JP2007054988A - Deodorization sheet and its thermoformed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorizing sheet capable of permanently developing an expected deodorizing effect even if the amount of the iron (II) compound kneaded with a resin base material is relatively little, and its thermoformed product. <P>SOLUTION: The deodorizing sheet is a multilayered sheet made of a thermoplastic resin wherein at least two layers are laminated and characterized in that the iron (II) compound is kneaded with a thermoplastic resin, which forms the outermost surface layer part. At this time, 0.1-10 pts.wt. preferably 0.5-4 pts.wt. of the iron (II) compound is compounded with 100 pts.wt. of the thermoplastic resin, which forms the outermost surface layer part or 10-100 pts.wt. of a filler and 0.1-10 pts.wt., preferably 0.5-4 pts.wt. of the iron (II) compound are compounded with 100 pts.wt. of the thermoplastic resin which forms the outermost surface layer part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has an effect of eliminating bad odor, and is optimally used as a single or composite material as an interior material for a room such as a wall covering in a house or as an interior panel for a vehicle such as an automobile. And its thermoformed product.

  Conventionally, activated carbon, ion generators, etc. are well known for eliminating and deodorizing bad odors, but the former deodorization with activated carbon is a method of adsorbing in fine porous holes, so it exhibits a deodorizing effect. Is relatively short and needs to be frequently replaced, and the deodorization method using the latter ion generator causes a running cost.

On the other hand, it is completely different from the deodorization / deodorization method described above, and it is proposed that a resin base material contains a composition based on an iron (II) compound that exhibits a wide adsorption capacity for malodorous substances. (For example, refer to Patent Document 1).
Although this iron (II) compound itself exhibits a semi-permanent deodorizing effect, in reality, even if the iron (II) compound is kneaded into a resin base material to form a film, the deodorizing effect as expected is not obtained. . This is the same even when a relatively large amount of iron (II) compound is kneaded into the resin base material.

JP-A-2-211240

  Based on such knowledge, the inventors of the present application have intensively studied how to produce the deodorizing effect as expected when the iron (II) compound is kneaded into a resin base material for commercialization. As a result, the present inventors have found that the iron (II) compound kneaded in the resin base material can be exhibited on the resin surface as much as possible to exhibit the deodorizing effect as expected, and the present invention has been completed.

  The object of the present invention is to provide a deodorizing sheet and a thermoformed product thereof that can permanently exhibit the deodorizing effect as expected even when a relatively small amount of iron (II) compound is kneaded into the resin base material. There is to do.

The deodorant sheet of the present invention that achieves such an object is a multilayer sheet made of a thermoplastic resin in which at least two layers are laminated, and an iron (II) compound is contained in the thermoplastic resin that forms the outermost surface layer portion. It is characterized by being kneaded (claim 1).
At this time, the iron (II) compound is blended in the range of 0.1 to 10 parts by weight, preferably in the range of 0.5 to 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin forming the outermost surface layer part (claim) Item 2) or 100 to 100 parts by weight of the thermoplastic resin forming the outermost surface layer part, 10 to 100 parts by weight of filler and 0.1 to 10 parts by weight of iron (II) compound, preferably 0. It is preferable to blend in the range of 5 to 4 parts by weight (Claim 3), and further to emboss the surface of the outermost surface layer part so that the surface area is wide (Claim 4).
Moreover, the thermoformed product according to the present invention is obtained by thermoforming the deodorizing sheet according to any one of claims 1 to 4 by a hot press molding or a hot vacuum forming method.

According to the deodorant sheet and the thermoformed product according to the present invention, an iron (II) compound is kneaded in the thermoplastic resin forming the outermost surface layer portion of the multilayer sheet made of thermoplastic resin in which at least two layers are laminated. Therefore, the iron (II) compound kneaded in the thermoplastic resin forming the outermost surface layer portion of the thermoplastic resin multilayer sheet naturally appears on the surface of the outermost surface layer portion. As a result, even if a relatively small amount of iron (II) compound is kneaded in the thermoplastic resin forming the outermost surface layer portion, the deodorizing effect as expected can be exhibited permanently.
Accordingly, it can be used in the form of a flat plate indoors, particularly in the walls and ceilings of toilets, and can be used as a molded product in interior bathroom vanities and automobile interiors.

The present invention is described in detail below.
The deodorizing sheet A according to the present invention is formed by using a thermoplastic resin multilayer sheet in which at least two layers or films made of a thermoplastic resin are laminated.
Incidentally, the deodorizing sheet A in the illustrated example is formed as a multilayer sheet having a total of three layers by laminating the surface layers 2a and 2b on both the front and back surfaces of the intermediate layer 1, respectively.

At this time, the thickness of the two surface layers 2a and 2b which are the outermost surface layer portions of the deodorant sheet A is sufficiently thinner (for example, 0.1 to 0.3 mm) than the thickness of the intermediate layer 1 (for example, 1.0 to 5.0 mm). And an iron (II) compound is kneaded in the thermoplastic resin forming the outermost surface layer portions (surface layers 2a, 2b).
When used in such a form that only the surface side is exposed, such as indoor interior materials, the iron (II) compound is kneaded only in the outermost surface layer portion (surface layer 2a) on the surface side in contact with the outside air. You may do it.

Examples of the iron (II) compound used in the present invention include ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous bromide, ferrous iodide, ferrous ammonium sulfate (Mole salt), etc. And iron (II) inorganic salts, and organic salts such as ferrous malate and ferrous fumarate.
These iron (II) compounds are known to have antibacterial, antifungal and antistatic properties, and in addition, have no adverse effects on the human body.

  Examples of the thermoplastic resin used in the present invention include olefin resins such as polypropylene, polyethylene, vinyl chloride, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylate ester copolymer, acrylic resins, and urethanes. And a synthetic resin formed by mixing one or more selected from thermoplastic resins, olefinic, styrene-based, acrylic-based, polyester-based, urethane-based thermoplastic elastomers, synthetic rubbers, and the like.

  These thermoplastic resin compositions include, in addition to iron (II) compounds, fillers such as calcium carbonate, silica, clay, barium sulfate, and talc, and coloring such as ultraviolet absorbers, antistatic agents, dyes and pigments. An agent, a flame retardant, a plasticizer, an antibacterial agent, an antifungal agent, and the like can be appropriately blended.

  When the iron (II) compound is kneaded with the thermoplastic resin forming the outermost surface layer portion (surface layer 2a and / or 2b) of the deodorant sheet A, the iron (II) compound is used with respect to 100 parts by weight of the thermoplastic resin. Is blended in the range of 0.1 to 10 parts by weight. When the blending ratio of the iron (II) compound is less than 0.1 parts by weight, the deodorizing effect due to the iron (II) compound cannot be expected, and even when blending more than 10 parts by weight, the improvement of the deodorizing effect is not recognized. It becomes useless. Therefore, as a result of the test, the iron (II) compound is preferably blended in the range of 0.5 to 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Furthermore, with respect to 100 parts by weight of the thermoplastic resin forming the outermost surface layer portion (surface layer 2a and / or 2b) of the deodorant sheet A, 10 fillers such as calcium carbonate, silica, clay, barium sulfate and talc are added. -100 parts by weight and 0.1-10 parts by weight of iron (II) compound may be blended.
When the filler to be added is less than 10 parts by weight, the effect of mixing the filler (improvement of rigidity, improvement of heat resistance, etc.) cannot be obtained.
Further, when the filler to be added is added in an amount of more than 100 parts by weight, the amount of the resin is reduced accordingly, so that the obtained product (sheet, molded product) becomes brittle and easily cracked. Furthermore, since most of the filler has a higher density than the resin, an excessive load is applied to the extruder when kneading with the resin. Therefore, it is not preferable to add more than 100 parts by weight of the filler except in special cases.

Thus, in order to manufacture this multilayer sheet A made of thermoplastic resin, it can be manufactured by a method similar to the conventional method using an apparatus similar to the conventional one. That is, the intermediate layer 1 and the surface layers 2a and 2b are separately formed, sheeted, and laminated. For the sheeting of each layer, a calendar device, an extrusion device, or the like can be used.
And the thermoformed product which made the desired shape can be obtained by thermoforming this thermoplastic resin multilayer sheet A by a hot press molding or a heat vacuum forming method.

  Furthermore, in order to improve the design of the thermoplastic resin multilayer sheet A, surface decoration processing such as printing, embossing and polishing is performed on the outermost surface layer portion (surface layer 2a and / or 2b). Can do. By embossing the surface of the outermost surface layer portion (surface layer 2a and / or 2b), the surface area as the outermost surface layer portion can be formed wider than when embossing is not performed. The high deodorizing effect as the multilayer sheet A can be expected.

Next, specific examples will be described.
<Example 1>
A polypropylene resin was used as the thermoplastic resin, and a polypropylene resin (PP composite) adjusted to MFR 3.6 by blending 30 parts by weight of calcium carbonate with 70 parts by weight of the polypropylene resin copolymer was used. The intermediate layer 1 forming the multilayer sheet A uses a PP composite material as it is, and the surface layer 2a as the outermost surface layer portion is EFNICA (trade name; south) as an iron (II) compound with respect to 100 parts by weight of the PP composite material. 1 part by weight of “Efnica Co., Ltd.” was blended and kneaded, and sheeted on the multilayer sheet A using an extruder.
As an extrusion apparatus, the intermediate layer uses a φ90 extruder, the surface layers 2a and 2b use a φ75 extruder, and the molten resin formed into three layers is extruded from a T-die through a feed block to form a multilayer sheet A Got.
At this time, the intermediate layer 1 is adjusted to have a thickness of 1.0 mm, and the surface layers 2a and 2b are adjusted to have a thickness of 0.3 mm, and on the surface side of one surface layer 2a in contact with the outside air. Is embossed with an embossing roll with a textured pattern, and the surface side of the other surface layer 2b that is not in contact with the outside air is formed smoothly with a mirror surface roll, resulting in a multilayer sheet A having a total thickness of 1.6 mm. It was.

<Example 2>
A thermoplastic resin multilayer sheet A obtained in Example 1 is uniformly heated with a heater and subjected to hot press molding to obtain a three-dimensional thermoformed product (vehicle interior panel). Obtained.

<Example 3>
ABS resin (MFR3.0) is used as the thermoplastic resin, and the resin forming the surface layer 2a is EFNICA (trade name; manufactured by Nanban EFNICA) as an iron (II) compound with respect to 100 parts by weight of the ABS resin. The intermediate layer 1 composed of 3 parts by weight of the ABS resin was adjusted so that its thickness was 2.0 mm, and the surface layers 2a and 2b were adjusted so that its thickness was 0.5 mm. And the surface side of both surface layers 2a and 2b was smoothly finished with a mirror-finished roll, and a multilayer sheet A having a total thickness of 3.0 mm was obtained.

<Comparative example>
Using a material in which 5 parts by weight of EFNICA (trade name; manufactured by Nanban EFNICA Co., Ltd.) is used as an iron (II) compound, a copolymer of polypropylene resin alone (MFR30) is used as the thermoplastic resin. Thus, a vehicle interior panel having a three-dimensional shape with a substantially S-shaped cross section was injection molded.
In addition, on one side of this injection-molded product, an embossing process similar to the embossing pattern formed on the surface side of the surface layer 2a in Example 1 is performed by an injection mold in which a surface of the mold cavity is provided with a leather pattern. Is formed.

[Evaluation methods]
Each of the multilayer sheets A obtained in Examples 1 to 3 and the comparative example was cut into a size of 100 mm × 100 mm to form test pieces, and each test piece was put in a hard vinyl chloride container having a capacity of 600 ml, and the test gas was supplied. The initial concentration of gas in the container and the change in gas concentration over time were measured. Acetaldehyde and formaldehyde were used as test gases.
The measurement results are shown in Table 1 below.

In Example 1, since the amount of the resin is 70% by weight, the amount of iron (II) compound that appears on the surface is large even when the amount of the iron (II) compound is 1% by weight, and the test gas decomposes in 1/3 of the time of the comparative example. It is understood that
In Example 2, since the multilayer sheet obtained in Example 1 was thermoformed, the surface on the side hitting the mold is rich in resin, and the deodorizing performance is almost equivalent to that of the comparative example. Since the amount of the compounded iron (II) compound is 1/5, if the amount of the compounded iron (II) compound is the same, the deodorizing performance can be said to be 5 times, so the deodorizing method is superior to the comparative example. It is understood that the performance is demonstrated.

On the other hand, in the comparative example, although the blending amount of the iron (II) compound is larger than those in Examples 1 and 2, the deodorization performance is inferior because the resin used has a good MFR of 30. It is thought to do.
That is, when injection molding is performed using a polypropylene resin copolymer, the fluidity is improved by keeping the pressure and flow rate during injection molding low in order to minimize the distortion remaining in the molded product. Therefore, even though the surface of the mold cavity is embossed, most of the surface of the product that is in direct contact with the mold becomes a resin component with good fluidity. Most of the compounded iron (II) compound enters the resin and does not exist on the surface of the molded product. As a result, it seems that although there are many blends of iron (II) compounds, the corresponding deodorizing performance cannot be expressed.
Further, in Example 1, the blending amount of the iron (II) compound is only about 0.4% with respect to the thickness of the entire multilayer sheet of 1.6 mm, and the iron (II) compound is compared with the comparative example (5%). Only about 1/13 of the amount is used.

  Next, in Example 3, the deodorizing performance from the start to 60 minutes was measured as the residual concentration of the test gas. The results are shown in Table 2 below.

In this Example 3, since no filler is blended in the thermoplastic resin, and in addition, the outermost surface layer portion (surface layer 2a and / or 2b) is not embossed, so that the surface area is as in Example 1. The deodorizing performance is inferior to that of Example 1.
However, almost the same deodorizing performance was exhibited for the comparative example, and the compounding amount of the iron (II) compound with respect to the wall thickness of 3.0 mm of the thermoformed product in Example 2 corresponds to 1%. For the examples, it is understood that the deodorizing performance is equivalent despite the amount of the iron (II) compound being 1/5.

The schematic cross section which shows an example of this invention implementation.

Explanation of symbols

A: Multilayer sheet 1: Intermediate layer 2a, 2b: (Outermost) surface layer

Claims (5)

  A deodorizing sheet comprising a thermoplastic resin multilayer sheet in which at least two layers are laminated, wherein an iron (II) compound is kneaded in a thermoplastic resin forming an outermost surface layer portion.   The deodorant sheet according to claim 1, wherein 0.1 to 10 parts by weight of the iron (II) compound is blended with 100 parts by weight of the thermoplastic resin forming the outermost surface layer part.   The consumption according to claim 1, comprising 10 to 100 parts by weight of a filler and 0.1 to 10 parts by weight of the iron (II) compound with respect to 100 parts by weight of the thermoplastic resin forming the outermost surface layer part. Odor sheet.   The deodorizing sheet of any one of Claims 1-3 formed by embossing the surface of the said outermost surface layer part. A thermoformed product obtained by thermoforming the deodorant sheet according to any one of claims 1 to 4.

Images