ultraviolet rays of 350 nm or less at 60 ° C., and a 4-hour process of leaving at 40 ° C. in an atmosphere of 95% or more humidity. Become. Using a color difference meter (color difference meter SZ- # 80 manufactured by Nippon Denshoku Industries Co., Ltd.), the color (L ₁ , a ₁ , b ₁ ) after 0 cycles of the weather resistance test and the color (L ₂ , a ₂ , b ₂ ) were measured, and the color difference (ΔE) was calculated by the following equation [1] using these measured values. ΔE = [(L ₁ -L ₂ ) ² + (a ₁ -a ₂ ) ² + (b ₁ -b ₂ ) ² ] [1] The results of the weather resistance test obtained as described above are shown in Table 2 below. , And Table 3.

[0038]

[Table 2]

[0039]

[Table 3]

As can be seen from the comparison between Tables 2 and 3, the antifungal layered silicate of the present invention has a longer time than the case where the antifungal organic compound is directly added to the resin imparting antifungal property. Even if immersed in warm water, the antifungal property is not lost and the antifungal effect is excellent in persistence. Further, the antifungal layered silicate of the present invention is less likely to cause discoloration and is excellent in weather resistance as compared with a case where the layered silicate serving as the host of the antifungal organic compound is not of the hydrogen type. Its properties are antibacterial, silver,
Even if a compound containing an antibacterial metal ion such as copper or zinc coexists, it is not damaged.

[0041]

The fungicidal layered silicate of the present invention is superior in water resistance, chemical resistance, heat resistance and persistence of the fungicide effect to conventional organic fungicides, and has less discoloration. Excellent weather resistance. According to these properties, the antifungal layered silicate of the present invention can be used for various rubbers, plastics and the like and films and sheets formed thereof, molded articles such as sheets, and various fibers, paper, leather,
It can impart antifungal properties to paints, adhesives, heat insulating materials, caulking materials, and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiro Hiragawa 1-1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi Prefecture Inside Nagoya Research Institute, Toagosei Co., Ltd. (72) Inventor Hideki Kato Funami-cho, Minato-ku, Nagoya-shi, Aichi No. 1, No. 1 Toagosei Co., Ltd. Nagoya Research Laboratory

Claims (1)

[Claims] 1. An antifungal layered silicate comprising a layered silicate in which the ion-exchangeable ions are hydrogen ions, wherein an antifungal organic compound is carried between layers.