JPH06287477A - Antifouling resin composition - Google Patents

Abstract

PURPOSE:To obtain an antifouling resin composition having extremely excellent antifouling properties for ordinary stains as well as specific stains caused by bacteria, fungi and yeasts. CONSTITUTION:The antifouling resin composition is composed of a resin having <=40dyne/cm critical surface tension, a silicone resin and an antimicrobial agent. This composition exhibits good water-repelling and antifouling effects due to the lowering of surface free energy which is a synergic action of the resin having <=40dyne/cm critical surface tension and the silicone resin and excellent antifouling property also to stain caused by microorganisms.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition having excellent stain resistance.

[0002]

2. Description of the Related Art It is generally said that polymer plastics have a low energy surface and metals have a high energy surface. High-energy surfaces are particularly sensitive to pollution, and traditional methods have been to protect the surface by painting or the like. On the other hand, polymer plastics, which are representative of low-energy surfaces, have been used in a large amount due to recent demands for cost reduction and product weight reduction. And although these polymer plastics are relatively insensitive to pollution, the development of polymer plastics products that are less likely to become dirty with the improvement of product quality and the increasing consumer health and cleanliness Is required.

Although the chemical constituents of soils are complicated and not all of them have been fully elucidated, the components of soils are generally dirt, oils and fats, proteins, carbohydrates, salts, Examples thereof include pigments and resins, and special stain components include bacteria and fungi. Usually, these components are not a single product but a complex form of stains. The form in which these stains adhere to the substrate can be classified as follows. a. A structure in which dirt particles are simply entangled in the structure of the outer surface of the substrate. b. This is due to the attractive force between the substrate and the molecules of dirt, and is called the Van der Waals force. c. Those that adhere due to the electrostatic properties of both. d. Those that are in a weak chemical bond with the surface molecules of the substrate. e. Dirt that has penetrated and diffused into the surface texture of the substrate. The following methods are effective as a method for preventing pollution in view of these types of dirt adhesion. 1. It improves the water repellency of the substrate surface and prevents dirt components from approaching the substrate surface. 2. Smooths the substrate surface and prevents physical adhesion. 3. The substrate is electrically neutralized. Among the above, it is considered most effective to prevent the stain component (1) from approaching the substrate.

Therefore, conventionally, the following methods have been mainly adopted as specific methods for preventing stains. 1) The substrate surface is made of a substance having a relatively small surface energy,
For example, it is treated with a coating material such as a silicone resin, a polyester resin, an acrylic resin, a urethane resin, a vinyl resin, and a fluorine resin to improve the contact angle of water on the surface so that stains are less likely to adhere. 2) A hard coat treatment is applied to the surface of the substrate to prevent stains due to improvement of smoothness and stains due to abrasion. 3) Add an antistatic agent to the substrate to make it electrically neutral and less likely to stain.

[0005]

However, in the conventional method of treating with a resin paint having a small surface energy or the method of treating with a hard coat, complicated steps such as a coating step, a drying step and a curing step are required, In addition, there is a problem that the durability of the coating film is not good because it is a very thin coating film together with the problem of adhesion to the substrate. Also, no consideration was given to special stains such as bacteria, mold, and yeast, which are the main causes of slimy skin.

Regarding the addition of the antistatic agent, there is a drawback that the antifouling effect is originally small and the effect does not last.

Therefore, the object of the present invention is that it has excellent water repellency and its effect continues, and it has excellent stain resistance not only to general stains but also to special stains caused by microorganisms such as bacteria, molds and yeasts. In addition, it is to provide a resin composition that has the above-mentioned properties and can be molded under the same resin molding conditions as in the past, and does not require complicated processes such as a coating process, a drying process, and a curing process.

[0008]

In order to achieve the above object, the present invention remarkably improves antifouling property by a resin composition in which a resin having a critical surface tension of 40 dyne / cm or less, a silicone resin and an antibacterial agent are combined.

In the present invention, the critical surface tension is 40 dyn.
Resins with e / cm or less include low density polyethylene, high density polyethylene, polypropylene, nylon 10.1
0, nylon 10, nylon 8.8, nylon 9.9,
Polystyrene, PMMA (polymethylmethacrylate),
AS (Acrylonitrile-styrene copolymer), ABS
(Acrylonitrile / butadiene / styrene copolymer), polyvinyl chloride and the like.

As the silicone resin in the present invention,
Examples include pure silicone resins such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane, and modified silicone resins obtained by reacting a pure silicone resin with a modifying resin such as an alkyd resin, polyester resin, acrylic resin, or epoxy resin. To be

According to a second aspect of the present invention, a resin 10 having a critical surface tension of 40 dyne / cm or less is used as a blending ratio of the silicone resin.
The amount is 0.5 to 15 parts by weight, especially 1 to 10 parts by weight, based on 0 parts by weight.

As the antibacterial agent in the present invention, as an inorganic antibacterial agent, silver salts such as silver nitrate, silver sulfate and silver chloride, silver,
Zeolite supporting copper, zinc or tin, and silver,
Examples thereof include silica gel supporting copper, zinc or tin.

As organic antibacterial agents, phenyl ether derivatives such as 10,10'-oxybisphenoxaarsine, N-haloalkylthio compounds such as cyclofluanide, 2- (4-thiazolyl) benzimidazole (TB
Examples thereof include imidazole derivatives such as Z), sulfone derivatives such as 2,3,5,6 tetrachloro-4- (methylsulfonyl) pyridine, and quaternary ammonium salts such as ceryldimethylethylammonium bromide.

The blending ratio of the antibacterial agent in the invention of claim 4 is such that the inorganic antibacterial agent has a critical surface tension of 40 dy.
0.5 to 3 with respect to 100 parts by weight of resin of ne / cm or less
It was made into a weight part.

The organic antibacterial agent according to the invention of claim 4 has a critical surface tension in the range of 0.05 to 1 part by weight with respect to 100 parts by weight of a resin having a critical surface tension of 40 dyne / cm or less.

[0016]

The resin composition excellent in stain resistance according to the present invention is
By blending a silicone resin with a resin having a critical surface tension of 40 dyne / cm or less, a very high water repellency and a good slipperiness such that the contact angle to water exceeds 100 ° can be expressed by the special synergistic effect of both resins. , Prevent the attachment of general dirt.

Further, the action of the antibacterial agent can effectively prevent the propagation of special stains such as bacteria, fungi and yeasts. Among them, the inorganic antibacterial agent has an effective antibacterial property especially against bacteria, and the organic antibacterial agent has an effective antibacterial property against particularly mold and yeast.

[0018]

The present invention will be described in more detail with reference to Examples. The resin having a critical surface tension of 40 dyne / cm or less is polypropylene resin (hereinafter abbreviated as PP), the silicone resin is ethylene vinyl acetate graft-polymerized with high molecular weight siloxane, and is safe as an organic antibacterial agent. For the TBZ and the inorganic antibacterial agents, which have a high concentration and are most often used, a zeolite carrying silver will be described as an example. However, the present invention is not limited to these examples.

The critical surface tension is 40 dyne / cm.
Even if a resin having a viscosity of more than 100 is blended with the silicone resin, the contact angle of the resin composition surface to water does not increase so much, and the effect of preventing stains is small.

The critical surface tension is 40 dyne / cm.
If an excessively large amount of a silicone resin is added to the following resin, the surface properties of the resin will deteriorate and the physical properties will change.

The proportion of the antibacterial agent or antifungal agent is
If the amount is too small, there is no antibacterial property or antifungal property. On the contrary, if the amount is too large, the resin is colored or bloomed, which is not preferable.

(Example 1) 100 parts by weight of PP resin, 0.5 parts by weight of silicone resin, 0.01 parts by weight of TBZ, and 0.05 parts by weight of silver zeolite were mixed well and molded by a molding machine to form a plate-shaped resin. I got a thing.

(Example 2) 100 parts by weight of PP resin, 1.0 part by weight of silicone resin, 0.1 part by weight of TBZ, and 0.5 part by weight of silver zeolite were mixed well and molded by a molding machine to form a plate-shaped resin. I got a thing.

(Example 3) 100 parts by weight of PP resin, 5.0 parts by weight of silicone resin, 0.25 parts by weight of TBZ, 0.75 parts by weight of silver zeolite were mixed well and molded by a molding machine to form a plate-shaped resin. I got a thing.

Example 4 100 parts by weight of PP resin, 10 parts by weight of silicone resin, 0.5 parts by weight of TBZ, 1.0 part by weight of silver zeolite were mixed well and molded by a molding machine to obtain a plate-shaped resin molded product. Obtained.

(Example 5) 100 parts by weight of PP resin, 15 parts by weight of silicone resin, 1.0 part by weight of TBZ, 2.0 parts by weight of silver zeolite were mixed well and molded by a molding machine to obtain a plate-shaped resin molded product. Obtained.

(Comparative Example) PP resin was molded by a molding machine in the same manner as in each Example to obtain a plate-shaped resin molded product.

The contact angle of each resin molded product obtained in each of the examples and comparative examples with water was measured by a contact angle measuring device (CA-Z type) manufactured by Kyowa Interface Science Co., Ltd. The stain resistance of each resin molded product was confirmed in accordance with JIS K3370.
In addition, the comparison of the stain resistance performance was performed by visual observation, and the stain condition in the comparative example was set as (△), worse (x), and better (○), and the relative evaluations were made (Table 1 )
Shown in.

[0029]

[Table 1]

Next, the resin moldings obtained in the respective examples and comparative examples were tested for antibacterial performance and mold resistance.

1 ml of the bacterial solution (general bacteria and E. coli) was dropped on each sample (50 × 50 mm), and the mixture was kept at 37 ° C. for 2 hours.
Cultured for 4 hours. Then, the bacteria were washed out with a sterilized phosphate buffer solution. The viable cell count in the washed-out solution was measured by the pour plate method using a cell count measuring medium. The results are shown in (Table 2).

[0032]

[Table 2]

Each sample (50 × 50 m) placed on the agar medium
m) is sprayed with Aspergillus niger bacterium solution, 25 ° C,
The culture was carried out for 7 days, and the results are shown in (Table 3).

[0034]

[Table 3]

[0035]

As described above, the stain-resistant resin composition of the present invention has a low surface energy due to the synergistic action of a resin having a surface tension of 40 dyne / cm or less and a silicone resin, and has a good antifouling property. Can be obtained. Also,
It exhibits excellent antifouling properties against special stains caused by microorganisms (bacteria, fungi, yeasts, etc.), so stains from various fields such as construction, home appliances, kitchen products, bath and sanitary products will adhere. Suitable for easy products.

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Claims (4)

[Claims] 1. A stain resistant resin composition comprising a silicone resin and an antibacterial agent dispersed in at least one resin selected from resins having a critical surface tension of 40 dyne / cm or less. 2. A silicone resin is blended in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of at least one resin selected from resins having a critical surface tension of 40 dyne / cm or less. Contamination resistant resin composition. 3. A silicone resin and an antibacterial agent are dispersed in at least one resin selected from resins having a critical surface tension of 40 dyne / cm or less, and the antibacterial agent is at least one of inorganic antibacterial agents. And a stain-resistant resin composition comprising at least one organic antibacterial agent. 4. An inorganic antibacterial agent is dispersed in an amount of 0.5 to 3 parts by weight and an organic antibacterial agent is dispersed in an amount of 0.05 to 1 part by weight per 100 parts by weight of a resin having a critical surface tension of 40 dyne / cm or less. The stain resistant resin composition according to claim 3.