JPH02225548A - Mildew-pr0ofing and algae-proofing resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in mildew-proofing and algae- proofing properties and heat resistance by mixing a vinyl chloride resin with 2-(4-thiazolyl)benzimidazole, 2-n-octyl-4-isothiazolin-3-one and a plasticizer. CONSTITUTION:A vinyl chloride resin of a mean particle diameter of 0.1-50mum is mixed with 0.001-0.8wt.% mixture of 2-(4-thiazolyl)benzimidazole with 2-n- octyl-4-isothiazolin-3-one in a weight ratio of 3:7-7:3 and a phosphate plasticizer (e.g. triethyl phosphate).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a fungicidal and algal-proofing resin composition that exhibits excellent antifungal and algae-proofing effects in various products made from vinyl chloride polymers.

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

For example, components related to building interior materials, such as wallpaper, flooring, agricultural films, various resin tableware for household use, garbage bags, garbage bags, triangular corners of sinks, etc., often get dirty and are exposed to high humidity environments. Because it is used in the industry, 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 add to the aesthetic appearance, but also cause deterioration of the quality 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 studied to impart a fungicidal or algae-proofing effect by kneading and molding. However, even when looking only at the fungicidal effect, the conventional techniques have had many problems as described below.

Conventionally, additives blended for the purpose of preventing mold in resin molded products include 10.10'-oxybisphenoxyarsine (hereinafter referred to as "compound"), 2-(4-thiazolyl)-
Compounds such as benzimidazole (hereinafter referred to as compound B), N-(fluorodichloromethylthio)-phthalimide (hereinafter referred to as compound C), and 2-n-octyl-4-isothiazolin-3-one (hereinafter referred to as compound R) are known. ing.

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, the compatibility between the resin composition and the compound blended for fungicidal purposes may be poor, and the inherent activity of the compound may not be fully demonstrated.For example, in resin molded products such as soft vinyl chloride polymers, A plasticizer is added, but Compound A has too high a solubility in the plasticizer. Therefore, in a resin composition in which Compound A is blended with a soft vinyl chloride resin,
There are problems such as the transfer rate of Compound A 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 <Li! Problem> The present invention solves the problems of the conventional techniques as described above, and provides a vinyl chloride resin composition with excellent antifungal and algae-proofing performance, which has been in great demand in recent years. In other words, the conditions required for an ideal antifungal and algal resin composition are: 1) It should exhibit high activity against a wide range of molds and %g; 2) The active ingredient should have high heat resistance, and the resin composition should Must be able to withstand high temperatures during molding 3) Highly safe for users and manufacturing workers 4) Compatibility between the active ingredient and the resin component is good, and the mold- and algae-proofing activity of the resin composition will last for a long time. The object of the present invention is to obtain a mold- and algae-proofing resin composition that has these properties.

<Means for Solving the Problems> In order to achieve the above object, the present inventors first conducted extensive research on resin compositions containing various additives having the effect of preventing mold growth. As a result, a mixture of 2-(4-thiazolyl)-benzimidazole (compound B), 2-n-octyl-4-inthiazolin-3-one (compound @5D), and a plasticizer were added to a vinyl chloride polymer. It has been found that the blended resin composition has very excellent properties.

In other words, Compound B and Compound R sufficiently withstand the high temperatures during molding of the vinyl chloride resin composition blended with the plasticizer of the present invention, and furthermore, by blending them at the same time, a high degree of resistance is achieved that cannot be predicted by each alone. It exhibited antifungal and antialgal activity.

Vinyl chloride polymers used in the present invention include vinyl chloride polymers, copolymers of vinyl chloride and vinyl acetate,
Examples include copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and acrylic esters, and mixtures thereof.

Among these, vinyl chloride polymers and copolymers of vinyl chloride and vinyl acetate are preferably used.

Examples of the plasticizer used in the resin composition of the present invention include phosphate ester plasticizers, phthalate plasticizers such as di-2-ethylhexyl phthalate, and adipine such as di-2-ethylhexyl adipate. Acid ester plasticizers, sepatic acid ester plasticizers such as di-2-ethylhexyl sebacate, azelaic acid ester plasticizers such as di-2-ethylhexyl azelate,
Citric acid ester plasticizers such as tributyl citrate, glycolic acid ester plasticizers such as butylphthalyl butyl glycolate, l-limellitic ester plasticizers such as tri-2-ethylhexyl trimellitate, etc. , di-2-ethylhexyl terephthalate, and other phthalic acid isomer ester plasticizers.

In particular, when a phosphate ester plasticizer is included as a plasticizer, a more excellent antifungal and algal effect is exhibited.

Examples of such phosphoric acid ester plasticizers include triethyl phosphate, tributyl phosphate, triphenyl phosphate, tri(2-ethylhexyl) phosphate, tricresyl phosphate, and the like.

In addition to the antifungal additives, synthetic resins, and plasticizers, the resin composition of the present invention may also contain stabilizers, antioxidants, ultraviolet absorbers, flame retardants, foaming agents, and coloring agents, if necessary. Compounding agents such as additives, fillers, antistatic agents, lubricants, crosslinking agents, and diluents can be added.

The resin composition containing a plasticizer of the present invention is not particularly limited in the molding method or the shape of the molded product, and is blended and kneaded using ordinary kneading equipment such as a ribbon blender, Henschel mixer, Banbury mixer, extrusion molding machine, injection molding machine, etc. Single-layer and multi-layer films and sheets, various containers, and molded products of various shapes are molded into resin moldings using ordinary molding machines such as molding machines, compression molding machines, calendar processing machines, and blow molding machines.

Among the resin compositions of the present invention, resin moldings related to architectural interior materials in which mold and algae prevention effects are particularly required are primarily vinyl chloride paste sol compositions in which a plasticizer is added to a vinyl chloride polymer. Molded products are often used, but the antifungal and algalgic resin composition of the present invention exhibits its effects particularly when a vinyl chloride paste sol composition is used. Preferably, the vinyl chloride polymer is a vinyl chloride polymer,
Copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and acrylic esters, and mixtures thereof, with an average particle size of 0.1 to 50 μm. A certain so-called paste vinyl chloride polymer is used.

The vinyl chloride paste sol composition contains a plasticizer as an essential component, and in addition to a fungicidal and algae-proofing agent, it also contains stabilizers, antioxidants, ultraviolet absorbers, flame retardants, foaming agents, colorants, and fillers as necessary. , antistatic agents, crosslinking agents, diluents, etc., and is fluid in the form of a paste at room temperature.

The vinyl chloride-based sol composition of the present invention is compounded and kneaded using a conventional kneading device for paste sol such as Laikai machine, Nigu, Hobart mixer, Disba, Inkroll, etc., and is subjected to coating, dipping, slush molding, rotary molding, etc. It is molded using a normal paste-sol molding method to form a resin molded product.

Due to its unique kneading method, the method using a vinyl chloride paste sol composition allows uniform dispersion of Compound B and Compound B, and is a suitable method for obtaining the resin composition of the present invention.

The compound B and compound R are blended in a weight ratio of 3 = 7 to 7:3, and their total amount is 0.8% by weight based on the resin composition. is preferable, and the weight ratio of compound B:compound R is 426 to 6;4,
And their total amount is o, oos~ with respect to the resin composition
0.81i% by weight is more preferable; if the weight ratio of compounds B and D is outside the above range, the control effect against a wide range of molds or algae will be reduced. In addition, if the total amount of compounds B and D is less than o or ooi weight percent, the durability and water resistance of the antifungal and algae effect will be insufficient, while if it exceeds 0.8 weight percent, it will be economical to achieve the desired effect. This is disadvantageous. Applications are not necessarily limited as long as they require anti-mold and algae effects, but include components related to building interior materials, such as wallpaper and flooring, general packaging films for foods, medicines, machinery, tools, etc., and housebuilding. , agricultural films for tunnel cultivation, 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 paper, metal foil, etc., power communication cables. Examples include insulation and sheaths for household use, various household tableware, containers, electrical and mechanical parts, interior and exterior products for automobiles, ships, etc., ropes, cloth, fishing nets, etc.

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

In addition, the evaluation of the antifungal and antialgal effects shown in the Examples and Comparative Examples was performed using the following test method.

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 a 5cm square size and placed on a potato dextrose agar medium.
After inoculating the mold by evenly spraying a mixed suspension of mold spores tll[1d, it was cultured at 28°C. 28, 56, and 84 days after inoculation, the development of mold was observed and evaluated. The test results are shown in Tables 1 and 2.

(Inoculum) Aspergillus niger
iger) Pencillius ciLrinua Chaetomum globosum
osum) Glioclum virens (Gliocl)
adius vtrens) Aureobasidium pullulans
) Paectlo*yces s
p,) Alternaria sp.
) (Evaluation criteria) No mold growth observed on the test piece ± Mold growth observed on 1/10th surface or less + 1
/10 to 1/4 where mold growth is observed on the 4th side
- Mold growth is observed on 1/2 side Mold growth is observed on 1/2 to 3/4 side Mold growth is observed on 1 3/4 side or more (2) Evaluation of mold prevention effect Test (water resistance test) Samples were placed in a 60°C constant temperature water bath (inner tank: F!143c)
m, width 24c+n.

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. Spray inoculated. 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 Tables 1 and 2.

(3) Algae prevention effect evaluation test A sample was cut into 5 cm square pieces and immersed in the following algae culture solution 200d.

2 d of water contaminated with algae was dropped into the culture solution in which the sample was immersed, and cultured for 2 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 Tables 1 and 2.

(Algae culture solution composition) Ca (NO3) z 1. og, KCI! ,0
．． 25gMg5O, 7HzOO, 25g, FeCl,
0,25gK HzP O-0,25g, tap water 1000Id (evaluation criteria) No algae adhesion on the sample + 1/2 or less of the algae on the sample 廿 More algae adhesion than 172 on the sample Example 1 Vinyl chloride resin for paste (Sumitomo Chemical: PxQIJ)
100 Parts by weight Di-2-ethylhexyl phthalate (plasticizer) Calcium carbonate (filler) 30 Titanium oxide (extending pigment) 10 Foaming agent (Oita Kagaku: A, ZH) 5 Stabilizer (Kyodo Yakuhin 2KF-
80A-8) Compound B (manufactured by Tokyo Kasei Kogyo ■) 0,2 Compound D (manufactured by Rohm and Haas: 5KANE@
M-8) 0.2 The above compound was made into a paste using an Ishikawa Raikai machine for 15 minutes to obtain a vinyl chloride paste sol.

This vinyl chloride paste sol was coated onto flame retardant paper to a thickness of 0.2 m using a roll coater, and heated and foamed in a tunnel furnace at 220'C for 60 seconds to obtain a foamed vinyl wallpaper sample. Table 1 shows the antifungal and antialgal effects of this molded product.

The foamed vinyl wallpaper obtained by this method is not colored by additives and exhibits excellent mildew and algae prevention effects with excellent durability and water resistance.

Examples 2-3 Example 1 by simply changing the blending amounts of Compound B and Compound R
A foamed vinyl wallpaper was made in exactly the same manner as in Example 1, and its anti-mildew and algae effects were tested in the same manner as in Example 1. The test results are shown in Table 1. None of the foamed vinyl wallpapers was colored by the additives, and exhibited excellent mold and algae prevention effects with excellent sustainability and water resistance.

Comparative Examples 1 to 3 Example 1 by simply changing the blending amounts of Compound B and Compound R
A foamed vinyl wallpaper was made in exactly the same manner as in Example 1, and its anti-mold and algae effect was tested in the same manner as in Example 1. The test results are shown in Table 1.

Comparative Example 1 is inconvenient because it has no antifungal and algal effect at all.

Comparative Example 2 has a weak and insufficient antifungal and algal effect.

In Comparative Example 3, the durability of the antifungal effect, the water resistance, and the antialgae effect are insufficient.

Example 4 Vinyl chloride resin (Sumitomo Chemical 5X-11F) 100
Part by weight di-2-ethylhexyl phthalate (plasticizer) mercaptotin 2 stearic acid 0. 3 compound 8
0. 1 Compound D
0. 1. Mix the above mixture thoroughly with a Henschel mixer, knead for 10 minutes with a mixing roll adjusted to 160°C, and then apply a pressure of 100kg/cd for 7 minutes with a press molding machine adjusted to 180"C to form a 1m thick sheet. This sample was cut to a size of 5 cm square and tested for mold and algae prevention effects in the same manner as in Example 1.The test results are shown in Table 2.The obtained PVC sheet was colored. It exhibits a long-lasting and water-resistant anti-mold and algae effect.

Comparative Example 4 A sheet was made in the same manner as in Example 4, except that Compound B and Compound R were not blended, and the antifungal and algal effect was tested in the same manner as in Example 1. The test results are shown in Table 2. The obtained sheet has no anti-mold and algae-preventing effect, which is disadvantageous.

Example 5 Vinyl chloride resin (Sumitomo Chemical 5X-11F) 100
Part by weight Di-2-ethylhexyl phthalate (plasticizer) Tricresyl phosphate (plasticizer) Mercaptotin 2 Stearic acid 0.3 Compound B
O,1 compound D
O, 1 The above formulation was thoroughly mixed with a Henschel mixer, and mixed with a mixing roll adjusted to 160°C for 10 minutes.
After kneading for 10 minutes, use a press molding machine adjusted to 180°C.
A sheet of one thickness was formed by applying a pressure of 0 kg/cd for 7 minutes. This sample was cut to a size of 5 cm square, and the fungicidal effect was tested in the same manner as in Example 1. The test results are shown in Table 2. The PVC sheet obtained by the method of Example 5 is free from coloration and exhibits an extremely excellent anti-mildew effect.

Examples 6-7 Example 4 was obtained by simply changing the blending amounts of compound B and compound R.
A sheet was made in exactly the same manner as in Example 1, and its fungicidal and algae-proofing effects were tested in the same manner as in Example 1. The test results are shown in Table 2. The sheet obtained was free from coloration and exhibited excellent anti-mold and algae effects with long-lasting properties and water resistance.

Example 8 Vinyl chloride resin (Sumitomo Chemical 5X-11F) 100 parts by weight Di-2-ethylhexyl phthalate (plasticizer) mercaptotin 2 Stearic acid 03 Compound B (2
-(4-thiazolyl)henzimidazole) 0.1 Compound D (2-n-octyl-4-isothiazoline-
3-one) 0.1 The above formulation was thoroughly mixed with a Henschel mixer, and 160
tI to °C! After kneading for 10 minutes using a knotted mixing roll, a 0.2-thick film containing a fungicide was formed using a calendar roll at a temperature of 180°C. The anti-mold and algae effect of this film is shown in Table 2. The obtained film exhibits an excellent anti-mold and algae effect in sustainability and water resistance.

Comparative Examples 5-6 Example 4 by simply changing the blending amounts of Compound B and Compound @D
A sheet was made in exactly the same manner as in Example 1, and its fungicidal and algae-proofing effects were tested in the same manner as in Example 1. The test results are shown in Table 2.The obtained sheet had no mildewproofing effect and was inconvenient.

Comparative Example 7 A sheet was made in the same manner as in Example 4, except that di-2-ethylhexyl phthalate (plasticizer) was not blended, and the antifungal and algae effect was tested in the same manner as in Example 1. The test results are not shown in Table 2. The sheet obtained is inconvenient because it has no antifungal and algae-preventing effect.

<Effects of the Invention> As is clear from the above Examples and Comparative Examples, the resin molded product according to the present invention, that is, the vinyl chloride resin molded product containing Compound B, the compound B, and a plasticizer, has excellent mildew and mildew resistance. It has algae and water resistance, and components related to architectural interior materials that require these properties, such as wallpaper and flooring, general packaging films for foods, medicines, machinery, tools, etc., greenhouses, tunnel cultivation, etc. Agricultural film, concrete roadbed, film for civil engineering works such as roofing, pipes for water supply and sewage, chemical factories, civil engineering work, etc., packaging materials laminated with paper, metal foil, etc., insulation and sheathing for power communication cables. various household tableware, containers, electrical, mechanical parts, interior and exterior items for automobiles, ships, etc., robes, cloth,
It can be seen that it is extremely suitable for fishing nets, etc. In addition, a molded article obtained by blending Compound B and Compound R with a vinyl chloride polymer without blending a plasticizer does not have sufficient mold and algae resistance and water resistance.

In addition, it can be seen that even if a vinyl chloride polymer is blended with a plasticizer, when Compound B or Compound R is used alone, sufficient antifungal and algal 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 in that n-octyl-4-isothiazolin-3-one is blended with a vinyl chloride polymer and a plasticizer is blended therein. (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 0.8% 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, characterized in that the plasticizer includes a phosphate ester plasticizer.