JPH09309957A - Functional material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional material which, despite the adoption of a system wherein functional inorg. particles having deodorant or antimicrobial functions are internally added to a molding, can exhibit significant deodorant and antimicrobial effects even when the amount of the added inorg. particles is relatively small, and can effectively inhibit the deterioration of the appearance, handle, mechanical strength, and surface properties, SOLUTION: This functional material comprises a plastic or rubbery molding (A) containing functional inorg. particles (a) having a deodorant or antimicrobial function and the surface of the molding (A) has been finely roughened. A particularly preferred roughening treatment is a low-temp. plasma treatment or a corona discharge treatment. The molding (A) may be optionally supported by a supporting material (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a functional material made of a molded product having a deodorizing or antibacterial function.

[0002]

2. Description of the Related Art Environmental improvement from the viewpoint of deodorization or antibacterial is nowadays performed at homes, workplaces, schools, hospitals, public buildings,
It has penetrated everywhere, including transportation.

[0003] Deodorants or antibacterial agents can be broadly classified into organic ones and inorganic ones, and both exhibit the desired effects. There is a tendency that growth is larger.

One of the applications of inorganic deodorants or antibacterial agents is one in which inorganic particles such as zeolite, glass, silica-alumina, etc. carrying antibacterial metal such as silver or its ions are internally added to a molded product. is there. It has also recently been reported that inorganic particles such as titanium oxide having a photocatalytic action are coated on glass, pottery, tiles, etc. to impart semi-permanent antibacterial properties.

[0005]

A molded article containing inorganic particles carrying an antibacterial metal such as silver or its ion is one in which safety and durability are taken into consideration. Since silver ion) exerts an antibacterial action by spilling out, its function depends on use conditions, and generally has a disadvantage of lacking immediate effect. Therefore, this kind of antibacterial product has an image of cleanliness, but it remains doubtful whether it has the expected antibacterial effect.

Inorganic particles having a photocatalytic action have been used for coating glass, pottery, tiles, etc., but there is little use for internally adding (internal addition, that is, kneading) plastics or rubber. It seems This is because when photocatalytic inorganic particles are internally added to a molded article made of plastics or rubber, a small amount of the particles exposed on the surface of the molded article causes less deodorization and the antibacterial effect to be significantly reduced, which does not reach a practical level. On the other hand, deodorization,
It is thought that if added in a large amount so that an antibacterial effect appears, the mechanical strength and various properties of the molded product itself are impaired, and the cost of the molded product as a whole becomes too high because the photocatalytic inorganic particles are expensive. . In addition, if the internal addition amount of the photocatalytic inorganic particles is increased, the organic substance (plastics or rubber-like molded product) itself is oxidized and decomposed, and the life of the molded product is shortened.

Under the above circumstances, the present invention adopts a method of internally adding functional inorganic particles having a deodorizing or antibacterial function to a molded product, but with a relatively small amount of internal addition, remarkable deodorization and It has an antibacterial effect, the appearance of the molded product,
It is an object of the present invention to provide a functional material that effectively suppresses deterioration of feeling, mechanical strength and surface characteristics.

[0008]

Means for Solving the Problems The functional material of the present invention comprises:
A molded article (A) made of plastics or rubber, in which functional inorganic particles (a) having a deodorizing or antibacterial function are internally added, and the surface of the molded article (A) is finely roughened. It is characterized by that.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

<Plastics or rubber moldings
(A)> The plastics or rubber molded product (A) is preferably a film / sheet-shaped or filament-shaped molded product, and includes a laminate, a woven fabric, a non-woven fabric, a knitted fabric,
It may be a secondary processed product such as cotton, thread, string, rope or net. Further, it may be an arbitrary molded product such as a pipe, a rod, a plate, or a molded product constituting a part or a product.

Examples of plastics or rubbers include polyolefin, amorphous polyolefin, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl alcohol copolymer, acrylic resin, acrylonitrile copolymer. Coalescing, polysulfone,
Polyether sulfone, polyarylate, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyparaxylene, polymethylpentene, fluorine resin, silicone resin, polyurethane, polyimide, phenol resin, urea resin, epoxy resin, acetyl cellulose, Thermoplastic elastomers (polyolefin elastomers, ethylene-vinyl acetate copolymer elastomers, polyamide elastomers, polyester elastomers, polystyrene elastomers, etc.), synthetic rubbers, natural rubbers, natural rubbers, and any other plastics or rubber materials Is used.

<Functional inorganic particles (a)> The functional inorganic particles (a) having a deodorizing or antibacterial function include inorganic particles carrying an antibacterial metal or its ions, inorganic particles having a photocatalytic action, or photoreduction. Examples include plated inorganic particles.

Of these, examples of the inorganic particles carrying antibacterial metal or its ion include zeolite, glass, silica alumina, apatite, zirconium phosphate, silica gel carrying antibacterial metal or its ion such as silver, copper and zinc. , Inorganic particles such as calcium silicate.

Examples of inorganic particles having photocatalytic action are X
It is an ultrafine titanium oxide with a linear grain size of 100 nm or less, and its surface is made of metal (gold, silver, copper, platinum,
Those modified with zinc, silicon, iron or the like) or metal compounds (zinc oxide, silicon oxide or the like) can also be preferably used.

The photoreduced plating inorganic particles are those obtained by reducing and immobilizing the photocatalyst layer by further coating with metal ions such as silver and copper.

<Internal addition method> The above-mentioned functional inorganic particles (a)
Is internally added to the plastic or rubber molding (A). That is, the functional inorganic particles (a) are blended with a molding raw material and used for molding. As a molding method, any molding method such as an extrusion molding method, an injection molding method, a compression molding method, an extrusion coating method, a melt blow method, a casting method (casting method), and a calender molding method is adopted. In molding, in addition to the above-mentioned functional inorganic particles (a), other inorganic particles, colorants, lubricants, stabilizers, plasticizers, antistatic agents, flame retardants, reinforcing fibers and the like can be added.

Plastic or rubber molding (A)
Although there is no particular limitation on the internal addition amount (compounding amount) of the functional inorganic particles (a) with respect to, based on the weight of the molded product after blending,
It is desirable that the amount is 0.1 to 40% by weight, preferably 0.5 to 30% by weight, and more preferably 1 to 20% by weight. Usually, 10% by weight or less is often sufficient. When the amount of the functional inorganic particles (a) is too small, the deodorizing / antibacterial effect is insufficient, while when the amount of the functional inorganic particles (a) is too large, the mechanical strength of the molded product (A) is low. Be damaged.

<Roughening treatment> And in the present invention,
After obtaining the molded article (A) of plastics or rubber containing the functional inorganic particles (a) internally, the surface of the molded article (A) is finely roughened. The roughening treatment may be performed at the same time as the molding.

Examples of the surface roughening method include electrical processing, optical processing, mechanical processing, and chemical processing.

Among these processing methods, electrical processing,
Particularly, a plasma treatment is preferable. The plasma treatment includes a low temperature plasma treatment, a corona discharge treatment, a glow discharge treatment, a plasma jet treatment and the like, and the low temperature plasma treatment and the corona discharge treatment are particularly important. Of these, the corona discharge treatment is also preferable in terms of equipment cost and lannig cost.

Among the above-mentioned low temperature plasma treatment methods, there are direct current discharge, alternating current low frequency discharge, high frequency and microwave discharge. The ion species constituting the plasma include air, nitrogen, oxygen, hydrogen, argon, helium, neon, nitrous oxide, nitric oxide, nitrogen dioxide,
Carbon monoxide, carbon dioxide, fluorine, chlorine, bromine, bromine cyanide, sulfur dioxide, hydrogen sulfide, ammonia, methane,
Various inorganic or organic gases such as ethane and propane are used, but usually air is sufficient. The degree of vacuum during the low-temperature plasma processing is set, for example, to about 0.01 to 10 Torr. Although the processing time varies greatly depending on the degree of vacuum, it is usually from several seconds to about 10 minutes. This is because the low temperature plasma treatment for a long time may lead to a decrease in strength of the molded product (A).

Among the above, corona discharge treatment is performed between the electrode connected to the high voltage generator and the metal roll by 0.5 to 0.6 mm.
It is a method in which a high-voltage corona is generated in a gap by applying a high voltage of several thousand to tens of thousands of V at a high frequency of several hundred KC / S, and a thin layer molded article is run in the gap for processing. . This activates the thin layer material surface. When a three-dimensional molded product is fixed on the support film and the support film is run, even the three-dimensional molded product can be subjected to corona discharge treatment.

Among the roughening treatment methods, optical treatment method, chemical treatment method, and mechanical treatment method include ultraviolet irradiation treatment, ozone treatment, sputter etching treatment, ion beam treatment, flame treatment, chromic acid treatment, and alkali treatment. Examples include treatment, sandblasting, and scratching with a blade, needle, file, etc.

<Functional Material> In this way, a molded article (A) is obtained in which the functional inorganic particles (a) having a deodorizing or antibacterial function are internally added and the surface is finely roughened.

This molding (A) can also be supported by a support material (B) which supports it. As the supporting material (B), ordinary molded products, metal materials, ceramic materials,
Woven cloth, non-woven cloth, knitted cloth, paper and any other material can be used. The method of laminating the molded product (A) and the support material (B), as well as the fiber as the molded product (A) and the support material (B)
It is also preferable to use it as a non-woven fabric, a woven fabric, or a knitted fabric in combination with the above fibers.

<Uses> The functional material of the present invention is used as wallpaper, partitions, flooring, footwear, clothing, bedding, rugs, filters, casings, various parts, various accessories (stationery, etc.), kitchen utensils, toiletries. It is used in a wide range of fields including household appliances, industrial appliances, public appliances, hospital appliances, horticulture appliances, agricultural appliances, livestock products, and marine products processing, including bathroom products, reception products, and office automation equipment.

<Function> The surface of the plastic or rubber molded article (A) to which the functional inorganic particles (a) having deodorant or antibacterial functions are internally added is subjected to plasma treatment (low temperature plasma treatment, corona discharge treatment, etc.). ) Or other methods for surface roughening, the thin oil film on the surface of the molded product (A) is removed, active radicals or functional groups are generated, and the molded product (A)
Fine irregularities and cracks may be formed on the surface. As a result, the internally added functional inorganic particles (a) are exposed on the surface of the molded product (A), and the effective surface area is significantly increased, and the roughened surface temporarily adsorbs and captures odorous components and microorganisms. As a result, the action of the functional inorganic particles (a) is likely to be exhibited, and the deodorizing and antibacterial ability is remarkably improved as compared with the case where such roughening treatment is not performed.

When the functional inorganic particle (a) is an inorganic particle having a photocatalytic action, it itself exerts an oxidizing action, but it is exposed to light while being used for deodorization and antibacterial, or deodorization.
If it is used for antibacterial and then irradiated with light, the deodorizing and antibacterial ability is restored, so that it can be reused repeatedly. The light at this time is most preferably ultraviolet light, but light from fluorescent lamps, white light, and sunlight are also sufficiently effective.

In the functional material of the present invention, even if the amount of the functional inorganic particles (a) internally added is relatively small, large deodorization,
Since the antibacterial ability is exhibited, deterioration of the appearance, feel, mechanical strength and surface characteristics of the molded article (A) is effectively suppressed. Further, as the functional inorganic particles (a), even when using inorganic particles having a photocatalytic action that may reduce the strength of the molded product (A) itself, the internal addition amount can be reduced, and the molded product ( If A) is supported by the support material (B), the required strength is secured, so there is no particular problem.

[0030]

EXAMPLES The present invention will be further described with reference to examples.

Example 1 As an example of inorganic particles having a photocatalytic action, titanium oxide "ST-31" for photocatalyst manufactured by Ishihara Sangyo Co., Ltd. was prepared. According to the description in the catalog, “ST-31” is anatase in crystal form, powder in form, and TiO ₂ content (110
81% by weight, the X-ray particle size is 7 nm, and the specific surface area (simple BET method) is 260 m ² / g.

30 parts of this titanium oxide for photocatalyst was mixed with 70 parts of low-density polyethylene, and the mixture was supplied to an extruder and melt-extruded linearly and pelletized to obtain master batch pellets.

Then, a predetermined amount of the masterbatch pellets is mixed with a new low-density polyethylene pellet and melt-extruded by an inflation molding method. The internal addition amount of titanium oxide for photocatalyst is 1.0% by weight, 3.0% by weight, and A 5.0% by weight film was obtained (thickness: 40 μm).
This was cut into a size of 30 mm × 60 mm to obtain a sample. For comparison, melt extrusion was performed using only new low-density polyethylene pellets to obtain sheets and samples of the same thickness.

<Deodorization Test / Effect of Internal Addition of Titanium Oxide> A glass bottle having a radius of 30 mm and a height of 70 mm was charged with trimethylamine.
Add 40 ml of 0.06% by weight aqueous solution, add phenolphthalein to see the state of decomposition of trimethylamine, and color. Add the above sample and seal it. Leave it in the field for 24 hours and 72 hours, and leave it in direct sunlight. After exposure to, the absorbance at 550 nm was measured. Table 1 shows the results
And shown in FIG.

[0035]

[Table 1]

<Deodorization Test / Effect of Low-Temperature Plasma Treatment> From the above preliminary test, the internal addition of titanium oxide for photocatalyst has a significant effect on deodorization, and the internal addition amount is 5.0% by weight based on the whole amount. I found the case to be good, so
About 5.0 wt% internal additive, using low temperature plasma processing equipment of Shiga Prefectural Industrial Technology Center, (a) gas: air, processing power: 10 W, processing time: 1
Min, vacuum degree: 0.2Torr (b) gas: air, processing power: 10W, processing time: 5
Minute, vacuum degree: 0.2Torr (C) Gas: Air, processing power: 100W, processing time: 1
Min, vacuum degree: low temperature plasma treatment was performed under the condition of 0.2 Torr.

In the deodorization test, 40 ml of an aqueous solution containing 0.014% by weight of ammonia was placed in a glass container having a volume of 50 ml, phenolphthalein was added for coloring, and further 30 mm × 6.
A sample with a size of 0 mm was put therein, and the sample was sealed, exposed to direct sunlight for 3 hours and 8 hours, and then the absorbance at 550 nm was measured. The results are shown in Table 2 and FIG. In Table 2, "-" is the case where the low temperature plasma treatment was not performed.

[0038]

[Table 2] TiO ₂ internal content Low temperature plasma absorbance (abs.) Sample No. (wt%) Treatment condition 3 hours later 8 hours later 0 0 − 0.219 0.203 5 5.0 − 0.176 0.138 5a 5.0 (a) 0.135 0.089 5b 5.0 (b) 0.139 0.071 5c 5.0 (c) 0.111 0.062

It can be seen from Table 2 and FIG. 2 that the low temperature plasma treatment has a significant effect on deodorization, especially under the condition of (c).

<Effect of Antibacterial Test / Low Temperature Plasma Treatment> From the above deodorant test, the internal addition amount of titanium oxide was
An excellent deodorizing effect is achieved when the low temperature plasma treatment is performed at 5.0% by weight and under the condition (C) (gas: air, treatment power: 100 W, treatment time: 1 minute, vacuum degree: 0.2 Torr). It was found that 5.0% by weight of the internal additive was subjected to low-temperature plasma treatment under these conditions, and an antibacterial test was conducted on the sample.

The antibacterial test was carried out by placing a sample having a size of 30 mm × 60 mm in 40 ml of water (containing free-falling bacteria) containing 0.1% by weight of a commercially available medium, sealing the sample, and leaving it to stand in the room under natural light. Bacterial growth was determined by measuring the 600 nm transmission after 96 and 104 hours. The results are shown in Table 3 and FIG.

[0042]

[Table 3] TiO ₂ internal content Low-temperature plasma transmittance (% T) Sample No. (wt%) Processing condition 96 hours later 104 hours later 0 0-84.0 ^## 70.6 ^## 5 5.0-91.8 ^# 85.9 ^## 5c 5.0 ha 99.0 ^* 95.6 ^* (Note) ^## indicates cloudiness and rotten odor. ^# Is slightly cloudy and slightly odorous. ^* Is transparent and odorless.

From Table 3 and FIG. 3, it is understood that the low temperature plasma treatment has a remarkable effect in terms of antibacterial property.

Example 2 <Effects of deodorant test / corona discharge treatment> Using the corona discharge treatment device manufactured by Kasuga Electric Co., Ltd. for the 5.0% by weight titanium oxide internal additive of Example 1, (A) weak, (B) Strong, 2
Corona discharge treatment was performed under the conditions. For reference, as described in Example 1, (a) gas: air, processing power: 10 W, processing time: 1
Min, vacuum degree: Low temperature plasma treatment was performed under the condition of 0.2 Torr.

In the deodorant test, 40 ml of an aqueous 0.001 wt% ammonia solution was placed in a glass container having a volume of 50 ml, and phenolphthalein was added to color the mixture.
A sample with a size of 0 mm was put therein, and the sample was sealed, exposed to direct sunlight for 1 hour, and then the absorbance at 550 nm was measured. The results are shown in Table 4 and FIG.
In Table 4, "-" indicates that no corona discharge treatment or low temperature plasma treatment was performed.

[0046]

[Table 4] Internal addition amount of TiO ₂ Absorbance removal rate after 1 hour of corona low temperature sample Sample No. (wt%) Discharge treatment Zuma treatment (abs.) (%) 0 0 − − 0.212 − 5a 5.0 − (a) 0.009 95.7 5d 5.0 slightly − 0.023 89.1 5e 5.0 Strong − −0.006 100

The same deodorizing test was conducted under different conditions (increasing the concentration of the aqueous ammonia solution) from the above. That is, 40 ml of an aqueous solution of 0.005% by weight of ammonia was placed in a glass container having a volume of 50 ml, phenolphthalein was added for coloring, and a sample of 30 mm x 60 mm was put in the container and sealed. After irradiation for 4 hours and 4 hours, the absorbance at 550 nm was measured. The results are shown in Table 5 and FIG. In Table 5,
"-" Indicates that no corona discharge treatment or low temperature plasma treatment was performed.

[0048]

[Table 5]  TiO_TwoInternal addition amount Corona low temperature plasticAbsorbance (abs.) Sample No. (wt%) Discharge treatment Zuma treatment After 2 hours After 4 hours 0 0 − − 0.468 0.470 5a 5.0 − (a) 0.239 0.142 5d 5.0 Weak − 0.244 0.1445e 5.0 Strong -0.203 0.082

<Effect of Antibacterial Test / Corona Discharge Treatment> Using the corona discharge treatment device manufactured by Kasuga Denki Co., Ltd. for the 5.0% by weight titanium oxide internal additive of Example 1, (A) weak,
Corona discharge treatment was performed under two conditions of (B) strong. For reference, the condition (c) described in Example 1 (gas: air, processing power: 100 W, processing time: 1 minute, vacuum degree:
Low temperature plasma treatment was performed at 0.2 Torr.

As in the case of Example 1, 40 ml of water containing 0.1% by weight of the commercial medium (including free-falling bacteria) was used for the antibacterial test.
Put a sample of 30mm × 60mm in the sample and seal it.
It was performed by allowing it to stand in the room under natural light. Propagation of the bacteria was determined by measuring the transmittance at 600 nm after 72 hours. The results are shown in Table 6 and FIG.

[0051]

[Table 6] Internal content of TiO ₂ Corona Transmissivity after low temperature plastic 72 hours Sample No. (wt%) Discharge treatment Zuma treatment (% T) 0 0 − − 70.8 5c 5.0 − (c) 89.7 5d 5.0 weak − 78.1 5e 5.0 strong − 83.9

It can be seen from Tables 4 to 6 that the deodorizing effect and the antibacterial effect are remarkably increased even by the corona discharge treatment, and the effect is comparable to the low temperature plasma polymerization.

Example 3 A polyester filament containing 5% by weight of titanium oxide for photocatalyst used in Example 1 was produced, and then a non-woven fabric was produced using the filament. Then, a hot melt adhesive powder was sprinkled on this non-woven fabric, and then a usual non-woven fabric made of polyester filament was laminated and adhered.

When this laminated non-woven fabric is used as a wallpaper, indoor odors are effectively removed, and even if it is pasted on a wall which is easy to condense, the ordinary non-woven wallpaper produces mold. Was not recognized.

Example 4 A non-woven fabric was produced by mixing the titanium oxide-added polyester filament for photocatalyst in Example 3 and a normal polyester filament in a weight ratio of 1: 1. When this non-woven fabric was used as a wallpaper, it effectively removed indoor odors, and even when it was pasted on a wall that is easy to condense, where normal non-woven wallpaper causes mold, no generation of mold was observed. .

Examples 5 to 7 The 5.0 wt% titanium oxide internal additive of Example 1 was irradiated with ultraviolet rays using a high-pressure mercury lamp (Example 5), and similarly treated with ozone (Example 6). ), And sand blasting (Example 7). In any case, the deodorizing effect and the antibacterial effect according to Examples 1 and 2 were obtained.

Example 8 95 parts by weight of polypropylene and 5 parts by weight of commercially available silver zeolite fine particles were mixed and melt-molded to give a thickness of 40.
Since a film of μm was obtained, this film was treated with gas: air, processing power: 100 W, processing time: 1 minute, vacuum degree:
Low temperature plasma treatment was performed under the condition of 0.2 Torr. This film was much more excellent in antibacterial property than the film not subjected to the low temperature plasma treatment.

Example 9 95 parts by weight of polypropylene and 5 parts by weight of commercially available fine particles of silver zeolite were mixed and melt-molded to obtain a thickness of 40.
A film having a thickness of μm was obtained.
Corona discharge treatment was performed in the same manner as in the above. This film is
The antibacterial property was remarkably superior to that of the film not subjected to corona discharge treatment.

[0059]

EFFECTS OF THE INVENTION The functional material of the present invention is notable for a relatively small amount of internal addition while adopting a method of internally adding functional inorganic particles having a deodorizing or antibacterial function to a molded product. Deodorization and antibacterial action are exhibited, and deterioration of the appearance, feel, mechanical strength and surface characteristics of the molded product is also effectively suppressed.

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[Procedure amendment]

[Submission date] August 14, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of drawings]

FIG. 1 is a graph showing the results of a deodorant test for checking the effect of titanium oxide internal addition.

FIG. 2 is a graph showing the results of a deodorant test for observing the effect of low-temperature plasma treatment.

FIG. 3 is a graph showing the results of an antibacterial test to see the effect of low temperature plasma treatment.

FIG. 4 is a graph showing the results of a deodorant test for observing the effect of corona discharge treatment.

FIG. 5 is a graph showing the results of a deodorant test for checking the effect of corona discharge treatment.

FIG. 6 is a graph showing the results of an antibacterial test for observing the effect of corona discharge treatment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location B32B 27/12 B32B 27/12 27/18 27/18 F C08J 7/00 302 C08J 7/00 302

Claims (5)

[Claims] 1. A plastic or rubber molded article (A) having internally added functional inorganic particles (a) having a deodorizing or antibacterial function, wherein the molded article (A) has a fine surface. A functional material characterized by being roughened. 2. A functional inorganic particle (a) having a deodorizing or antibacterial function is an inorganic particle carrying an antibacterial metal or an ion thereof, a photocatalytic inorganic particle, or a photoreduction plated inorganic particle. The described functional material. 3. The roughening treatment is an electrical treatment, an optical treatment,
The functional material according to claim 1, which is a chemical treatment or a mechanical treatment. 4. The functional material according to claim 3, wherein the electrical treatment of the surface roughening treatment is a low temperature plasma treatment or a corona discharge treatment. 5. A molded article (A) to which a functional inorganic particle (a) is internally added and whose surface is finely roughened is supported by a supporting material (B) which supports it. The functional material according to claim 1, which is characterized in that.