JPS63196657A - Mildewproofing molded product of resin - Google Patents

Abstract

PURPOSE:To obtain the molded product of a resin, which has heat resistance capable of withstanding fabrication which must be carried out at relatively high temp. and a mildewproofing effect over a wide range, by molding a resin compsn. contg. a specified benzimidazole and an oxide compd. blended therewith. CONSTITUTION:A molded product of a resin is obtd. by molding a resin compsn. obtd. by blending 2-(4-thiazolyl)benzimidazole (additive A) and 2-pyridinethiol 1-oxide or a metal salt thereof (additive B) with a resin. If desired, said resin compsn. may contain compounding ingredients such as a plasticizer, a stabilizer, an antioxidant, an ultraviolet absorber, a flame retarder, a blowing agent, a colorant, a filler, an antistatic agent, a lubricant, a crosslinking agent, etc. Examples of the metal salt are alkali metal, alkaline earth metal, iron, copper, zinc, nickel and tin salts. The additive A is used in an amount of 10-90wt.% based on the total amount of the additives A and B. The additives A and B are used in an amount of 0.02-0.8wt.% in total based on that of the resin compsn.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a resin molded product having an antifungal effect.

<Conventional Technology> In recent years, with the increase in the number of houses built using prefabricated construction methods with high airtightness and with the spread of heating as people's lives have improved, mold damage in houses has been rapidly increasing. In general, resins such as polyvinyl chloride resin and polyethylene resin are said to be relatively resistant to mold growth, but the plasticizers and stabilizers added to these resins to improve their physical properties can become a nutrient source for mold, and can also cause mold growth. Dirt that adheres to the surface of resin moldings made from such resin compositions also serves as a source of nutrients, so if resin moldings are used in a well-ventilated, well-heated room, the moderate temperature and high humidity may cause mold and mildew. Mold is generated and rapidly accumulates and propagates, especially in soft vinyl chloride resin molded products, where polyplasticizers are added to impart flexibility, so the occurrence and propagation of mold is remarkable.

Mold is a type of living organism, but resin molded products that have grown out of animals or plants will decompose and deteriorate due to mold, resulting in a decline in the physical properties of the molded product. In addition, mold itself is relatively large and secretes various pigments, so the beauty and design of resin molded products used for interior materials such as wallpaper and flooring can deteriorate due to dirt and coloring caused by mold. be exposed.

Furthermore, many of the mold spores cause allergic diseases and asthma in humans, and mold odors attract people into homes, causing problems such as wallpaper, etc. Mold that grows and grows on resin molded products used for flooring and other interior materials is a major hindrance to living a healthy life. In addition, mold contains a large amount of moisture, which, in combination with its deteriorating effects, is a cause of electrical failure.

Mold that grows and propagates in resin molded products in this way is causing unexpectedly great harm, so mold can grow and propagate in resin molded products.
Since it is necessary to suppress the growth of mold, methods and anti-mold treatment techniques are needed to prevent mold from forming. These methods and techniques include the following four items.

i) Select and use materials that are resistant to mold growth.

i) Use under conditions where mold is unlikely to grow.

ii) Keep the room clean and avoid dirt on the surfaces of resin molded products.

■) Apply fungicide.

In method i), the selection range of materials becomes very narrow, and the physical properties, texture, and cost of the material must be sacrificed, which is not practical. Method U) can significantly prevent the growth of mold by ensuring good ventilation in the room, but it is undesirable because it goes against the demands of the times for energy conservation, as it significantly reduces the efficiency of air conditioning and heating. Even with method 1ii), it is practically impossible to always keep the surface of the resin molded product completely clean, and when the resin molded product itself contains a large amount of nutritional sources, such as a soft vinyl chloride resin molded product, There is a limit. Method iv) has drawbacks such as the cumbersome application process, uneven application, and poor sustainability of the effect, which requires frequent application.

In order to give practical resin molded products essential mold resistance under the actual usage atmosphere and usage conditions, additives that have the effect of preventing the growth of mildew are mixed into the resin composition and molded. has been widely considered.

Rubber Digest's polymer selection ■ [Mold without soaking plastics] contains 2-(4-thiazole)-benzimidazole, N-(fluorocarbon mold) as additives that are kneaded into resin molded products such as resin. Chloromethylthio)-phthalimide, N-dimethyl-N'-phenol-
N'-(fluorodichloromethylthio)-sulfamide, 10.10'-oxybisphenoxyarsine is mentioned. However, when these additives are used alone, the mold-preventing effect is insufficient because each additive has its own weak mold growth-preventing effect. Furthermore, N-dimethylto'-phenol-N'-(fluorodichloromethylthio)-sulfamide has a thermal decomposition temperature of 1
10.10'-Oxybisphenoxyarsine has a unique odor, which causes discomfort to workers during the resin molding process. .

In addition, in order to compensate for the insufficiency of the fungicidal effect due to the use of fungicides alone, Japanese Patent Application Laid-open No. 146648/1983 discloses the following:
It has been shown that two types of additives, 2-(4-thiazolyl)benzimidazole and N-fluorodichloromethylthiophthalimide, are blended and mixed into a thermoplastic resin material and then molded.

However, the thermal decomposition temperature of N-fluorodichloromethylthiophthalimide is 180°C, which is insufficient heat resistance for resin molding, and its mildew-preventing effect is rather weak, so it is not sufficient to prevent a wide range of molds. Shows no mold effect.

<Problems to be Solved by the Invention> The present invention solves the problems of the conventional technology as described above, and provides sufficient heat resistance to withstand molding processes that require relatively high temperatures, and excellent mold resistance against a wide range of molds. The objective is to obtain a resin molded product that exhibits effects.

Means for Solving Problems〉 The present inventors have studied the anti-mold effect of resin molded products obtained by blending and mixing various mildew additives that have the effect of preventing mold growth with a resin composition and molding the mixture. , 2-(4-thiazolyl)benzimidazole (additive A) and 2-pyridinethiol-
The mixture with 1-oxide or its salt (Additive B) has no unpleasant odor during blending, crosstalk, and molding, and the resulting resin molded product is excellent due to the synergistic effect of Additive A and Additive B. The present invention was completed by discovering that it exhibits an anti-fungal effect and has excellent durability.

The resin composition of the present invention is a vinyl chloride polymer, a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinyl chloride and acrylic ester, a copolymer of ethylene and vinyl acetate, etc. Graft polymers in which vinyl chloride is graft-polymerized to copolymers of polymerization.

polymers such as acrylonitrile, styrene and butadiene copolymers, methacrylic acid ester copolymers, polyethylene, polypropylene, 811l polycarbonate, polyamide, polyurethane, polyethylene terephthalate, nitrocellulose, epoxy resin, unsaturated polyester resin, etc. The fungicide of the present invention and, if necessary, a plasticizer, stabilizer, antioxidant, extraneous radiation absorber, flame retardant, foaming agent, coloring agent, filler, antistatic agent, lubricant, crosslinking agent, etc. It is obtained by adding the agent.

In particular, the vinyl chloride paste sol composition of the present invention contains a vinyl chloride polymer, a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinyl chloride and acrylic ester, and a copolymer of vinyl chloride and vinylidene chloride. These mixtures contain as essential components a vinyl chloride polymer for paste with an average particle size of 0.1 to 60μ and a plasticizer, and in addition to a fungicide, stabilizers, antioxidants, and ultraviolet rays are added as necessary. absorbent,
It is a paste-like substance that is fluid at room temperature and contains compounds such as flame retardants, foaming agents, colorants, fillers, antistatic agents, crosslinking agents, and diluents.

The resin composition of the present invention is compounded and kneaded using a conventional mixing device such as a ribbon blender, Henschel mixer, or Banbury mixer, and is then mixed using an extrusion molding machine, injection molding machine, compression molding machine, or
It is molded into a resin molded product using a normal molding machine such as a calendar processing machine or a blow molding machine.

The vinyl chloride paste sol composition of the present invention is produced by Laikai Machine,
It is compounded and kneaded using ordinary paste-sol mixing equipment such as a kneader, Hobart mixer, disperser, and ink roll, and then molded using ordinary paste-sol molding methods such as coating, dipping, slush molding, and rotary molding to form a resin molded product. be done.

In the method using a vinyl chloride paste sol composition, due to its unique crosstalk method, additive A and additive B are uniformly dispersed, and this method is suitable for obtaining the resin molded article of the present invention. Furthermore, since the vinyl chloride paste sol composition contains a plasticizer that can serve as a nutrient source for mold as an essential component, the synergistic mold-preventing effect by mixing Additive A and Additive B of the present invention is more significantly exhibited.

Additive A used in the present invention is 2-(4-thiazolyl)
It is benzimidazole. Additive B is 2-pyridinethiol-1-oxide or a metal salt thereof. The metal salts include alkali metal salts, alkaline earth metal salts, iron salts, copper salts, zinc salts, lead salts, nickel salts and tin salts.

Among them, zinc salts and tin salts are particularly preferably used. Particularly preferred are zinc salts that are stable at relatively high molding temperatures of 180"C or higher.The blending ratio of additive A and additive B is such that the total amount of additives An excellent synergistic effect is produced when A is present in an amount of 10 to 90% by weight, particularly preferably 70% by weight of 8G-S.A sufficient synergistic effect cannot be obtained when the amount of additive A is less than 10% by weight or more than 90% by weight5.

The total amount of Additive A and Additive B added to the entire resin composition is 0.02 to 0.8% by weight, particularly preferably 0.02 to 0.8% by weight.
It is desirable that the content be 0.08 to 0.5% by weight. If it is less than 0.02% by weight, the antifungal effect is insufficient, and if it is less than 0.8% by weight.
The above method is not only economically disadvantageous, but also causes discoloration of the resin molded product, resulting in other inconveniences.

The resin molded product of the present invention is not particularly limited, but includes sheets,
It has the shape of a film, coating layer, or various molded products. Applications are not necessarily limited as long as they require a fungicidal effect, but examples include interior materials, packaging materials, parts for various electrical appliances, parts for industrial goods, building materials, wire covering materials, and household goods. The molded product of the present invention is particularly effective for heat sinks for coolers, shower curtains, and interior materials used in places where mold is likely to grow and propagate.

In particular, in the mold-proof resin molded products of the present invention molded using the vinyl chloride paste sol composition, such as vinyl wallpaper, shoe sheen floors, carpet backing materials, and vinyl-coated gloves, additives A and B are used. A synergistic antifungal effect is clearly exhibited by mixed use.

Example 1 Vinyl chloride resin for paste (Sumitomo Chemical: PQLT) 1
00! j1 part di2 ethylhexyl phthalate
60 Calcium carbonate
80〃Titanium oxide 10〃
Foaming agent (Oigoku Kagaku: AZ) i) 5/
/Stabilizer (Kyodo Yakuhin: KF-80A-8)
8 Minor additive A (2-(4→azolyl)benzimidazo 1) 0.15 // Additive B (2-viridiotodo l-oxide zinc salt) 0.15 & the above mixture was processed using an Ishikawa-type Raikai machine. It was made into a paste over 15 minutes to obtain a vinyl chloride paste sol. This vinyl chloride paste sol was coated on flame retardant paper to a thickness of 0.2 mm using a roll coater, heated and foamed for 60 seconds in a 22G'C tunnel furnace,
A foamed vinyl wallpaper sample was obtained.

This sample was cut into a size of 551 squares, placed on a potato dextrose agar medium, and a mixed mold spore suspension 1- consisting of the following seven species was evenly sprinkled on top of the sample.
The cells were cultured at ℃ for 28 days. The test results are shown in Table 1.

Aspergillus nigerpenicillium citrinum chaetomium globosmugliocladium virens aureobasidium pullulans bacilomyces alternaria The other two types of molds are cultured molds that grew and multiplied on vinyl wallpaper.

The foamed vinyl wallpaper obtained by the method of Example 1 was not colored by the additive, and exhibited excellent mold effects due to the synergistic effect of Additive A and Additive B.

Examples 2 to 5 Example 1 by simply changing the blending amounts of Additive A and Additive B
Foamed vinyl wallpaper was made in exactly the same manner as in Example 1, and its antifungal effect was tested in exactly the same manner as in Example 1. The test results are shown in Table 1.

All of the foamed vinyl wallpapers are not colored by additives and exhibit excellent antifungal effects due to the synergistic effect of additives A and B.

Comparative Examples 1° to 18 Example 1 by simply changing the blending amounts of Additive A and Additive B
Foamed vinyl wallpaper was made in exactly the same manner as in Example 1, and its antifungal effect was tested in exactly the same manner as in Example 1. The test results are shown in Table 1.

Comparative Example 1 is disadvantageous because it is aged and has no antifungal effect. In Comparative Example 2 and Comparative Example 8, Additive A and Additive B did not have a mutual effect, and the antifungal effect was insufficient.

Example 6 Bee chloride-based graft resin (Note 1) (Sumitomo GxF) 1
00111tS Mercaptotin 2
〃Stearic acid QJ tt additive A (2-(4→azol)penzimitic acid 1)
0.05 tt addition j5B (2-pyridinethiol-
1-oxyhxin鉦廁υ0.06 // (Note 1) A resin made by graft polymerizing vinyl chloride to ethylene vinyl acetate copolymer, with an ethylene vinyl acetate copolymer content of 55% by weight and a degree of polymerization of 1400. be.

Thoroughly mix the above formulation in a Henschel mixer,
After mixing for 10 minutes with a mixing roll adjusted to 0”C,
A 1-inch thick sheet was molded using a press molding machine adjusted to 180° C. under a pressure of 100 kg/− for 7 minutes. This sample was cut into a size of 5G square, and the antifungal effect was tested in the same manner as in Example 1. The test results are shown in Table 2. There is no coloration caused by additives, and the synergistic effect of additives A and B provides excellent antifungal effects.

Comparative Example 4 A sheet was made in the same manner as in Example 5, except that the amounts of Additive A and Additive B were not mixed, and the antifungal effect was tested in the same manner as in Example 1. The test results are shown in Table 2. Because Additive A and Additive B are not included, mold occurs and grows.

Procedural Amendment May 2j, 1988 Commissioner of the Patent Office Black 1) Mr. Akihiro 1, Indication of the Case 1988 Patent Application No. 28588 2, Title of Invention Mildewproof TfIi Fat Molding 8, Person Making Amendment Case Relationship with Patent Applicant Address 5-15 Kitahama, Higashi-ku, Osaka Name (2
09) Sumitomo Chemical Co., Ltd. Representative Mori
Hideo (and 1 other person) 4. Agent address: 5-15-6 Kitahama, Higashi-ku, Osaka City. Date of amendment order: April 28, 1988 (shipment date). 6. Specification subject to amendment, page 14, 7. Please refer to the attached sheet for details of the amendment.

and

Claims (2)

[Claims] (1) 2-(4-thiazolyl)benzimidazole and 2
- A mold-proof resin molded product characterized by molding a resin composition in which pyridinethiol-1-oxide or its metal salt is blended into a resin. (2) The resin molded article according to claim 1, wherein the resin composition is a vinyl chloride paste sol composition containing a vinyl chloride polymer and a plasticizer.