JPH03167103A - Mildew-proofing and algicidal resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition showing excellent mildew-proofing and algicidal effects by blending a polyolefin-based resin with 2-(4-thiazolyl) benzimidazole and 2-n-octyl-4-isothiazolin-3-one. CONSTITUTION:A polyolefin-based resin is blended with preferably 0.001-1.0wt.% 2-(4-thiazolyl)benzimidazole and 2-n-octyl-4-isothiazolin-3-one in a ratio of preferably (3:7)-(7:3) (weight ratio) to give a mildew proofing and algicidal resin composition. An ethylene homopolymer, propylene homopolymer and an ethylenevinyl acetate copolymer are preferable as the polyolefin-based resin. Films or molded articles obtained from the composition shows excellent mildew-proofing properties and algicidal properties and durability. This composition is extremely suitable for packaging of foods, drugs, etc., films for agriculture, construction of civil engineering, etc., pipes, sheaths, ropes, fishing nets, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a mold- and algae-proofing resin composition that exhibits excellent mold- and algae-proofing effects in various products made from polyolefin resins.

<Prior Art> In recent years, damage caused by mold and algae to resin products has become a problem.

For example, resin moldings related to architectural interior materials, agricultural films, various resin tableware for household use, garbage bags, garbage bags, triangular corners of sinks, etc. often get dirty and are used in humid environments. The possibility of mold and algae growth is extremely high.

When mold and algae grow on these products, the mold and algae on the surface not only impair the aesthetic appearance but also cause deterioration of the crystallinity of the product.

Additionally, mold and algae that grow on these products contaminate the environment and cause new pollution. Furthermore, mold or its spores are often harmful to the human body.

For the reasons mentioned above, there is a need for effective mold and algae prevention methods for resin products. One of these is adding additives that have the effect of inhibiting the growth of mold or algae to resin molded products.
It has been widely considered to impart an anti-mold or algae effect by kneading and molding. However, even when looking only at the anti-mold effect, conventional techniques have many problems such as the following. Ta.

Conventionally, additives that have been blended for the purpose of preventing mold in resin molded products include to, 10"-oxybisphenoxyarsine (hereinafter referred to as "compound"), and 2-(4-thiazolyl).
-benzimidazole (hereinafter referred to as compound B), N-(
Compounds such as fluorodichloromethylthio)-phthalimide (hereinafter referred to as compound C) and 2-n-octyl-4-isothiazolin-3-one (hereinafter referred to as compound R) are known.

However, when each of the above compounds B, C, or D is used alone in a resin composition, its antifungal effect cannot be said to be sufficient.

On the other hand, although Compound A has a strong fungicidal effect, it has problems such as a unique odor and toxicity.

In addition, there are cases where the resin composition and the compound blended for fungicidal purposes are not compatible, and the inherent activity of the compound cannot be fully exhibited. For example, a plasticizer is usually added to resin molded products such as soft vinyl chloride polymers, but Compound A has too high solubility in the plasticizer. Therefore, in a resin composition in which a compound is blended with a soft vinyl chloride resin,
There are problems such as the rate at which the compound transfers to the surface of the molded product is too fast, and the durability of the antifungal effect and water resistance are poor.

Compound A Compound B Compound C Compound D <Problems to be Solved by the Invention> The present invention solves the problems of the conventional techniques as described above, and provides a resin composition with excellent anti-mold and anti-algae properties, which has been in great demand in recent years. It provides: In other words, the conditions required for an ideal mold- and algae-proofing resin composition are: 1) It should exhibit high activity against a wide variety of molds and algae, and 2) The active ingredient should have high heat resistance and be able to be used during resin molding. 3) High safety for users and manufacturing workers 4) Good compatibility between the active ingredient and the resin component, and the antifungal and antialgal activity of the resin composition lasts for a long time. and excellent water resistance. The object of the present invention is to obtain a fungicidal and algaeproof resin composition having these properties.

Means for Solving the Problems In order to achieve the object described in item L, the present inventors first conducted extensive research on resin compositions containing various additives that have the effect of preventing mold growth. As a result, a resin composition in which a mixture of 2-(4-thiazolyl)-benzimidazole (compound B) and 2-n-octyl-4-isothiazolin-3-one (compound D) was blended with a polyolefin resin was extremely It was discovered that it has excellent properties.

That is, Compound B and Compound RI sufficiently withstood the high temperatures during the molding process of the resin composition of the present invention, and by blending them together, they exhibited a high antifungal activity that could not be predicted by each alone.

In addition, as a result of examining resins that are compatible with the mixture of compounds B and D, we found that when the mixture of compounds B and D is blended with various resins such as polymethyl methacrylate and polystyrene,
It has been found that, while no antifungal effect was observed, a particularly high antifungal effect is exhibited when blended with a polyolefin resin, and its durability and water resistance are also excellent.

Furthermore, it has been found that polyolefin resins containing Compounds B and D also exhibit high algae-proofing properties.

That is, the present invention is characterized in that 2-(4-thiazolyl)-benzimidazole (compound B) and 2-n-octyl-4-isothiazolin-3-one (compound D) are blended into a polyolefin resin. It is a mold-proofing and algae-proofing resin composition.

Polyolefin resins used in the present invention include α-olefin homopolymers such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene-butene 1 copolymers, and ethylene-4-methyl-1-pentene copolymers. , ethylene-hexene copolymer and propylene
Ethylene-α-olefin copolymer such as butene 1 copolymer or propylene-α-olefin copolymer ff1 (
Examples include L-ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, and ionomer resin.

These resins have a melt index of 0.3g/10
The melt index is preferably 0.5 g/10 min or more and 30 g/10 min or less from the viewpoint of moldability, molded product strength, etc.

If the melt index is less than 0.3 g/10 minutes, molding processability will decrease, and if the melt index is less than 80 g/10 minutes,
If the heating time exceeds 10 minutes, the strength of the molded product will weaken, which is not preferable.

The compound B and compound R are blended in a weight ratio of 3 = 7 to 7:3, and their total amount is 0.001% to 1.0% by weight based on the resin composition. is preferable, and the weight ratio of compound B:compound R is 4:6 to 6:4,
And their total amount is 0.005 to 0.005 to the resin composition.
If the weight ratio of compounds B and D, which is more preferably 1.0% by weight, is outside the above range, the control effect against a wide range of molds or algae will decrease. Furthermore, if the total amount of compounds B and D is less than 0.001% by weight, the durability and water resistance of the anti-mold and algae effect will be insufficient, while if it exceeds 1.0% by weight, it will be economically disadvantageous. Not only this, but also the resin molded product becomes discolored and sticky, which is undesirable.

The resin composition of the present invention comprises a polyolefin resin and a compound B.
and D in a predetermined ratio, roll it according to a conventional method,
It can be obtained by kneading using a Nigu, Banbury mixer, a single-screw or twin-screw extruder, or the like.

The amounts of compounds B and D to be blended into this resin composition may be such that the obtained resin composition is used as is to form a molded product, or a resin composition containing a high blended amount of compounds B and D ( (referred to as a masterbatch).

The yIrJ composition of the present invention is not particularly limited in the molding method or the shape of the molded product, and may be formed into a single layer, ? It is possible to easily mold single-layer films and sheets, molded articles of various shapes by injection molding, and various containers etc. by blow molding.

Furthermore, in the resin composition of the present invention, in addition to the above-mentioned anti-fungal additives, stabilizers, antioxidants, ultraviolet absorbers, M refractors, foaming agents, colorants, fillers, Compounding agents such as antistatic agents, lubricants, crosslinking agents, and diluents can be added.

Applications are not necessarily limited as long as they require mold and algae prevention effects, but include resin moldings for building interior materials, general packaging films for foods, medicines, machinery, tools, etc., greenhouses and tunnel cultivation. Agricultural films such as concrete roadbeds, films for civil engineering works such as roofing, pipes for water and sewage systems, chemical factories, civil engineering works, etc., packaging materials laminated with metal foils, insulation for power communication cables, etc. For sheaths, various household tableware, containers, electrical, mechanical parts, interior and exterior products for automobiles, ships, etc., ropes, cloth,
Examples include fishing nets.

<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.

In order to demonstrate that the resin composition of the present invention exhibits excellent antifungal and antialgal effects, the following evaluation test was conducted.

(1) Antifungal effect evaluation test sample was cut into 5 cm square pieces and placed on a potato dextrose agar medium, and from above the following 7 types were prepared.
A mixed suspension of mold spores (lid) was evenly sprayed to inoculate the mold, and then cultured at 28°C. 28 days after vaccination, 5
After 6 and 84 days, the mold growth was observed and evaluated. The test results are shown in Table 2.

(Inoculum) Aspergillus niger
iger) Penicillium citrinum Chaetomium globosum
osum) Glioclum virens (Gliocl)
adjum vrrans) Aureobasidium pullulans
Paecilomyces sp.
, ) Alternaria sp.
) (Evaluation basis $) No mold growth observed on test piece ± Mold growth observed on 1/10 surface or less + 1
il where mold growth is observed on the /10 to 1/4 side
Mold growth is observed on the 1/4 to 1/2 side t1/
Mold growth is observed on 2 to 374 surfaces.t 3z Mold growth is observed on 4 or more surfaces.
3cm, width 24cm.

After 48 hours of immersion in a 10 cm deep (with rotary pump) sample, the sample was cut into 5 cm square pieces and placed on a potato dextrose agar medium. was inoculated by spray. After this,
The cells were cultured at 28°C and evaluated after 28 days according to the evaluation criteria described above. The test results are shown in Table 2.

(3) Algae prevention effect evaluation test sample was cut into a 5CI1) square size and immersed in the following algae culture solution 200-.

Two drops of algae-contaminated water were added to the culture solution in which the sample was immersed, and cultured for two weeks in a greenhouse (room temperature 24-27°C). After culturing, the immersed samples were taken out, and the state of adhesion of algae on the sample surface was observed and evaluated. The test results are shown in Table 2.

(Algae culture solution composition) Ca (NOs)g 1. Og, KCl 0.
25g.

Mg5C)s・70zO0,25g, F e C
1z 0125g.

KH! PO40.25g, tap water 1000d (
Evaluation criteria) No algae adhesion on the sample (10) No more than 1/2 of the sample has Atsushi H adhesion (2) More than 1/2 of the sample has algae adhesion Example 1 Low-density polyethylene (Sumitomo Chemical Co., Ltd.) Product name manufactured by Kogyo Co., Ltd.
Sumirikisen G301, density 0.920 g/c+1
, melt index 20g/10min) to compound B (
(manufactured by Tokyo Chemical Industry Co., Ltd., 2-(4-thiacyl)benzimidazole) and Compound D (manufactured by Rohm and Haas, trade name 5KANE M-8 (2-n-octyl-4-isothiazolin-3one)), respectively. Mix 2.5% by weight and use a Banbury type kneader to mix 150% by weight.
Kneaded for 10 minutes at
-MB) was obtained.

Next, low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumikisen F20B-1, density 0.924 g
/cd, melt index 1.5 g/10 min) and the above PE-MB was blended in an amount of IO weight % to form a film at an extrusion temperature of 180°C using a blown film forming machine.

The resulting film was transparent and had a thickness of 100 μm.

Table 2 shows the antifungal and antialgal effects of this film.

Example 2 Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Evati) H201), vinyl acetate content 15% by weight, melt index 3 g/10 min) using PE- Inflation film molding was carried out in the same manner as in Example 1 except that MB was blended in an amount of 10% hydrogenated vinegar to obtain a transparent film with a thickness of 75 μm. Table 2 shows the antifungal and antialgal effects of this film.

Examples 3 to 4 Low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumirikisen G701, density 0.918 g/cd, melt index 7 g/10 minutes) and high-density polyethylene (manufactured by Shindaikyo Petrochemical Industries, Ltd., Using Chubu Polyethylene 4010 (trade name, density 0.957 g/cd, melt index 5 g/10 min), 20% by weight of PE-MB used in Example 1 was blended with each polyethylene. The blend was molded in a 10 oz injection molding machine at a molding temperature of 220°.
Injection molded at C1 mold temperature 50°C, length 100×
A plate-shaped molded product with a width of 150 m and a thickness of 2 cm was obtained. Table 2 shows the antifungal and antialgal effects of these molded products.

Example 5 Polypropylene (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumitomo Noblen W501, melt index 8g/1
Compound B and Compound R shown in Example 1 were mixed at 0.25 wt. A polypropylene composition containing an algaecide was prepared. The composition was injection-molded using a 10-ounce injection molding machine at a molding temperature of 250°C and a mold temperature of 50°C, and
A plate-shaped molded product having a size of 0 mm and a thickness of 2 III m was obtained. Table 2 shows the antifungal and antialgal effects of this molded product.

Example 6 The polypropylene used in Example 5 was converted to Sumitomo Noblen A.
Z564 (melt index, 30g/10 minutes)
, and the blending amounts of compound B and compound R were each 0.1
A polypropylene composition containing a fungicide and algaecide was prepared in the same manner as in Example 5 except that the weight percentage was changed, and then a plate-shaped injection molded article was obtained. Table 2 shows the antifungal and antialgal effects of this molded product.

Example 7 Polypropylene (manufactured by Sumitomo Chemical Co., Ltd., product name Sumitomo Noblen W50L Melt Index 8g/10
3% by weight of Compound B O and Compound D O
. The mold-proofing and algae-proofing effects of this molded product are
Shown in the table.

Example 8 Polypropylene (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumitomo Noblen W501, melt index 8g/1
0 min) of Compound B O,002% by weight and Compound D
A polypropylene composition containing a fungicide and algaecide was prepared in the same manner as in Example 5 by blending 0.003% by weight, and then a plate-shaped injection molded article was obtained. Table 2 shows the antifungal and antialgal effects of this molded product.

Comparative Examples 1 to 3 Polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd.)
Product name Sumipex MHO), polystyrene (same as above, product name Nisbrite 8) or acrylonitrile
Using a butadiene-styrene copolymer (manufactured by Sumitomo Nogatatsuta Co., Ltd., trade name Talalastic M1), 0.25% by weight each of Compound B and Compound R shown in Example 1 were blended with these resins. A resin composition containing a fungicide and algaecide was produced in the same manner as in Example 5, and then a plate-shaped injection molded product was obtained. Table 2 shows the mold and algae prevention effects of these molded products.

Comparative Examples 4 to 1) Sumirikisen G of low density polyethylene used in Example 3
701 or Sumitomo Noblen W501, the polypropylene used in Example 5, was blended with each compound as shown in Table 1, kneaded in a Banbury kneader, and granulated to produce a polyethylene or polypropylene composition. Alternatively, a plate-shaped injection molded product was obtained in the same manner as in Example 6.

Table 2 shows the antifungal and antialgal effects of these molded products.

Compound B: Higashi Tokyo Kasei Kogyo Remanufactured 2-(4-Thiazo Compound D: Ryl)benzimidazole Manufactured by Rohm and Haas Co., Ltd. Product Name: 5KANE H-8 [Effects of the Invention] As is clear from the above Examples and Comparative Examples, this invention The film or molded product of the invention, that is, the polyolefin resin film or molded product containing Compound B and Compound B, has excellent anti-mold and algae properties and water resistance, and is suitable for use in architectural interior materials that require these properties. resin composition,
General packaging films for foods, medicines, machinery, tools, etc.
Agricultural films for greenhouses and tunnel cultivation, concrete roadbeds, films for civil engineering works such as roofing, pipes for water supply and sewage systems, chemical factories, civil engineering works, etc., packaging materials laminated with paper, metal foil, etc., power communications. For cable insulation and sheathing, various household tableware, containers, electricity,
It can be seen that it is extremely suitable for mechanical parts, interior and exterior parts of automobiles, ships, etc., robes, cloth, fishing nets, etc. In addition, molded articles obtained by blending Compound B and Compound R with polymethyl methacrylate, polystyrene, or acrylonitrile-styrene-butadiene copolymer do not have sufficient antifungal and algal properties.

Furthermore, it can be seen that even with polyolefin resins, when Compound B or Compound R is used alone, sufficient antifungal and algae-proofing properties and water resistance cannot be obtained as in the above case.

Claims (3)

[Claims] (1) 2-(4-thiazolyl)benzimidazole and 2
- A fungicidal and algae-proofing resin composition characterized by blending n-octyl-4-isothiazolin-3-one into a polyolefin resin. (2) 2-(4-thiazolyl)benzimidazole and 2
-N-octyl-4-isothiazolin-3-one is present in a weight ratio of 3:7 to 7:3, and the total amount thereof is 0.001% to 1.0% by weight based on the resin composition. Item 1. The resin composition according to item 1. (3) The resin composition according to claim 1 or 2, wherein the polyolefin resin is an ethylene homopolymer, a propylene homopolymer, or an ethylene-vinyl acetate copolymer.