JP4871248B2 - Iron-based deodorant, deodorizing thermoplastic resin and fiber processed product containing deodorant - Google Patents

Description

  The present invention relates to an iron-based deodorant, a thermoplastic resin having a deodorizing property containing the iron-based deodorant, and a fiber processed product having a deodorizing property to which the iron-based deodorant is attached. .

  Conventionally, inorganic, organic, natural, and combinations thereof have been developed as deodorant compositions, and research on photocatalysts using titanium oxide has been actively conducted recently. A photocatalyst can repeatedly decompose organic substances such as odorous substances by irradiation with ultraviolet rays, and has attracted attention as a safe and low-cost deodorant composition. In order to obtain photocatalytic activity, it is necessary to be in an excited state with light of an ultraviolet level, and its use is generally limited such as use in a place where sunlight can reach or use where a black light irradiation device can be placed. It was a thing. For this reason, it is known to contain a cluster of iron ions or a metal compound in order to exhibit deodorant performance even with light at a visible light level (for example, Patent Document 1 or 2).

  On the other hand, what consists of an iron compound and a chelating agent is known as a deodorant composition which does not require light, such as an ultraviolet-ray (for example, patent document 3 or 4). A deodorant composition comprising an iron compound and a chelating agent can be used as a paint by mixing with a pigment such as titanium dioxide, or can be used as a resin molded product by kneading with a resin.

Japanese Patent No. 2876524 Japanese Patent No. 3791150 Japanese Patent Publication No. 04-16182 Japanese Patent No. 3665970

  However, in the case of a photocatalyst, from the viewpoint of the deodorizing function, the deodorizing performance is not yet sufficient, and when it is used attached to or blended with a fiber processed product or a plastic molded product, There was a possibility of deteriorating the fibers and resin. In addition, the iron-based deodorant consisting of an iron compound and a chelating agent can be used in a place where it is not exposed to ultraviolet rays, and there is no possibility of deteriorating the resin, but when it adheres to or blends with a resin material. Since the deodorizing function is exhibited only in the portion exposed on the surface that can come into contact with the odorous substance, the expected desired performance cannot be exhibited, and further improvement of the deodorizing performance has been demanded.

  The present invention relates to an iron-based deodorant capable of stably exhibiting deodorant properties even in a place where it is not exposed to ultraviolet rays, a thermoplastic resin having a deodorizing property, and a deodorizing property. An object is to provide a processed fiber product.

In order to achieve the above object, the iron-based deodorant of the present invention comprises a divalent iron compound, a chelating agent, a porous material, and fine particle titanium oxide having an anatase type crystal structure with a particle size of 100 nm or less. To do.

  Since this invention is comprised as mentioned above, there exists an effect as described below.

  Stable and excellent deodorant performance even in places where it is exposed to ultraviolet rays, even when it is not exposed to it, it can be removed over a long period of time even when an iron-based deodorant is attached to the substrate. Deodorizing function can be exhibited without any problems.

  Embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic perspective view of a plastic molded product having a deodorizing property (deodorized plastic molded product) showing an example of use of the present invention.

In the deodorized plastic molded product 1, a skin material 3 is laminated on the surface of a plastic molded product body 2 made of a thermoplastic resin. The skin material 3 is made of a cloth 4 having a weight per unit area of 600 g / m ² or less, preferably within a range of 10 to 400 g / m ² , and an iron-based deodorant 5 containing a divalent iron compound on the back surface of the cloth 4. The back surface to which the iron-based deodorant 5 is attached is opposed to the surface of the plastic molded body 2 and is joined.

  The iron-based deodorant according to the present invention is characterized by comprising a divalent iron compound, a chelating agent, a porous material, and fine particle titanium oxide having a particle diameter of 100 nm or less.

  FIG. 2 shows the steps of a method for producing a deodorized plastic molded product, (a) is an explanatory view showing a state in which a skin material and a parison are arranged between molds that are opened, and (b) is a mold-clamped division. It is explanatory drawing which shows the state which pinched the parison by the type | mold.

  (1) As shown in FIG. 2A, the surface of the cloth 4 is made to face the cavity surface 11a of the one split mold 11 between the one split mold 11 and the other split mold 12 which are opened. Arrange.

  (2) After the step (1), the melted parison 13 is extruded from the extrusion head 10 of the extruder and disposed between the back surface of the cloth 4 and the other split mold 12.

  (3) After the step (2), the mold is clamped to hold the parison 13 between the pinch-off portions 11b and 12b of the one split mold 11 and the other split mold 12.

  (4) After the step (3), a pressurized fluid is introduced into the parison 13 through blowing means (not shown), and the cloth 4 disposed on the cavity surface 11a and the other side by the internal pressure of the pressurized fluid The split mold 12 is expanded into a shape that follows the cavity surface 12a.

  (5) After the step (4), after cooling, the mold is opened and the deodorized plastic molded product is taken out.

  That is, by interposing the iron-based deodorant according to the present invention between the back surface of the cloth and the surface of the plastic molded body, the iron-based deodorant is not substantially exposed on the surface of the cloth, A plastic molded product (deodorized plastic molded product) having a deodorizing property capable of continuously exhibiting a stable deodorizing performance is obtained.

The skin material is a cloth made of synthetic fibers such as polyester, polypropylene, polyamide, acrylic, polyurethane, and can be selected from woven fabric, knitted fabric, non-woven fabric, and the like. In particular, when the use of the deodorized plastic molded article is an automobile interior material, a nonwoven fabric having a weight per unit area within a range of 10 to 400 g / m ² is preferable from the viewpoint of blocking ultraviolet rays and improving air permeability. . If the weight per unit area is less than 10 g / m ^2, the unevenness of the outer surface of the molded product body is reflected on the surface up to the minute one, so that the appearance is likely to be damaged. On the contrary, if the weight per unit area is larger than 600 g / m ² , the three-dimensional shape reproducibility is inferior, and furthermore, it becomes difficult to contact the odor substance with the deodorant and the deodorization function cannot be exhibited. However, the skin material can be selected within a range that does not inhibit the odorous substance from coming into contact with the deodorant, and can be a multilayer in which a resin sheet is laminated on the surface of the nonwoven fabric.

  The method of supporting the iron-based deodorant on the fiber can use means such as surface adhesion, impregnation, melt-kneading and the like, and is not particularly limited, but is preferably a resin in order to enhance the deodorizing activity. A method of using an aqueous slurry liquid containing an emulsion as a binder and adhering to the fiber surface by spray drying, dipping, coating, or the like is used. In this case, fibers having an SP value of 9.5 or more, such as polyester, polyamide, acrylic, and polyurethane, are preferably used.

The SP value is a solubility parameter, and is obtained as the square root of the cohesive energy density (cal / cm ³ ).

  By using a fiber having an SP value of 9.5 or more, the adhesion of the iron-based deodorant to the fiber is improved, and the durability of the product can be enhanced.

  The plastic molded product body uses a thermoplastic resin such as polyethylene, polypropylene, polystyrene, polyester, polyamide, and vinyl chloride resin. As the thermoplastic resin, it is preferable to use a resin having an SP value of less than 9.5, such as polyethylene, polypropylene, and polystyrene. By using a resin whose resin has an SP value of less than 9.5, the hygroscopicity of the plastic molded product body can be suppressed and the durability can be enhanced.

  In the case of blow molding, the thermoplastic resin preferably has a melt tension of 1 gf or more and a melt flow rate of 2 g / 10 min or less. When the melt tension is less than 1 gf or the melt flow rate exceeds 2 g / 10 min, the parison drawdown is large and it is difficult to obtain a molded article stably.

  The plastic molded product body is not limited to the above-described blow molding, and can be molded by a method of melting other known thermoplastic resins such as sheet blow molding and injection molding and molding in a mold.

  For example, in the case of injection molding, a cloth with an iron-based deodorant attached to the back side of the cavity surface of one of the split molds is placed with its surface facing the mold, and then the mold is clamped and then melted into the cavity. The thermoplastic resin is injected and filled to injection-mold the plastic molded product body, and at the same time, the cloth is adhered and laminated.

  The iron-based deodorant is used as an aqueous slurry containing a binder and water.

  Examples of the divalent iron compound include ferrous sulfate, ferrous chloride, ferrous bromide, ferrous iodide and other inorganic salts of iron (II), ferrous gallate, malic acid Examples thereof include organic salts of iron (II) such as ferrous iron and ferrous fumarate.

  Any chelating agent can be used as long as it has a chelating ability for ions. For example, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, 1,2-diaminocyclohexanetetraacetic acid, hydroxyethyl Polyaminocarboxylic acids such as ethylenediaminetriacetic acid and dihydroxyethylglycine or water-soluble salts thereof; polyaminophosphoric acids such as ethylenediaminetetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid) or water-soluble salts thereof; citric acid, gluconic acid, etc. Oxycarboxylic acid or a water-soluble salt thereof, alkyl diphosphonic acid or a water-soluble salt thereof, and the like. These chelating agents can be used alone or in the form of a mixture. In the present invention, it is particularly preferable to use polyaminocarboxylic acids such as EDTA and iminodiacetic acid and their water-soluble salts (sodium salt, potassium salt, etc.). The chelating agent reacts and stabilizes with divalent iron ions contained in the iron-based deodorant. The amount of chelating agent used is chelating 0.1-50%, preferably 2-30%, more preferably 5-20% of the ferrous ion [Fe (II)] present in the aqueous resin liquid. Any proportion may be used.

In the present invention, as a preferable combination of a divalent iron compound and a chelating agent, a combination of iron sulfate and EDTA can be shown. In this case, when a specific amount of EDTA used is shown, iron sulfate (FeSO ₍₄ · 7H ₂ O) per 100 parts by weight of EDTA is 1 to 80 parts by weight, preferably 20 to 60 parts by weight. Chelating agents stabilize iron ions in water and prevent precipitation of iron ions.

  As a method for adding the divalent iron compound and the chelating agent to the aqueous resin solution, in addition to the method of adding the divalent iron compound and the chelating agent as they are to the aqueous resin solution, preferably, the divalent iron compound and the chelating agent are added. A method of adding in the form of an aqueous solution containing both of the agent can be employed. When added as an aqueous solution containing a divalent iron compound and a chelating agent, the concentration of the divalent iron compound is 5 to 30% by weight, preferably 10 to 20% by weight. Moreover, it is also preferable to contain alum in this aqueous solution.

  Examples of the porous material include zeolite, white clay, activated clay, diatomaceous earth, montmorillonite, sepiolite, kaolin, bentonite, silica, alumina, titania, zirconia, magnesium oxide and the like. The porous material adsorbs and stabilizes an active ingredient containing divalent iron ions and traps malodorous substances as an adsorbent.

  The pH of the aqueous slurry is preferably 6 to 10, more preferably 7 to 9. If an aqueous slurry having a pH of less than 6 is used, the deodorizing performance of acetaldehyde is lowered. An aqueous slurry having a pH of 9 or more decreases the stability of divalent iron ions.

  As the titanium oxide, titanium dioxide having a particle size of 100 nm or less, preferably 50 nm or less, and having an anatase type crystal structure is preferably used. In order to improve the deodorizing performance of the iron-based deodorant according to the present invention, titanium oxide having a so-called photocatalytic function is added, which is different from that for obtaining a deodorizing function by a photocatalyst. That is, the iron-based deodorant to which the photocatalytic titanium oxide is added has a feature that the deodorization performance is remarkably improved regardless of the presence or absence of light in the ultraviolet ray or visible light region.

  As the binder, resins used in conventional water-based paints can be used. Examples of such resins include acrylic emulsions, styrene-butadiene emulsions, and vinyl acetate emulsions.

  If necessary, inorganic powders such as magnesium compounds and lithopone can be added to the iron-based deodorant of the present invention. Addition of these inorganic powders improves the foamability of the coating film. Examples of the magnesium compound include magnesium hydroxide, magnesium oxide, magnesium carbonate and the like. These inorganic powders are 5-50 weight% in a composition, Preferably it is 10-40 weight%, More preferably, it is 20-35 weight%.

  Further, if necessary, a pH adjuster, a colorant, a dispersant (surfactant), a thickener (water-soluble polymer), a flame retardant (antimony oxide), and the like can be blended. When an iron-based deodorant is used as a coating on a solid surface such as a wall, floor, or ceiling, an appropriate amount of an aqueous emulsion paste containing titanium dioxide or zinc oxide can be added. The addition amount of these titanium dioxide and zinc oxide is 1 to 40 weight% in a composition, Preferably it is 5 to 30 weight%. The pH of the composition of the present invention is not particularly limited, but is usually 6 to 9, preferably 7 to 8.

The iron-based deodorant of the present invention is preferably attached at a rate of 0.1 mmol / m ² or more with respect to the fiber processed product. If it is less than 0.1 mmol / m ² , the deodorizing performance is lowered.

  The removal rate of the odor gas can be adjusted by changing the water dilution ratio of the iron-based deodorant composed of an aqueous slurry in consideration of the needs and cost of a plastic molded product having a deodorizing property.

In addition, in the plastic molded article having deodorizing properties according to another embodiment, the fiber constituting the fabric having a weight per unit area of 10 to 600 g / m ² has an SP value of 9.5 or more, and a pigment is applied to the fiber surface. An iron-based deodorant containing a substantially colorless divalent iron compound not contained is supported, the plastic molded product has an SP value of less than 9.5, a melt flow rate of 1 gf or more and a melt flow rate. Is composed of a thermoplastic resin of 2 g / 10 min or less.

(Preparation of deodorant)
After dissolving 10 parts of ferrous sulfate and heptahydrate (FeSO ₄ .7H ₂ O) and 10 parts of ethylenediaminetetraacetic acid disodium (EDTA-2Na) as a chelating agent in 100 parts of water, zeolite 20 And 1 part of a nonionic surface active agent (Rheodor, manufactured by Kao Corporation) as a dispersant are mixed with stirring uniformly, and then magnesium sulfate, sodium sulfate and sodium bicarbonate as a pH adjuster are added in appropriate amounts. An aqueous slurry having a pH of about 8 was prepared and used as a mixed solution A. After adding 20 parts of an aqueous acrylic resin emulsion (solid content: 10 wt%) to 80 parts of this mixed liquid A, it was diluted 8 times with water to obtain mixed liquid B.

  Next, a deodorant solution was prepared using the mixed solution B, photocatalytic titanium oxide sol, titanium oxide for pigment, and titanium tetrachloride.

Example 1 0.5 parts of titanium oxide sol (solid content 30 wt%, particle size 30 nm) and 200 parts of water were added to 100 parts of the mixed solution B and mixed uniformly to obtain a deodorant solution C1. Next, 1.8 ml of the C1 solution was attached to the surface of the 200 cm ² non-woven fabric by spraying, and then dried at 100 ° C. for 10 minutes to prepare Sample D1.

Subsequently, the following acetaldehyde deodorization test was performed on the sample D1, and the deodorization performance was evaluated. Acetaldehyde deodorizing gas sampling valve to the test, using a closed vessel 17.5L which established a 10w fluorescent lamp holders and small fan, put the sample area 200 cm ² in a sealed container, acetaldehyde (gas) 0.3 ml It is injected into the reactor, and the concentration of acetaldehyde is quickly measured with a detector tube, and this value is taken as the initial concentration (a) volppm. At this time, the ultraviolet irradiance with a wavelength of 300 nm to 400 nm on the sample surface was less than 0.01 W / m ² (indoor light level). After a certain time, the gas concentration is measured and set to (b) volppm. The removal rate (c) is obtained from (a) and (b) by the following equation.

    Removal rate (%) = (ab) / a × 100

  Next, the same operation was carried out without putting a sample, and when there was a decrease in gas concentration of 1 volppm or more, this value was subtracted from the removal amount (ab) and corrected.

  Example 2: Acetaldehyde deodorization test was conducted in the same manner as in Example 1 except that the sample D1 was turned off with a cover attached to a sealed container to block the light and measured in a dark place. The deodorant performance was evaluated.

Example 3 Deodorant solution C1 was applied to the nonwoven fabric by spraying at a rate of 90 g / m ² on the back side of the nonwoven fabric having a weight per unit area of 400 g / cm ² manufactured by needle punching using polyester fibers. Then, it was dried at 100 ° C. for 15 minutes. Thereafter, the nonwoven fabric was set in a split mold, and blow molding was performed using a polypropylene resin having a melt tension of 3.5 gf and a melt flow rate of 0.5 g / 10 min to obtain a deodorized plastic molded product. A sample D2 was obtained by cutting out (length) 12.5 cm × (width) 16 cm from the deodorized plastic molded product. The adhesion amount of the iron-based deodorant was 0.7 mmol / m ² as an iron compound. For sample D2, an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorization performance.

  Example 4 1.0 part of titanium oxide sol and 199 parts of water were added to 100 parts of the mixed solution B and mixed uniformly to obtain a deodorant solution C2. Sample D3 was prepared in the same procedure as in Example 1 and an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorizing performance.

  Example 5: 0.1 part of titanium oxide sol and 200 parts of water were added to 100 parts of the mixed liquid B and mixed uniformly to obtain a deodorant solution C4. Sample D4 was prepared in the same procedure as in Example 1 and an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorization performance.

  Example 6: 0.5 parts of titanium oxide sol and 284 parts of water were added to 15 parts of the mixed liquid B and mixed uniformly to obtain a deodorant solution C4. Sample D5 was prepared in the same manner as in Example 1, and an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorization performance.

Comparative Example 1: The mixture B was diluted 3 times with water to obtain a deodorant solution C5, and then adhered to the nonwoven fabric at a rate of 1.8 ml / 200 cm ² and dried at 100 ° C. for 10 minutes to give a sample D6. An acetaldehyde deodorization test was conducted in the same manner as in Example 1, and the deodorization performance was evaluated.

Comparative Example 2 10 parts of titanium oxide sol, 30 parts of colloidal silica and 110 parts of water were mixed with stirring to prepare a photocatalyst solution C6. Sample D7 in which photocatalyst liquid C6 was adhered to the nonwoven fabric at a rate of 1.0 ml / 200 cm ² was prepared. After that, after sample D7 was put into the reactor, a chemical lamp was installed in the container, and the sample was pretreated by irradiating with ultraviolet rays (sunlight level in the vehicle) with a wavelength of 300 nm to 400 nm and an irradiance of 1 W / m ² for 1 hour. The measurement was performed according to the method of Example 1 except that acetaldehyde gas was introduced while the lamp was turned on.

Comparative Example 3 As in Comparative Example 2, a sample D7 pretreated with a chemical lamp for 1 hour was used to conduct an acetaldehyde deodorization test and evaluate the deodorizing performance. However, a white fluorescent lamp was used as the lamp in the container, and measurement was performed while irradiating the sample surface with light. The irradiance of the sample surface at a wavelength of 300 nm to 400 nm was 0.2 W / m ² .

Comparative Example 4 As in Comparative Example 2, a sample D7 pretreated with a chemical lamp for 1 hour was used to conduct an acetaldehyde deodorization test and evaluate the deodorizing performance. However, the measurement was performed without lighting the lamp in the container. The ultraviolet irradiance with a wavelength of 300 nm to 400 nm on the sample surface was less than 0.01 W / m ² (indoor light level).

  Comparative Example 5: 0.5 parts of titanium oxide sol and 298 parts of water were added to 1.5 parts of the mixed liquid B and mixed uniformly to obtain a deodorant solution C7. Sample D8 was prepared in the same procedure as in Example 1 and an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorization performance.

  Comparative Example 6: In order to compare the types of titanium oxide, 0.3 part of titanium oxide for pigment (particle diameter 250 nm) and 200 parts of water were added to 100 parts of the mixed solution B to prepare a deodorant solution C8. Sample D9 was prepared in the same procedure as in Example 1 and an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorization performance.

Comparative Example 7: To compare the types of titanium oxide, 0.7 part of titanium tetrachloride and 199 parts of isopropyl alcohol were added to 100 parts of the mixed solution B, and then diluted with water twice to obtain a deodorant solution C9. It was adjusted. A sample D10 was prepared by adhering the deodorant solution C9 to the nonwoven fabric at a rate of 3.6 ml / 200 cm ² , and an acetaldehyde deodorization test was performed in the same manner as in Example 1 to evaluate the deodorization performance.

  The evaluation results of the deodorizing performance are shown in Table 2. For samples D1, D2 and D3, the acetaldehyde concentration was below the detection limit of the detector tube in less than 1 hour, so the removal rate was above this value.

From Table 2, deodorant of the present invention exhibits excellent deodorizing performance against the acetaldehyde, without ultraviolet irradiation Ru can exhibit the deodorizing performance.

It is a model perspective view of the plastic molded product which has the deodorizing property concerning this invention. 1 shows an embodiment of a method for producing a deodorized plastic molded article according to the present invention, and (a) is an explanatory view showing a state in which a skin material and a parison are arranged between molds that are opened, (b) ) Is an explanatory view showing a state in which the parison is clamped by the clamped split mold.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Deodorized plastic molded product 2 Plastic molded product main body 3 Skin material 4 Cloth 5 Iron-type deodorant 10 Extrusion head 11 One split type 11a, 12a Cavity surface 11b, 12b Pinch off part 12 The other split type 13 Parison

Claims (5)

An iron-based deodorant comprising a divalent iron compound, a chelating agent, a porous material, and fine particle titanium oxide having an anatase type crystal structure having a particle diameter of 100 nm or less.   A thermoplastic resin having deodorizing properties, wherein the iron-based deodorant according to claim 1 is contained in a thermoplastic resin. A fiber processing products, textile processing products having deodorant, characterized in that depositing the iron-based deodorant of claim 1, wherein. A fiber processed article having deodorizing properties, wherein the iron-based deodorant according to claim 1 is attached to the fiber processed article at a rate of 0.1 mmol / m ² or more. The iron-based deodorant according to claim 1, textile processing products having deodorant, characterized in that to a weight per unit area is not 10 adhered to the back surface of the fabric within the range of 400 g / m ^2.

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