JP2003226789A - Mildewproofing vinyl acetate based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl acetate based resin composition excellent in mildewproofness for microorganisms in a wide range, particularly a resin composition comprising a polyvinyl alcohol, Vinylon (R), or a polyvinyl acetal, for forming a film or for fibers, excellent in mildewproofness at a low cost. <P>SOLUTION: The mildewproofing vinyl acetate based resin composition is characterized in that it contains an antibacterial and mildewproofing agent composition having as active ingredients imazalil alone, or its mixture with at least one selected from the group consisting of TBZ and BCM. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifungal vinyl acetate resin composition containing an antibacterial / antifungal agent composition.

[0002]

2. Description of the Related Art Most vinyl acetate resins are used for packaging materials such as clothes by making colorless and transparent film moldings, and are widely used for fibers, adhesives, paints, wire coatings, and other moldings. It is applied. However, when the environment in which these applied products are used is high temperature, high humidity, large temperature / humidity difference, or when dew condensation or dirt adheres to the products, microbes such as mold are generated. . As a result, the aesthetics of the product may be impaired, which leads to accelerated deterioration of the product itself and markedly reduced value of the product. Generally, antibacterial and antifungal agents have been used for the prevention, but they have not always been able to exert a sufficient antifungal effect.

[0003]

Most of the conventional antibacterial and antifungal agents are colored by the reaction between the antibacterial and antifungal agent and the crosslinking agent (aldehydes such as formalin) in the resin when added to the resin. The antibacterial and antifungal agents that can be used are extremely limited because the discoloration due to UV irradiation and ultraviolet irradiation is observed, the physical properties of the resin are affected, and the manufacturing conditions of various products are often under acidic conditions with hydrochloric acid. Was there. Specifically, TBZ and BCM
Have been used. However, these antibacterial and antifungal agents show variations in efficacy depending on the type of the target microorganisms, especially Ulocladium botrytis and Alternaria alternat.
The effect on black molds such as e is extremely weak, and it is necessary to increase the addition amount of these antibacterial and antifungal agents in order to obtain a practically sufficient antifungal effect, resulting in an increase in the cost of the product. Was there.

Therefore, the object of the present invention is to improve the antifungal properties of vinyl acetate resin compositions having excellent antifungal properties against a wide range of microorganisms, particularly polyvinyl alcohol, vinylon or polyvinyl acetal for film forming and fibers. It is to provide an excellent resin composition at low cost.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a specific antibacterial / fungal agent among the conventional antibacterial / mildew agents, or a combination thereof is used to obtain acetic acid. The present invention has been accomplished by discovering that when used in a vinyl-based resin, it exhibits an excellent antifungal effect against all molds and does not cause the vinyl acetate-based resin to be colored or discolored. That is, the present invention is (±) -1- [2- (2,4-
Dichlorophenyl) -2- (propenyloxy) ethyl] -1H-imidazole or an acid addition salt thereof (hereinafter referred to as imazalyl) alone or containing imazalil and 2- (4-thiazolyl) benzimidazole or an acid addition thereof. An antibacterial / mildew composition containing as an active ingredient at least one selected from the group consisting of salts (hereinafter referred to as TBZ) and methyl 2-benzimidazolylcarbamate or acid addition salts thereof (hereinafter referred to as BCM) An antifungal vinyl acetate-based resin composition is provided.

In the present invention, imazalil is used alone, or with imazalil, TBZ and / or BCM
When the antibacterial / mildewproofing composition consisting of is added to the vinyl acetate-based resin, the vinyl acetate-based resin composition has excellent antifungal properties with a small addition amount as compared to the case of using TBZ or BCM alone. In particular, it was found that a resin composition for film molding or fiber can be obtained. In particular, the vinyl acetate-based resin composition of the present invention exhibits remarkable antifungal property against black mold which cannot be suppressed by the conventional antibacterial and antifungal agents.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The antibacterial and antifungal agent used in the present invention includes imazalil alone or imazalil and T
An antibacterial and antifungal composition comprising BZ and / or BCM as an active ingredient.

The official name of Imazalil is "(±)-
1- [2- (2,4-dichlorophenyl) -2- (propenyloxy) ethyl] -1H-imidazole "and is represented by the following structural formula.

Examples of the acid which constitutes the acid addition salt of imazalil include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, lactic acid and sulfonic acid derivatives. The imazalil as described above can be used in the present invention, for example, obtained from Janssen (Belgium) under the trade name of "imazalil". Although imazalil can be used alone in the present invention, it is preferably used in combination with other specific antibacterial / antifungal agents. The case of combined use will be described below.

The official name of TBZ mixed with the above imazalil is "2- (4-thiazolyl) benzimidazole" and is represented by the following structural formula. Examples of the acid that constitutes the acid addition salt of TBZ include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, lactic acid and sulfonic acid derivatives.

The official name of BCM mixed with the above imazalil is "methyl 2-benzimidazolylcarbamate" and is represented by the following structural formula. Examples of the acid that constitutes the acid addition salt of BCM include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, lactic acid, and sulfonic acid derivatives.

Any of the above TBZ and BCM can be obtained from the market and used in the present invention. When used in combination with imazalil, any one of them may be blended with imazalil, or 2 You may mix a seed. The compounding amount of TBZ is in the range of 1 to 2000 parts by mass, preferably 10 to 1000 parts by mass, per 100 parts by mass of imazalil. B
The compounding amount of CM is 1 to 20 per 100 parts by mass of imazalil.
The amount is 00 parts by mass, preferably 10 to 1000 parts by mass.

When the compounding ratio of TBZ or BCM to imazalil is less than the above range, microorganisms (mainly molds)
Antibacterial activity against is not always sufficient. On the other hand, if the compounding ratio of TBZ or BCM to imazalil exceeds the above range, the effect of preventing coloring and discoloration of the resins is not sufficient. Also, TB against Imazalil
The compounding method of Z and / or BCM may be a simple mixing of the respective components, or the respective components may be blended in a suitable solvent or various other additives of vinyl acetate resin before use. Furthermore, imazalil and TBZ and / or B are used in the step of forming a film or fiber from vinyl acetate resin.
CM and CM may be added to the resin. Furthermore, you may add by a masterbatch system.

The present invention is characterized in that the above-mentioned imazalil alone or the antibacterial and antifungal composition blended as described above is included in a vinyl acetate resin. Examples of the vinyl acetate resin used in the present invention include polyvinyl acetate, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate-acrylic monomer copolymer, partial or complete saponification thereof. Thing or acetal compound,
Examples thereof include polyvinyl alcohol (hereinafter referred to as PVA), vinylon, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, polyvinyl nitrate and polyvinyl cinnamate polyvinyl ether, and these resins have a hydroxyl group and have a certain degree of hydrophilicity. The effect of the present invention is remarkable in the resin.

Particularly in the present invention, the vinyl acetate resin is P
It is effective when it is a VA resin (including vinylon resin). A preferred PVA resin has, for example, a polymerization degree of 1
PV with 000-2000 and saponification degree of 95-99.99%
PVA resin (mainly for vinylon film) prepared by mixing 5 to 30 parts by mass of glycerin with 100 parts by mass of A resin,
P with a degree of polymerization of 500 or more and a saponification degree of 60-99.99%
PVA resin (mainly for water-soluble PVA film) obtained by mixing 3 to 30 parts by mass of glycerin with 100 parts by mass of VA resin, PVA resin having polymerization degree of 1000 to 2000 and saponification degree of 90% or more (mainly for biaxially stretched PVA film) ) And the like.

The amount of the imazalil alone or the antibacterial / antifungal composition containing imazalil added to the vinyl acetate resin is 0.1% per 100 parts by mass of the vinyl acetate resin.
001 to 2 parts by mass, preferably 0.01 to 1 part by mass. Imazalil alone, or the addition amount of the antibacterial and mildewproofing agent composition containing imazalil is less than the above range, the product made of vinyl acetate resin does not have sufficient mildew proofing properties particularly against black mold, while, Even if the amount of the above-mentioned imazalil alone or the antibacterial / antifungal composition containing imazalil exceeds the above range, the effect of preventing coloration / discoloration is not necessarily improved depending on the amount added, which is not preferable in terms of cost.

The antifungal vinyl acetate-based resin of the present invention obtained as described above is, for example, a film for packaging clothes, foods and many other packaging, fibers, other molded articles, adhesives,
It may be in the form of paint, wire coating material, or the like. These various molded products produce mold, especially black mold, when the environment of use is high temperature, high humidity, large difference in temperature and humidity, and when dew condensation or dirt adheres to the product. Is sufficiently suppressed, its aesthetics, quality and commercial value are maintained for a long time.

The above-mentioned imazalil alone or the antibacterial / antifungal composition containing imazalil and the vinyl acetate resin to which these agents are added, which are used in the present invention, are as described above. Various known additives such as a colorant, an ultraviolet absorber, a plasticizer, an antistatic agent and the like can be added to the resin composition of the invention. Further, an antibacterial / antifungal agent other than the above may be used in combination.

Specific examples of antibacterial and antifungal agents other than the above which can be used in combination include zinc bis (2-pyridinethio-1-oxide) and α- [2- (4-chlorophenyl) ethyl].
-Α- (1,1-dimethylethyl) -1H-1,2,4
-Triazole-1-ethanol, N- (fluorodichloromethylthio) -phthalimide, 2,4,5,6-tetrachloroisophthalonitrile, N- (trichloromethylthio) -4-cyclohex-1,2-dicarboximide, N, N-dimethyl-N '-(fluorodichloromethylthio) -N "-phenylsulfamide, 2,3,3
5,6-Tetrachloro-4- (methylsulfonyl) pyridine, diiodomethyl-p-tolylsulfone, 5-
Chloro-2-methyl-4-isothiazolin-3-one,
2-Methyl-4-isothiazolin-3-one, 2-n-
Octylisothiazolin-3-one, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3-
Iodo-2-propynylbutyl carbamate, Nn-
Butyl-1,2-benzylisothiazolin-3-one,
1,2-dibromo-2,4-dicyanobutane, polyhexamethylene biguanide or acid addition salts thereof and the like can be mentioned.

[0020]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. However, the present invention is not limited to these examples. In the text, “part” or “%” is based on mass unless otherwise specified. Reference Example 1 An example of the composition of the antibacterial / antifungal agent used in the present invention is shown in Table 1 below.

[0021] TBZ: 2- (4-thiazolyl) benzimidazole
Lactate BCM: 2-benzimidazolyl methyl imazalil carbamate: (±) -1- [2- (2,4-dichlorophenyl) -2- (propenyloxy) ethyl] -1H-
Imidazole

The antibacterial and antifungal compositions and imazalil shown in Table 1 above were tested for their respective antibacterial activities against various microorganisms when TBZ and BCM were used alone, and the minimum inhibitory concentration (MIC) against the various microorganisms was measured. Examined. The results are shown in Tables 2 and 3 below. The test method is as follows. (1) Medium used: 1% glucose broth liquid medium was used for yeast and bacteria. Potato dextrose medium is used for mold. (2) Culture condition: 30 ° C. × 3 days culture for yeast and bacteria. Cultivate the mold at 25 ° C for 7 days.

[0023]

(4) Measuring method After sterilizing each medium, each drug was dissolved to a predetermined concentration, and 1 platinum loop was inoculated from each of the microorganisms previously cultured on the slant agar medium. The cells were cultured under conditions suitable for the above conditions, and after a certain period of time, the growth was visually observed for the presence or absence of growth. (5) Judgment The minimum inhibitory concentration was determined from the situation at each concentration of each drug and is shown in Tables 2 and 3 below.

[0025]

[0026] From the above results, the above TBZ or BC can be obtained by using imazalil alone or by combining imazalil with TBZ and imazalil with BCM, respectively.
It was recognized that the antibacterial properties have a synergistic effect in comparison with the use of M alone, and that they are useful drugs which complement each other in antibacterial properties against many kinds of microorganisms.

Example 1 (including comparative examples) A mixture of 50 parts of imazalyl sulfate and 50 parts of TBZ hydrochloride, 50 parts of imazalyl sulfate and 50 parts of BCM hydrochloride.
Part of PVA resin (polymerization degree 1300, saponification degree 95.5%, glycerin 20 parts / PVA 100 parts) to a concentration shown in Table 4 below.
Was added to. This was rolled into a sheet having a thickness of 2 mm and solidified to prepare a trial sheet. As a comparative control, a sheet to which the above-mentioned TBZ hydrochloride and BCM hydrochloride alone were added so as to have the concentrations shown in Table 4 below was also manufactured at the same time.

The above-mentioned trial sheet was used to evaluate the antibacterial and antifungal effect, and the obtained results are shown in Table 4 below. The test method is as follows. 40 mm × on a potato dextrose agar medium fixed on a 9 cm dish.
Place a prototype plate cut to 40 mm, spray a single spore suspension of the following bacterial species, 28 ± 2 ° C and RH 98%
Culture was carried out for 4 weeks. The bacterial species used were those shown in Reference Example 1 above.

The evaluation of the antifungal effect was expressed in three stages as shown below. Evaluation 3: No growth of test bacteria is observed on the surface of the sample. Evaluation 2: The growing area of the test bacteria on the sample surface does not exceed 1/3. Evaluation 1: The growing area of the test bacteria on the sample surface exceeds 1/3.

[0030]

From the results shown in Table 4 above, the antibacterial and antifungal composition containing imazalil alone or containing imazalil, which is used in the present invention, was excellent in vinyl acetate resin even at a low addition amount with respect to all tested fungi. Shows antifungal properties (however, imazalyl sulfate alone is not antifungal to Pen.fu. ). In contrast, TBZ hydrochloride and BCM
In each hydrochloride alone, it is clear that Alt.Alt. And Ulo.Bot. Mildew resistance is insufficient for such,
The superiority of the antibacterial and antifungal composition of imazalil used alone or the antibacterial and antifungal composition containing imazalil to the vinyl acetate-based resin is clear.

Example 2 (including comparative examples) PVA (polymerization degree 800, saponification degree 70%, glycerin 10)
(Parts / PVA 100 parts), the same test as in Example 1 was carried out under the following conditions, and the results are shown in Table 5. The drugs used are the drugs A to H, the drugs a to h, imazalil alone, TBZ alone and BCM alone shown in Reference Example 1. In addition, all the test strains, culture conditions, and determination methods are described in Example 1.
It carried out similarly to.

[0033]

From the results of Table 5 above, TBZ and BCM
In the use of each alone, the mildew- proofing effect against Alt.alt and Ulo.bot. Is weak, and with imazalil used alone in the present invention, the mildew- proofing effect is weak only against Pen.fu.
The other antibacterial and antifungal compositions containing imazalil showed excellent antifungal effect to all the tested fungi.

Example 3 (including Comparative Example) Each test sheet was prepared in the same manner as in Example 1 except that PVA (polymerization degree 1200, saponification degree 91%) was used, and each test sheet was colored by ultraviolet rays. I checked. For the coloring by ultraviolet rays, the degree of coloring was examined by irradiating ultraviolet rays for 500 hours with a fade meter, and the results are shown in Table 6 below.
The evaluation of the degree of coloring was displayed in three levels according to the following criteria. ◯: No coloring is recognized. Δ: Some coloring is recognized. X: Clear coloring is recognized.

[0036] From the results shown in Table 6 above, the antibacterial and antifungal composition containing imazalil alone or containing imazalil used in the present invention is clearly superior to TBZ sulfate and BCM sulfate in vinyl acetate resin. To be

[0037]

INDUSTRIAL APPLICABILITY The present invention, as shown in Reference Examples and Examples, comprises imazalil alone or imazalil and TB.
By adding an antibacterial and antifungal agent containing Z and / or BCM as an active ingredient to vinyl acetate resin, synergistically high antibacterial and antifungal effect is exhibited compared to the case where each agent is used alone. To do. Further, since the antibacterial and antifungal effect is exhibited with a low concentration of the additive, it is possible to reduce the cost and minimize the influence of the antibacterial and antifungal agent on the physical properties of the vinyl acetate resin.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 29/14 C08L 29/14 (72) Inventor Nobuko Horisaki 1157-16 Yubune, Oyama-machi, Sunto-gun, Shizuoka Stock Company Taisho Technos Laboratory F term (reference) 3E067 AB01 AB71 AB96 BA17A BB14A BB22A CA13 CA21 GC05 4J002 BE021 BE041 BE061 BF021 EU106 FD186

Claims (4)

[Claims] 1. (±) -1- [2- (2,4-Dichlorophenyl) -2- (propenyloxy) ethyl] -1H
-Imidazole or an acid addition salt thereof (hereinafter referred to as imazalil) alone, or imazalil and 2
-(4-thiazolyl) benzimidazole or an acid addition salt thereof and at least one selected from the group consisting of methyl 2-benzimidazolylcarbamate or acid addition salts thereof, and an antibacterial and antifungal composition are contained. A mildew-proof vinyl acetate-based resin composition comprising: 2. The vinyl acetate resin is vinyl acetate resin,
Copolymers of vinyl acetate with other monomers, their partial or complete saponification products, polyvinyl alcohol, vinylon,
Polyvinyl formal, polyvinyl acetoacetal,
The mildew-proof vinyl acetate resin composition according to claim 1, which is at least one selected from the group consisting of polyvinyl butyral, polyvinyl nitrate, and polyvinyl cinnamate polyvinyl ether. 3. The mildew-proof vinyl acetate resin composition according to claim 1, wherein the vinyl acetate resin is a polyvinyl alcohol resin for film molding or a vinylon resin for film molding. 4. The protective film according to claim 1, wherein the vinyl acetate-based resin is at least one resin selected from the group consisting of polyvinyl formal resin for film molding or fibers, polyvinyl acetoacetal resin and polyvinyl butyral resin. A moldable vinyl acetate resin composition.