JP2004262991A - Antibacterial, highly damping resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial, highly damping resin molding useful for a wide range of applications and having excellent antibacterial properties and high damping properties. <P>SOLUTION: The antibacterial, highly damping resin molding is produced by incorporating an iodine composite and a low-molecular-weight organic material having a high dipole moment into a base resin. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

表１から、検体１および検体２のいずれについても、大腸菌については３５℃２４時間後、測定−１、測定−２、測定−３のいずれもケースでも、完全に死滅しており、また白癬菌についても、生菌数が大幅に減少しており、検体１および検体２が抗菌効果に優れていることが確認された。
反発弾性試験
上記実施例１および比較例２の各サンプルについて反発弾性を測定した。その結果を図５に示した。尚、反発弾性の測定は、図４に示す装置を用いて行った。
すなわち、図４に示す金属台上に各サンプルを置き、これに５００ｍｍの高さから直径１０ｍｍの鋼球を落下させ、その跳ね返りの高さをｈとし、このｈに基づき次式に従って反発弾性（％）を測定した。また測定は、各サンプル毎１０回ずつ行い、それらの平均高さｈより求めた。反発弾性（％）＝（ｈ／５０）×１００
図５から、ヨウ素包接体およびＤＣＨＢＳＡの両方を配合した実施例１に係るサンプルと、ＤＣＨＢＳＡのみを配合し、ヨウ素包接体を使用していない比較例２のサンプルとは、いずれも同様に優れた反発弾性（衝撃吸収性）を示し、かつヨウ素包接体の配合が反発弾性に悪影響を与えないことが確認された。
粘弾性試験
上記実施例１および２並びに比較例１の各サンプルについて、動的粘弾性（ｔａｎδ）を測定した。その結果を図６に示した。尚、動的粘弾性（ｔａｎδ）の測定は、動的粘弾性測定試験装置（レオバイブロンＤＤＶ−２５ＦＰ、株式会社オリエンテック製）を用いて行った。
【００４３】
図６から、ヨウ素包接体およびＤＣＨＢＳＡのいずれも配合していない比較例１のサンプルに対し、ＤＣＨＢＳＡの含有量を３重量部とした実施例１、およびＤＣＨＢＳＡの含有量を１重量部とした実施例２については、それぞれ配合量に従ってｔａｎδが高くなると共に、そのピークが高温側へとシフトしていることが確認された。尚、ｔａｎδが高いということは、低反発性（衝撃吸収性）に優れているということもなり、この粘弾性試験によっても、実施例１および２のサンプルが衝撃吸収性に優れていることが確認された。
【００４４】
【発明の効果】
本発明の成形物は、ベース樹脂中にヨウ素複合体と高双極子能率を有する有機低分子材料とを含むことから、広範な用途に適用可能であり、かつ優れた抗菌性と高減衰性とを兼備する。
【図面の簡単な説明】
【図１】ベース樹脂における双極子の状態を示した模式図。
【図２】エネルギーが加わったときのベース樹脂における双極子の状態を示した模式図。
【図３】ヨウ素複合体と高双極子能率を有する有機低分子材料とを含むベース樹脂における双極子の状態を示した模式図。
【図４】反発弾性の測定装置を示す模式図。
【図５】実施例１に係るサンプルと比較例２に係るサンプルの反発弾性を示すグラフ。
【図６】実施例１および２に係るサンプルと比較例１に係るサンプルの各温度におけるｔａｎδを示すグラフ。
【符号の説明】
１１・・・ベース樹脂
１２・・・双極子[0001]
[Industrial applications]
The present invention, for example, shoes, inner soles, clothing such as slippers, rackets and bat grip bands, sporting goods such as gloves for gloves, carpets, kitchen mats, living goods such as bath mats, wallpaper, wall materials, ceiling materials, A wide range of building materials such as flooring, household equipment such as toilet seats, toilets, and bathtubs, household appliances such as washing machines, vacuum cleaners, refrigerators, dishwashers, and electrical equipment such as cameras, videos, radios, stereos, and computers. The present invention relates to an antibacterial high-damping resin molded article applicable to various uses. More specifically, the present invention relates to an antibacterial high-damping resin molded article having both excellent antibacterial properties and high damping properties.
[0002]
[Prior art]
Iodine has excellent antibacterial properties comparable to halogenated antibacterial agents, and its antibacterial effect is independent of the pH value of its environment, and has a broad antibacterial spectrum that is active against a wider range of bacteria and viruses. It is known as having an antibacterial substance. In addition, iodine has the advantage of being relatively safe for the human body and excellent in safety.
[0003]
However, iodine is volatile, has a high solid vapor pressure, and has a property of rapidly losing its antibacterial effect over time, particularly when exposed to high temperatures.
[0004]
Due to such properties of iodine, various devices have been devised for application to resin molded products.
[0005]
For example, an iodine complex in which iodine is supported on an organic carrier or an inorganic carrier and absorbed to form a complex to control the release rate of iodine is also an example. As organic carriers to be complexed with iodine, for example, polyvinylpyrrolidone, polyether glycol, polyacrylic acids, polyamides, polyoxyalkylenes, starches, polyvinyl alcohol and the like are known. Examples of the inorganic carrier include activated carbon, zeolite, diatomaceous earth, calcium silicate and the like.
[0006]
An antibacterial resin molded product in which iodine is composited by applying this composite technology has been proposed. For example, there is an antibacterial resin molded product containing polyacetalized polyvinyl alcohol (PVA / I complex) complexed with iodine.
[0007]
This antibacterial resin molded product is formed from a polyacetalized polyvinyl alcohol complexed with iodine into a foam, a sheet, a film, or the like, and the molded product comes into contact with water or water vapor to release and release iodine ions, Antibacterial properties are exhibited (for example, see Patent Document 1).
[0008]
[Patent Document 1]
JP-A-2-299662 (Claims, pages 4 to 20)
[0009]
[Problems to be solved by the invention]
However, when the above-described iodine composite is blended into a base resin such as polyethylene, polypropylene, hard polyvinyl chloride, or polystyrene, which is widely used as a resin material of a molded article, and molded, the molding temperature is 200 ° C. Because of the above, iodine is released at the time of molding, and there is a problem that a sufficient amount of effective iodine cannot be secured.
[0010]
For this reason, the type of the base resin of the antibacterial resin molded product that can be molded using the iodine composite is limited to a resin having a low molding temperature, and its use is also narrowly limited.
[0011]
In the process of studying an antibacterial resin molded product using an iodine complex, the present inventors have found that by including an organic low-molecular material having high dipole efficiency in the base resin, the molding temperature of the base resin can be reduced. And found that the molded article can be provided with high damping properties, and based on this finding, completed the present invention.
[0012]
The present invention has been made in view of the above technical problem, and provides an antibacterial and high-attenuating resin molded article that is applicable to a wide range of uses and has both excellent antibacterial properties and high-attenuating properties. The purpose is.
[0013]
[Means for Solving the Problems]
In order to achieve the above object, the present invention has as its gist an antibacterial high-attenuating resin molded article characterized by containing an iodine complex and an organic low-molecular material having a high dipole efficiency in a base resin. .
[0014]
The antibacterial high-damping resin molded product of the present invention (hereinafter, simply referred to as molded product) includes, for example, clothing such as shoes, inner soles and slippers, rackets and bat grip bands, sports equipment such as gloves for gloves, carpets, Living goods such as kitchen mats and bath mats, building materials such as wallpaper, wall materials, ceiling materials, flooring materials, household equipment such as toilet seats, toilet bowls, bathtubs, and household appliances such as washing machines, vacuum cleaners, refrigerators, dishwashers, etc. It can be applied to a wide range of uses such as cameras, videos, radios, stereos, and electrical equipment such as computers.
[0015]
As the base resin in the molded article of the present invention, for example, vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, polymethyl acrylate, polymethyl methacrylate, and ethylene-vinyl acetate copolymer Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl alcohol copolymer such as ethylene-vinyl alcohol copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, chlorinated polyethylene, etc. Polyolefin, polystyrene, styrene-based resin such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide-based resin such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12, and the like; Po Ester, polycarbonate, polyacetal, polyphenylene sulfide, polyether ether ketone, polyether nitrile, modified polyphenylene ether, polyether sulfone, polysulfone, fluororesin, polyarylate, polyamideimide, polyetherimide, and thermoplastic polyimide, biodegradable resin Or a mixture of two or more selected from the group of unsaturated polyesters, epoxies, phenols, melamines, urethanes, and silicon resins, or a mixture thereof. Can be appropriately selected for use.
[0016]
The base resin contains an iodine complex and an organic low molecular weight material having a high dipole efficiency. Examples of the iodine complex include, for example, triiodide (iodide) such as iodine, sodium iodide or potassium iodide, polyether glycols, polyacrylic acids, polyamides, polyoxyalkylenes, starches, polyvinylpyrrolidone and polyvinyl An iodine hole which is supported on an iodine carrier such as an alcohol and absorbed to form a complex is exemplified.
[0017]
In addition, the above-mentioned iodohole is used as a guest molecule, and is used as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, cyclodextrin such as cyclocyclodextrin, gelatin, lactose, carboxymethylcellulose, gum arabic or the like. An iodine clathrate included in a host molecule composed of a mixture of two or more kinds is also included in the category of the iodine complex of the present invention.
[0018]
The above-mentioned iodine clathrate has a sufficient antibacterial effect and thermal stability when clathrated so that host molecules and guest molecules are present at a weight ratio of 99: 1 to 50:50. Is preferred. Further, among the above-mentioned iodine clathrates, an iodine clathrate in which cyclodextrin is used as a host molecule and clathrates iodine is preferable because it has excellent iodine retention properties and excellent thermal stability and dispersibility.
[0019]
The effective iodine content of the iodine complex is desirably at least 5%, preferably 5 to 20%, from the viewpoint that sufficient antibacterial properties can be exhibited.
[0020]
Which type of iodine complex is used depends on the strength and duration of the required antibacterial activity (eg, the effective amount of iodine, the amount of iodine released per unit time, etc.), the temperature and pressure during production, and the operating environment. It may be appropriately determined in consideration of such factors.
[0021]
The iodine complex is desirably contained at a ratio of 0.1 to 30 parts by weight, more preferably 1 to 25 parts by weight, and most preferably 5 to 25 parts by weight based on 100 parts by weight of the base resin. . When the content of the iodine complex is less than 0.1 part by weight, a sufficient antibacterial effect may not be obtained. When the content exceeds 30 parts by weight, the antibacterial effect is too strong, There is a possibility that adverse effects such as non-uniform dispersion or reduction in mechanical strength of the molded product may occur.
[0022]
Examples of organic low molecular weight materials having a high dipole efficiency include N, N-dicyclohexylbenzothiazyl-2-sulfenamide (DCHBSA), 2-mercaptobenzothiazole (MBT), dibenzothiazyl sulfide (MBTS), N -Cyclohexylbenzothiazyl-2-sulfenamide (CBS), N-tert-butylbenzothiazyl-2-sulfenamide (BBS), N-oxydiethylenebenzothiazyl-2-sulfenamide (OBS), A compound having a benzothiazyl group such as N, N-diisopropylbenzothiazyl-2-sulfenamide (DPBS);
2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" tetrahydrophthalimide) having a benzene ring having an azole group bonded to a nucleus and a phenyl group bonded thereto. Methyl) -5'-methylphenyl} -benzotriazole (2HPMBB), 2- {2'-hydroxy-5'-methylphenyl} -benzotriazole (2HMPB), 2- {2'-hydroxy-3'-t- Butyl-5'-methylphenyl} -5-chlorobenzotriazole (2HBPCB), 2- {2'-hydroxy-3 ', 5'-di-t-butylphenyl} -5-chlorobenzotriazole (2HDBPCB) A compound having a benzotriazole group,
A compound having a diphenyl acrylate group such as ethyl-2-cyano-3,3-di-phenyl acrylate;
Alternatively, one or more compounds selected from compounds having a benzophenone group such as 2-hydroxy-4-methoxybenzophenone (HMBP) and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (HMBPS). Mixtures can be mentioned.
[0023]
The low-molecular organic material having a high dipole efficiency has a function of lowering the molding temperature of the base resin. According to the experiment of the present inventor, for example, when molding this using polyethylene as a base resin, the molding temperature is 120 to 180 ° C., but by including an organic low molecular material in the base resin, the molding temperature is increased. Was 100 to 160 ° C.
[0024]
Similarly, polypropylene has a molding temperature of 140-190 ° C at 120-180 ° C, polystyrene has a molding temperature of 160-200 ° C at 140-180 ° C, and polyacetal has a molding temperature of 200-220 ° C of 160-200 ° C. ° C was confirmed.
[0025]
By including the organic low-molecular material in the base resin in this manner, molding at a low temperature becomes possible, so that iodine is released at the time of molding, and a problem that a sufficient amount of effective iodine cannot be secured is less likely to occur. .
[0026]
Organic low molecular weight materials with high dipole efficiency, when incorporated in the base resin, dramatically improve the energy absorption performance of the molded product, such as shock absorption, vibration attenuation, or sound absorption. There is a function to make it.
[0027]
Before the application of energy such as impact, vibration, or sound, the arrangement of the dipoles 12 in the base resin 11 is stable as shown in FIG. However, as shown in FIG. 2, when energy such as impact, vibration, or sound is applied to the base resin 11, a displacement occurs in the dipole 12 existing inside the base resin 11, and as a result, Each dipole 12 will be placed in an unstable state, and each dipole 12 will attempt to return to the stable state shown in FIG. At this time, energy is consumed.
[0028]
It is considered that energy displacement performance such as shock absorption, vibration damping, or sound absorption is generated through the displacement of the dipole inside the base resin and the energy consumption due to the restoring action of the dipole. From such a mechanism of energy consumption, it is understood that the amount of the dipole moment inside the base resin 11 greatly affects each performance. According to the experiments by the present inventors, it was found that the larger the amount of dipole moment in the inside of the base resin 11, the higher the energy attenuation of the base resin 11.
[0029]
The above-described organic low molecular weight material having a high dipole efficiency has a function of dramatically increasing the amount of dipole moment in the base resin, and by including this in the base resin, as shown in FIG. As described above, the amount of the dipole moment in the base resin increases to three times or ten times under the same conditions. Along with this, the energy consumption due to the dipole restoring action when the above-mentioned energy is added will also increase drastically, and as a result, the energy attenuation (shock absorption, It is considered that vibration damping property or sound absorbing property is generated.
[0030]
The effects of lowering the molding temperature of the base resin of the organic low molecular weight material having high dipole efficiency and dramatically improving the energy damping properties (such as shock absorbing property, vibration damping property, or sound absorbing property) of the molded article are as follows. Depending on the type of the base resin and the organic low-molecular material blended therein, the amount of energy applied to the molded product may vary depending on the application and use conditions. By setting the content of the material to a ratio of 0.1 to 30 parts by weight, a certain effect can be obtained.
[0031]
When the content of the organic low-molecular-weight material is out of the above range, not only the above two effects cannot be obtained, but also sufficient antibacterial properties cannot be obtained, or the mechanical strength of the molded product is reduced. There is a possibility that the adverse effect of the above may occur.
[0032]
The molded product of the present invention can be formed into various shapes according to its use and use state, such as a sheet, a film, a rod shape, a spherical shape, and a cylindrical shape. Depending on the shape, various conventionally known molding methods such as roll molding, compression molding, injection molding, extrusion molding, and casting can be used. Further, the molded article of the present invention can also take the form of a foam molded article obtained by foam molding, and further improve impact absorption, sound absorption, and weight reduction.
[0033]
Incidentally, in the molded product of the present invention, in addition to the above-mentioned iodine complex and organic low molecular weight material, in the base resin, depending on its use and use state, for example, mica scales, glass pieces, calcium carbonate, barite, sedimentation An inorganic filler such as barium sulfate or the like can be filled, and additives such as an antioxidant, a reinforcing agent / a reinforcing agent, an antistatic agent, a flame retardant, a lubricant, a foaming agent, and a coloring agent can be appropriately mixed.
[0034]
Further, the molded article of the present invention is formed into a form such as a sheet, a film, or a foamed sheet, and is further selected from one or more selected from another resin sheet, metal foil, woven fabric, knitted fabric, nonwoven fabric, and paper. And a composite form by lamination.
[0035]
Further, the molded article of the present invention comprises an antibacterial high-attenuating resin containing an iodine complex and an organic low-molecular material having a high dipole efficiency in the base resin described above, from the group consisting of woven fabric, knitted fabric, nonwoven fabric and paper. A form in which a selected base material is coated or impregnated and included may be employed.
[0036]
It should be noted that the present invention is not limited to the following embodiments, but can be freely modified and implemented within the scope described in the claims.
[0037]
【Example】
Example 1
Powdered iodine clathrate (CDI-10, effective iodine content 10%, Nihoho Chemical Co., Ltd.) based on 100 parts by weight of base resin constituting low resilience foam (SSA-06, manufactured by Sanwa Kako Co., Ltd.) ) 20 parts by weight and 3 parts by weight of DCHBSA (Suncellar DZ, manufactured by Sanshin Chemical Industry Co., Ltd.) were blended, and this mixture was foamed at a molding temperature of about 160 ° C. to obtain a sample.
[0038]
Example 2
A sample was obtained in the same manner as in Example 1 except that the amount of DCHBSA was changed to 1 part by weight based on 100 parts by weight of the base resin.
[0039]
Comparative Example 1
A low resilience foam (SSA-06, manufactured by Sanwa Kako Co., Ltd.) in which neither an iodine clathrate nor DCHBSA was blended was used as a sample.
[0040]
Comparative Example 2
A sample was obtained in the same manner as in Example 1 except that the amount of DCHBSA was set to 3 parts by weight based on 100 parts by weight of the base resin, and that no iodine clathrate was used.
[0041]
The samples according to Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to an antibacterial test, a rebound resilience test and a viscoelastic test to evaluate the antibacterial properties and the damping properties (shock absorbing properties) of each sample. .
4. Antibacterial activity test The antibacterial activity tests of the sample (Sample 1) according to Example 1 and the sample (Sample 2) according to Example 2 were conducted according to JIS Z 2801 “2000“ Antibacterial processed product-Antibacterial test method / antibacterial effect ”5. 2 Test method for plastic products etc.].
The test was performed on two strains, Escherichia coli ATCC 43895 (Escherichia coli, serotype O157: H7, verotoxin type I and type II producing strains), and Trichophyton rubrum TIMM 2659 (Trichophyton). A 0.005% dioctyl sodium sulfosuccinate solution was used as a liquid preparation solution.) The viable cell count conditions were the pour plate culture method (25) using a potato dextrose agar medium “Eiken Chemical Co., Ltd.” (Cultured at ± 1 ° C. for 7 days). In addition, a polyethylene film was used as a non-processed test piece.
[0042]
Table 1 shows the results of the antibacterial activity test.

From Table 1, it was found that Escherichia coli was completely killed after 24 hours at 35 ° C. in all cases of Measurement-1, Measurement-2, and Measurement-3. Also, the number of viable bacteria was significantly reduced, and it was confirmed that Sample 1 and Sample 2 had excellent antibacterial effects.
Rebound resilience test The rebound resilience of each sample of Example 1 and Comparative Example 2 was measured. The results are shown in FIG. In addition, the measurement of the rebound resilience was performed using the apparatus shown in FIG.
That is, each sample was placed on the metal table shown in FIG. 4, a steel ball having a diameter of 10 mm was dropped from a height of 500 mm, and the height of the rebound was defined as h. %) Was measured. The measurement was performed 10 times for each sample, and the average height h was obtained. Rebound resilience (%) = (h / 50) × 100
From FIG. 5, the sample according to Example 1 in which both the iodine clathrate and DCHBSA were blended, and the sample in Comparative Example 2 in which only DCHBSA was blended and no iodine clathrate was used, were all the same. It was confirmed that they exhibited excellent rebound resilience (shock absorption) and that the inclusion of the iodine clathrate did not adversely affect the resilience.
Viscoelasticity test The dynamic viscoelasticity (tan δ) of each of the samples of Examples 1 and 2 and Comparative Example 1 was measured. FIG. 6 shows the result. The measurement of the dynamic viscoelasticity (tan δ) was performed using a dynamic viscoelasticity measurement test apparatus (Reo Vibron DDV-25FP, manufactured by Orientec Co., Ltd.).
[0043]
From FIG. 6, with respect to the sample of Comparative Example 1 in which neither the iodine clathrate nor the DCHBSA was blended, Example 1 in which the content of DCHBSA was 3 parts by weight, and the content of DCHBSA in which the content was 1 part by weight. In Example 2, it was confirmed that tan δ increased in accordance with the blending amount, and that the peak shifted to a higher temperature side. Incidentally, a high tan δ means that the sample has excellent resilience (impact absorption), and the viscoelasticity test shows that the samples of Examples 1 and 2 are also excellent in impact absorption. confirmed.
[0044]
【The invention's effect】
Since the molded product of the present invention contains an iodine complex and an organic low molecular weight material having high dipole efficiency in the base resin, it can be applied to a wide range of uses, and has excellent antibacterial properties and high attenuation properties. Combined.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing a state of a dipole in a base resin.
FIG. 2 is a schematic diagram showing a state of a dipole in a base resin when energy is applied.
FIG. 3 is a schematic view showing a state of a dipole in a base resin containing an iodine complex and an organic low-molecular material having a high dipole efficiency.
FIG. 4 is a schematic view showing a rebound resilience measuring device.
FIG. 5 is a graph showing the rebound resilience of the sample according to Example 1 and the sample according to Comparative Example 2.
FIG. 6 is a graph showing tan δ at each temperature of the samples according to Examples 1 and 2 and the sample according to Comparative Example 1.
[Explanation of symbols]
11 ... base resin 12 ... dipole

Claims (10)

An antibacterial high-attenuating resin molded product comprising an iodine complex and an organic low molecular weight material having high dipole efficiency in a base resin. 2. The antibacterial high-attenuation resin molded article according to claim 1, wherein the iodine complex is an iodine clathrate having cyclodextrin as a host molecule. The antibacterial high-attenuation resin molded product according to claim 2, wherein the iodine composite is contained in a ratio of 0.1 to 30 parts by weight based on 100 parts by weight of the base resin. One or more organic low molecular weight materials having high dipole efficiency are selected from a compound having a benzothiazyl group, a compound having a benzotriazole group, a compound having a diphenylacrylate group, and a compound having a benzophenone group. The antibacterial high-damping resin molded product according to claim 1, which is a mixture. The antibacterial and high attenuation property according to claim 1 or 4, wherein the organic low molecular weight material having high dipole efficiency is contained in a ratio of 0.1 to 30 parts by weight based on 100 parts by weight of the base resin. Resin molding. The antibacterial high-damping resin molded product according to any one of claims 1 to 5, wherein the antibacterial high-damping resin molded product is a sheet. 7. The antibacterial high-damping resin molded product according to claim 6, wherein the antibacterial resin molded product is a foam sheet. The antibacterial high-attenuation resin molded product according to any one of claims 1 to 5, wherein the antibacterial high-attenuation resin molded product is a film. The antibacterial high-damping resin molded product according to claim 6, wherein one or more selected from the group consisting of a resin sheet, a metal foil, a woven fabric, a knitted fabric, a nonwoven fabric, and paper are laminated. An antibacterial high-damping resin molded product. A base resin selected from the group consisting of a woven fabric, a knitted fabric, a nonwoven fabric, and a paper, containing an antibacterial high-attenuating resin containing an iodine complex and an organic low-molecular material having a high dipole efficiency in a base resin An antibacterial high-damping resin molded product characterized by the following.

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