JP2002317120A - Minus ion-generating composition, and minus ion- generating coating, molded article, laminated sheet and fiber containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a safe, minus ion-generating composition capable of fully exhibiting minus ion effects in small amounts enough to permit molding. SOLUTION: The minus ion-generating composition which generates a minus ion is comprised of a baddeleyite powder and a binder material. Incorporation of baddeleyite into the minus ion-generating composition permits to safely enjoy the minus ion effects without caring about radioactive rays and the like. Baddeleyite can exhibit sufficient minus ion effects with a small amount added to the binder material, and therefore the composition is improved in molding properties and can be widely applied in various life scenes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative ion generating composition for generating negative ions, a negative ion generating paint containing the composition, a molded product, a laminated sheet, and a fiber.

[0002]

2. Description of the Related Art In recent years, attention has been paid to the so-called negative ion effect. This negative ion effect is
When there are many negative ions in the air, inhaling the air gives a sedentary action to the human body, and means various effects such as analgesia, good sleep, antitussive, antiperspirant, refreshing feeling, and fatigue prevention.
For example, forests have many negative ions,
It is known that these effects can be enjoyed by bathing in a forest or the like.

[0003] Here, as a device for artificially generating negative ions, there is a negative ion generator utilizing high-voltage discharge. However, devices which can enjoy the negative ion effect at a lower cost include tourmaline and monazite. 2. Description of the Related Art A negative ion generating composition formed into a film or fibrous shape by molding a resin composition to which a powder is added is known. By using such a negative ion generating composition as an interior decoration material such as furniture, wallpaper, etc., water molecules in the air are decomposed and many negative ions can be generated in the air. A living room space capable of giving an effect can be formed.

[0004]

However, tourmaline, which is widely known as a negative ion generating substance, is required to obtain a sufficient effect even when actually added to a resin or the like.
There is a problem in that it must be added in a large amount, and it is difficult to produce an actual molded product having a sufficient negative ion effect. On the other hand, in the case of monazite, although a sufficient negative ion effect can be exhibited even with a small amount of addition,
It is known that monazite emits weak radiation to generate negative ions, which poses a problem that the human body is rather undesirable.

An object of the present invention is to provide a safe negative ion generating composition which can exhibit a sufficient negative ion effect with a moldable amount.

[0006]

In order to achieve the above-mentioned object, the present applicant has reported that an ore powder containing at least 80 wt% of zirconia (ZrO ₂ ) and hafnia (HfO ₂ ) exhibits a large negative ion effect and generates The present invention has been made based on the finding that the radiation dose to be applied is extremely weak. Specifically, the negative ion generating composition of the present invention is a negative ion generating material that generates negative ions, and contains 80 wt% of zirconia and hafnia.
% Or more, and a binder material.

[0007] Here, it is particularly preferable to employ badelite as the ore powder. Badelite is a mineral containing zirconia (ZrO ₂ ) as a main component (for example, 95% or more), and its theoretical values are Zr 67% and O ₂ 26%
And contains a small amount of hafnium oxide. Further, the average particle size of the buderite powder is preferably 0.1 μm to 50 μm, more preferably about 0.1 μm to 20 μm. For the production of the powder, a so-called ordinary crusher or mill for milling minerals, if necessary, They can be obtained by using these multiple times and pulverizing in multiple stages.

[0008] Further, the amount of addition of the baddelite is 1% with respect to the binder material in order to exhibit the negative ion effect.
wt% to 80 wt%. When the content is 1 wt% or less, the negative ion effect is not exhibited, and when the content is 80 wt% or more, the amount of the added paddleite relative to the binder material is too large, so that it may be molded into a desired shape or used as a paint containing the paddleite. It will be difficult.

According to the present invention, the negative ion generating composition contains 80 wt% of zirconia and hafnia.
By including the ore powder including the above, the negative ion effect can be safely enjoyed without considering radiation or the like. In addition, in the case of badderite, since a sufficient negative ion effect can be exhibited only by adding a small amount to the binder material, the moldability of the composition is improved, and it can be widely used in various situations in daily life. it can.

In the above description, as the above-mentioned binder material, cement, natural resin or synthetic resin, natural rubber or synthetic rubber, etc. used for concrete, building materials and the like can be considered. By using various cements such as alumina cement and Portland cement, concrete, mortar, etc. as a binder material, a negative ion generating composition can be used as a building material used for building wall materials, floor materials, etc. A living room space that can enjoy the ion effect can be configured. In addition, by adopting a natural resin or a synthetic resin, a natural rubber or a synthetic rubber as a binder material, it can be developed as a paint containing a negative ion generating composition, a resin molded product, a fiber, etc. It can be enjoyed with molded products such as resin.

Examples of natural resins include pine tar, shellac, dammar, balsam and the like. As a synthetic resin,
Thermosetting resins and thermoplastic resins are exemplified. As thermosetting resins, epoxy resins, unsaturated polyester resins,
Phenol resin, urea melamine resin, polyurethane resin, silicone resin and the like are mentioned, and these resins may be used alone or in combination of two or more.
As the thermoplastic resin, polyvinyl chloride resin, polyolefin resin, polystyrene resin, polyamide resin, polyester resin, polyurethane resin, acrylic resin, ABS resin, ionomer, methacryl resin, polyvinyl alcohol, cellulose plastic Similarly, these resins may be used alone or in a combination of two or more. Natural rubber includes cis 1,4-polyisoprene. Examples of the synthetic rubber include styrene butadiene rubber, isoprene rubber, ethylene propylene rubber, chloroprene rubber, nitrile rubber, urethane rubber and the like.

The fiber material serving as the binder material constituting the negative ion generating fiber containing the negative ion generating composition includes synthetic resin fiber material, semi-synthetic resin fiber material,
And recycled fibers and the like can be employed. As the synthetic resin fiber material, nylon, polyester, polyurethane, vinylon, vinylidene, polyvinyl chloride, acrylic, polyethylene, polypropylene and the like can be adopted. As the semi-synthetic resin fiber material, acetate, diacetate, triacetate and the like can be adopted. Rayon or the like can be used as the recycled fiber.

As a method for converting the anion-generating fiber into a fiber, melt spinning, wet spinning, dry spinning, dry-wet spinning and the like can be mentioned, and a spinning method suitable for the fiber material may be selected. Further, although not particularly limited, conjugate spinning having a core-sheath cross-sectional structure or the like can also be used. As such a fiber having a core-in-sheath structure, a fiber in which a paddleite powder is blended on the fiber surface to enhance the negative ion generating effect, and the core portion is not blended with the padelite powder, and the fiber strength is maintained. On the other hand, in consideration of dyeing and the like, a fiber having a core-sheath structure in which the paddleite powder is blended in the core and not blended in the sheath may be considered.

[0014] Of these resins or rubbers, more preferred are those based on polyolefins. Examples of the polyolefin-based resin or rubber include thermoplastic polyolefin-based elastomer (TPO), linear low-density polyethylene (LLDPE), and polypropylene (P
P). In addition, when such a badelite powder is mixed with a resin or rubber, a plasticizer, a stabilizer, a filler, an antioxidant, an antibacterial agent, an antistatic agent, an ultraviolet absorber, a foaming agent used for blending of a general resin are used. An agent, a flame retardant, etc. may be added as needed.

By adopting a resin or rubber as a binder material of such a negative ion generating material, it can be applied to films, sheets, molded products, paints, adhesives, leather, textile materials, sealing materials, fibers and the like. Therefore, the negative ion generating material can be used for a wide range of applications.

When the binder material is the aforementioned resin or rubber, it is preferable that an antistatic agent is added. Here, as the antistatic agent, anionic, cationic, nonionic or amphoteric ones can be employed. Examples of the anionic antistatic agent include fatty acid salts, higher alcohol sulfates, aliphatic amines, amide sulfates, alkylallyl sulfonates, and dibasic fatty acid ester sulfones. Examples of the cationic antistatic agent include fatty acid amine salts, quaternary ammonium salts, and alkylpyridium salts. Examples of the nonionic antistatic agent include polyoxyalkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkylamines, amides, sorbitans (polyoxyethylene sorbitan alkyl esters), and the like. Examples of the amphoteric antistatic agent include a betaine type and an imidazoline type. In addition, other than those used as such surfactants, block copolymer compounds of polyethylene glycol, polyoxyethylenediamine, polyether, polyester, and polyamide may be employed as nonionic high molecular weight antistatic agents. Can be.

In the case of a negative ion generating paint to which an antistatic agent has not been added, a negative charge can be obtained by performing an antistatic treatment on the surface to be coated or applying it to a metal plate such as aluminum which does not need to be subjected to the antistatic treatment. An ionic effect can be exhibited. In addition, when a negative ion generating film formed from a negative ion generating composition into a film shape and no antistatic agent is added, the negative ion generating film is laminated and adhered to an antistatic treatment-treated base fabric or a cellulose-based base fabric. It is preferable to use a laminated sheet. Thereby, since the base fabric has an antistatic effect, it is possible to prevent the film from being charged, and similarly, it is possible to reliably exert the negative ion effect.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing a badelite powder according to an embodiment of the present invention will be described. Badelite ore imported from South Africa is first crushed by a wet ball mill (ball: iron). Next, an aqueous sulfuric acid solution is added to the ball mill to remove iron, and then washed with water in the mill. Finally drain the water, dry at about 500 ° C. and crush. As a result, a badelite powder having an average particle size of about 0.7 μm was obtained.

[0019]

EXAMPLES (1) Example 1 Diisodecyl phthalate (DIDP) as a plasticizer and Ba- as a stabilizer were added to a polyvinyl chloride resin (PVC).
Zn, zinc stearate, and the baddelite powder according to the embodiment were mixed in a composition shown in Table 1 using a two-roll mill, and the resulting sheet was ester / rayon (35) with a urethane-based adhesive. / 65) to obtain a PVC leather. Negative ions generated from the film obtained in Example 1 were measured with a negative ion measuring device (manufactured by Alpha Lab), and the number of negative ions was 300 / min.
○ a case that occurred cm ³ or more, the case of less than 200 to 300 / cm ³ △, was assessed in the case of less as ×. Table 1 shows the evaluation results of Example 1.

[0020]

[Table 1]

As can be seen from the results of the ion measurement of Example 1 shown in Table 1, it was confirmed that PVC leather containing badelite had an effect of generating negative ions.

(2) Examples 2 to 6 and Comparative Example 1 Next, an antistatic material was added to the binder material to evaluate how the negative ion generation effect of baddelite was affected. A TPO (thermoplastic polyolefin-based elastomer) compound having a composition shown in Table 2,
Baderite powder according to the embodiment, as an antistatic agent,
Irgastat P18 (polymer-based antistatic agent based on polyamide-based copolymer: manufactured by Ciba Specialty Chemicals), Chemistat 1100, 2500, 3
No. 033 (Sanyo Chemical Industries, Ltd.) and the mixture shown in Table 3 using a two-roll mill and extrusion molding to obtain a sheet containing badelite powder. On the other hand, Comparative Example 1 was prepared in the same manner as in Example 2 except that Baderite was not added to the TPO compound in Table 2.
In the same manner as in Nos. 6 to 6, a sheet was obtained.

[0023]

[Table 2]

Negative ions generated from the films obtained in the respective Examples and Comparative Examples were measured with a negative ion measuring device (manufactured by Alpha Lab), and the amount of generated negative ions was 300 pieces / cm ³ or more. ○, 200 ~
The case of less than 300 pieces / cm ³ was evaluated as Δ, and the case of less than 300 pieces / cm ³ was evaluated as x. Table 3 shows the evaluation results of the examples.

[0025]

[Table 3]

Among Examples 2 to 6, it was confirmed that the films according to Examples 2 to 5 had a large negative ion generating effect. Since Comparative Example 1 does not contain badelite, it can be seen that there is no negative ion generation effect. On the other hand, it was found that Example 6 had a weak negative ion generation effect despite containing badelite. From this, it is assumed that the negative ion effect is greatly affected by the chargeability of the sheet. If the antistatic agent is not added, or if the amount of the antistatic agent is small, the negative ion effect is not affected. May be compromised.

(3) Examples 7 to 9 In Examples 7 and 8, a polyester base cloth was laminated and adhered to the sheet containing the baddelite powder obtained in Example 6, and a laminated sheet containing the badelite was obtained. I got In Example 9, a cotton cloth was laminated and adhered to the sheet containing the badelite powder obtained in Example 6 to obtain a laminated sheet containing the badelite. Negative ions generated from the laminated sheet obtained in each example were measured with a negative ion measuring device (manufactured by Alpha Lab), and when the amount of generated negative ions was 300 / cm ³ or more, 、, 200 to 3
The case of less than 00 pieces / cm ³ was evaluated as Δ, and the case of less than 00 was evaluated as ×. Table 4 shows the evaluation results of the examples.

[0028]

[Table 4]

In Examples 8 and 9, the amount of negative ions generated was 300 pieces / cm ³ or more, and it was confirmed that the negative ion generating effect was large. In Example 7 in which the antistatic treatment was not performed, the negative ion generation effect was weak. Accordingly, it is confirmed that a sheet containing baddelite using a resin as a binder material has a negative ion generating effect essentially, but may not exhibit a sufficient negative ion effect depending on the charging state of the sheet. Was.

(4) Example 10, Comparative Example 2 The solvent composition was 15% toluene, 15% butanol, 7% isopropyl alcohol, 8% butyl acetate, and 1% ethyl acetate.
A 5% by weight acrylic one-part paint was added with 5 parts by weight of the badderite powder according to the embodiment, and a commercially available aluminum plate surface was spray-coated with a paint containing a paddleite to obtain a coated plate. On the other hand, a coated plate obtained by spray-coating the surface of a commercially available aluminum plate with the above-mentioned acrylic one-pack coating material to which no baderite powder was added was used as Comparative Example 2. When negative ions generated from both coated plates were measured by a negative ion measuring device (manufactured by Alpha Lab), the coated plate according to Example 10 had a negative ion generation amount of 3
The number was 00 / cm ³ or more, and the effect of generating negative ions was confirmed. On the other hand, in the coated plate according to Comparative Example 2, such a negative ion effect was not recognized.

(5) Example 11, Example 12, Comparative Example 3, Comparative Example 4 (Example 11) Melt kneading of polypropylene resin (Idemitsu Petrochemical Co., Ltd., J-3054H) with addition of baddelite powder. Then, a molded product was obtained by injection molding. (Example 12) A polypropylene resin (Idemitsu Petrochemical Co., Ltd. J-3054H) to which a badelite powder and an antistatic agent (Chemistat 1100) were added was melt-kneaded to obtain a molded product by injection molding.

Comparative Example 3 The same polypropylene resin as in Example 11 was injection molded as it was to obtain a molded product. Comparative Example 4 A molded product was obtained by injection molding by adding only the antistatic agent of Example 12 to the same polypropylene resin as in Example 11. Negative ions generated from the molded products obtained in Example 11, Example 12, Comparative Example 3, and Comparative Example 4 were measured with a negative ion measuring device (manufactured by Alpha Lab). Table 5 shows the formulations of the examples and comparative examples, and the results of negative ion measurement.

[0033]

[Table 5]

That is, when a resin or rubber is used as a binder material, an antistatic agent is added together with the resin or rubber, or a film subjected to an antistatic treatment having a static elimination effect or a laminate laminated with a metal plate is used. It can be seen that the negative ion generating effect can be reliably exhibited.

(6) Example 13 and Comparative Example 5 (Example 1)
3) 20% by weight of badelite powder in nylon 66, 280 ° C
The mixture was melt-mixed with a twin-screw kneading extruder at the temperature described above to obtain a resin compound. Using an extruder type compound spinning machine,
The core portion is made of polyester, and the sheath portion is made of a resin compound containing the above-mentioned nylon 66 and badderite powder. Each is melted separately, spun as a composite fiber from a core-sheath type spinneret, and heated with a 160 ° C. drawing hot roller. After setting, it was rolled up to obtain a 70 denier, 24 filament drawn yarn.
The yarn was knitted by a circular knitting machine to produce a leg-shaped knit of pantyhose. (Comparative Example 5) Without blending Badelite with nylon 66,
A knit was produced in the same procedure as in Example 13.

Negative ions generated from the knits obtained in Example 13 and Comparative Example 5 were measured with a negative ion measuring device (manufactured by Alpha Lab), and the knit according to Example 13 showed negative ions generated. Quantity is 30
0 / cm ³ or more. On the other hand, in the knit according to Comparative Example 5, almost no negative ions were generated, and it was confirmed that the fiber containing the baddelite powder according to the present invention exhibited a negative ion generating effect.

(7) Example 14 and Comparative Example 6 (Example 14) Using a mortar material mixed at a mixing ratio of 1 shown in Table 6, a 10 cm square and a 5 mm thickness were formed.
After curing for 3 hours in an environment of ℃, the mold was removed to obtain a mortar plate. (Comparative Example 6) A mortar plate was obtained in the same procedure as in Example 14, except that the mixing ratio 2 shown in Table 6 was used.

Negative ions generated from the mortar plates obtained in Example 14 and Comparative Example 6 were measured with a negative ion measuring device (manufactured by Alpha Lab), and the amount of generated negative ions was 300 particles / cm ³ or more. ○, 20 in case of
The case of 0 to less than 300 pieces / cm ³ was evaluated as Δ, and the case of less than 0 was evaluated as ×. Table 6 shows the evaluation results of Example 14 and Comparative Example 6.

[0039]

[Table 6]

Cement is adopted as a binder material of the badderite powder, and a mortar plate formed of the cement can be used.
It was confirmed that it had a sufficient negative ion generating effect, and it was confirmed that the mortar plate according to Comparative Example 6 in which the badelite powder was not blended had no negative ion generating effect.

[0041]

According to the present invention as described above, since the radiation dose of baddelite is extremely weak, the negative ion effect can be safely enjoyed, and it is sufficient to add a small amount to the binder material. Since the composition can exhibit a significant negative ion effect, the moldability of the composition is improved, and the composition can be widely used in various situations in daily life.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08J 5/18 CEZ C08J 5/18 CEZ C08K 3/22 C08K 3/22 C09D 7/12 C09D 7/12 201/00 201 / 00 D01F 1/10 D01F 1/10 F term (reference) 4F071 AA01 AA10 AA14 AA19 AA20 AB30 AH19 BC01 BC07 4F100 AJ04B AJ06 AK01A AK15 AK52G AR00A BA02 DE01 DG11B EC18 EC182 GB66 GB90 4J002 AA001 BB 001 001 001 001 001 GK00 4J038 AA011 BA021 BA221 BA231 CA021 CB001 CB061 CB101 CC021 CD021 CE021 CG141 CP081 DA041 DA141 DA161 DB001 DD001 DD181 DG031 DH001 DL031 HA216 HA491 NA20 PC08 PC10 4L035 BB31 DD18 EE20 FF04 FF10 FF10 FF04 FF10 FF10 FF10 FF10 FF10 FF10 FF10 FF10

Claims (9)

[Claims] 1. A negative ion generating composition for generating negative ions, wherein zirconia (ZrO ₂ ) and hafnia (HfO ₂ ) are contained in a composition.
A negative ion generating composition comprising: an ore powder containing 0 wt% or more; and a binder material. 2. The negative ion generating composition according to claim 1, wherein the ore powder is badelite. 3. The negative ion generating composition according to claim 1, wherein the binder material is one of a resin and a rubber. 4. The negative ion generating composition according to claim 1, wherein the binder material is cement. 5. A negative ion generating paint comprising the negative ion generating composition according to any one of claims 1 to 3. 6. A negative ion generating molded product obtained by molding the negative ion generating composition according to any one of claims 1 to 3. 7. The negative ion generating molded product according to claim 6, wherein the molded product is formed into a film. 8. A negative ion generating laminated sheet, wherein the film-like negative ion generating molded product according to claim 7 and a base cloth or a cellulosic base cloth are laminated and bonded. 9. A negative ion generating fiber comprising the negative ion generating composition according to any one of claims 1 to 3.