JP2005200586A - Antibacterial polyvinyl acetal porous body - Google Patents
Antibacterial polyvinyl acetal porous body Download PDFInfo
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- JP2005200586A JP2005200586A JP2004009794A JP2004009794A JP2005200586A JP 2005200586 A JP2005200586 A JP 2005200586A JP 2004009794 A JP2004009794 A JP 2004009794A JP 2004009794 A JP2004009794 A JP 2004009794A JP 2005200586 A JP2005200586 A JP 2005200586A
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- polyvinyl acetal
- silver
- porous body
- porous material
- antibacterial agent
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 55
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 17
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 title abstract 4
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 44
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 241000206607 Porphyra umbilicalis Species 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 150000001241 acetals Chemical class 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011354 acetal resin Substances 0.000 claims description 13
- 229920006324 polyoxymethylene Polymers 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- -1 for example Substances 0.000 abstract 1
- 230000000855 fungicidal effect Effects 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 241000243142 Porifera Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241001474374 Blennius Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001346815 Spongia officinalis Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Edible Seaweed (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
この発明は、海苔製造機用の脱水スポンジ、身体の水滴を拭き取るスポンジ、食器、調理器具の拭き取り用スポンジ、化粧用スポンジ、浴用スポンジ等のスポンジ類一般に好適な、吸水性、柔軟性、弾力性、拭き取り性に優れたポリビニルアセタール系多孔質体、特に抗菌性に優れたポリビニルアセタール系多孔質体に関する。 This invention is a dehydrating sponge for laver making machines, a sponge for wiping body water droplets, tableware, a sponge for wiping cooking utensils, a sponge for cosmetics, a bath sponge, etc., and is generally suitable for water absorption, flexibility, elasticity The present invention relates to a polyvinyl acetal porous material excellent in wiping properties, and particularly to a polyvinyl acetal porous material excellent in antibacterial properties.
ポリビニルアセタール系多孔質体は、吸水性、通気性、弾力性、柔軟性等を有するため、様々な用途に広く用いられているが、このポリビニルアセタール系多孔質体は、乾燥時には硬化してその柔軟性や弾力性が失われるため、湿潤状態で使用、また保管されるのが一般的である。 Polyvinyl acetal porous materials are widely used in various applications because of their water absorption, breathability, elasticity, flexibility, etc., but this polyvinyl acetal porous material is cured when dried. Since it loses its flexibility and elasticity, it is generally used and stored in a wet state.
しかし、このポリビニルアセタール系多孔質体を湿潤状態で使用、保管した場合には、菌やかびが発生しやすく、衛生上好ましくなく、防黴剤や抗菌剤を添加することが一般的に行われている。添加方法としては、ポリビニルアルコール（ＰＶＡ）水溶液にアルデヒド類、酸触媒、気孔形成材とともに抗菌剤を加え、アセタール化反応終了後、未反応のアルデヒド類、酸触媒および気孔形成材を除去して、ポリビニルアセタール系多孔質体に抗菌剤を包含させる、いわゆるプレミックスする方法とポリビニルアセタール系多孔質体を製造した後、抗菌剤溶液を含浸させる、いわゆる後含浸処理法がある（たとえば特許文献１又は特許文献２参照）。 However, when this polyvinyl acetal porous material is used and stored in a wet state, it tends to cause bacteria and fungi, which is unfavorable for hygiene, and generally adding an antifungal agent or an antibacterial agent. ing. As an addition method, an antibacterial agent is added to the polyvinyl alcohol (PVA) aqueous solution together with an aldehyde, an acid catalyst, and a pore-forming material, and after the acetalization reaction is completed, the unreacted aldehyde, the acid catalyst, and the pore-forming material are removed, There is a so-called premixing method in which an antibacterial agent is included in a polyvinyl acetal porous material, and a so-called post-impregnation treatment method in which an antibacterial agent solution is impregnated after producing a polyvinyl acetal porous material (for example, Patent Document 1 or Patent Document 2).
前者のプレミックス法では、反応時酸触媒を使用するため、酸によって分解しない抗菌剤を選ぶ必要があり、また、ポリビニルアセタール系多孔質体との親和性が低いと反応後の洗浄で抗菌剤が脱落してしまう場合が多い。後者の後含浸法では、抗菌剤がポリビニルアセタール樹脂に付着しているだけのため、使用時や水洗時に流出して抗菌性が急激に低下してしまう。抗菌性を持続させるため、アクリル樹脂等をバインダーとして用いる方法もあるが、バインダー樹脂でポリビニルアセタール系樹脂表面が覆われるためその特長である高い親水性や適度な柔軟性や弾力性を損なってしまう。 In the former premix method, since an acid catalyst is used during the reaction, it is necessary to select an antibacterial agent that is not decomposed by acid. If the affinity with the polyvinyl acetal porous material is low, the antibacterial agent is washed after the reaction. Often fall off. In the latter post-impregnation method, since the antibacterial agent is only attached to the polyvinyl acetal resin, the antibacterial property is drastically lowered due to outflow during use or washing with water. In order to maintain antibacterial properties, there is a method of using an acrylic resin or the like as a binder, but since the surface of the polyvinyl acetal resin is covered with the binder resin, its high hydrophilicity, moderate flexibility and elasticity are impaired. .
ところで、近年直接食品に触れる調理具や食器等に銀、亜鉛または銅系無機抗菌剤が安全性の高い抗菌剤として使用されているが、ポリビニルアセタール系多孔質体にプレミックス法で添加するには、酸に強く、ポリビニルアセタール樹脂への親和性の高い銀、亜鉛または銅系無機抗菌剤が必要である。これらの抗菌剤は、ゼオライトやアパタイトを担持体とするものが広く使われているが、いずれも酸によって抗菌剤を担持している担持体が溶解したり、あるいは担持体とポリビニルホルマール樹脂との親和性が低く、抗菌剤を多孔質内に固定化することが困難であった。 By the way, in recent years, silver, zinc, or copper inorganic antibacterial agents have been used as highly safe antibacterial agents in cooking utensils or tableware that directly touch food, but they are added to polyvinyl acetal porous materials by the premix method. Requires an acid, silver, zinc or copper inorganic antibacterial agent with high affinity for polyvinyl acetal resin. As these antibacterial agents, those having zeolite or apatite as a carrier are widely used. In either case, the carrier carrying the antibacterial agent is dissolved by an acid, or the carrier and the polyvinyl formal resin are dissolved. The affinity was low and it was difficult to fix the antibacterial agent in the porous material.
そこで、本発明の課題は使用時や水洗によっても抗菌剤の流出が抑えられ、長期間防黴性や抗菌性が持続させることができ、親水性、柔軟性、弾力性等に優れたポリビニルアセタール系多孔質体を提供することにある。 Therefore, the object of the present invention is to prevent the outflow of the antibacterial agent even when used or washed with water, and can maintain the antifungal property and the antibacterial property for a long time, and is excellent in hydrophilicity, flexibility, elasticity, etc. It is to provide a porous system.
上記の課題を解決するため、本発明者らは鋭意検討の結果、特定の無機抗菌剤が酸に強く、またポリビニルホルマール樹脂との親和性が高く、使用時や水洗によっても流出が抑えられ、抗菌性が長期間持続させることができることを見出し、本発明を完成させたものである。 In order to solve the above-mentioned problems, the present inventors have intensively studied, the specific inorganic antibacterial agent is strong against acid, and has a high affinity with the polyvinyl formal resin, and the outflow can be suppressed even when used or washed with water. The inventors have found that antibacterial properties can be maintained for a long period of time and have completed the present invention.
すなわち、本発明のポリビニルアセタール系多孔質体は、立体的網目状組織からなるポリビニルアセタール樹脂によって銀、亜鉛、銅またはそれらの化合物のうちいずれか１種以上を含む無機抗菌剤が直接包括、固定化されたものである。中でも銀、または銀化合物が抗菌力と安全性から特に好ましく使用できる。 That is, the polyvinyl acetal porous material of the present invention is directly covered and fixed with an inorganic antibacterial agent containing at least one of silver, zinc, copper or a compound thereof by a polyvinyl acetal resin having a three-dimensional network structure. It has been Among these, silver or a silver compound can be particularly preferably used from the viewpoint of antibacterial activity and safety.
銀、亜鉛、銅またはそれらの化合物がシリカまたはリン酸ジルコニウムを主成分とする担体に担持されたものであることが好ましい。 It is preferable that silver, zinc, copper or a compound thereof is supported on a carrier mainly composed of silica or zirconium phosphate.
本発明のポリビニルアセタール系多孔質体では、銀、亜鉛または銅原子の含有量が多孔質体重量に対して、０．００５〜０．２％であることが好ましく、特に０．０１１〜０．１０８％であることが好ましい。 In the polyvinyl acetal-based porous body of the present invention, the content of silver, zinc or copper atoms is preferably 0.005 to 0.2% with respect to the weight of the porous body. It is preferably 108%.
本発明のポリビニルアセタール系多孔質体では、３０％圧縮強度が５ｋＰａ〜２５ｋＰａ、保水率が６００〜１２００％であることが好ましい。 In the polyvinyl acetal porous material of the present invention, it is preferable that the 30% compression strength is 5 kPa to 25 kPa, and the water retention is 600 to 1200%.
さらに、本発明のポリビニルアセタール系多孔質体は、海苔製造機用の脱水スポンジに使用することが可能である。 Furthermore, the polyvinyl acetal porous material of the present invention can be used as a dehydrated sponge for laver making machines.
本発明のポリビニルアセタール系多孔質体は、銀、亜鉛、銅またはそれらの化合物のうちいずれか１種以上を含む無機抗菌剤を立体的網目状組織からなるポリビニルアセタール樹脂によって直接包括、固定化されることで、持続性のある抗菌性に優れたものとなる。 The polyvinyl acetal porous material of the present invention is directly entrapped and immobilized by a polyvinyl acetal resin composed of a three-dimensional network with an inorganic antibacterial agent containing any one or more of silver, zinc, copper or a compound thereof. By this, it will be excellent in the lasting antibacterial property.
本発明のポリビニルアセタール系多孔質体は、吸水性、通気性、弾力性、柔軟性等の特性を有するため、洗車用、浴用、台所用等の一般家庭用拭き取り材として、また種々の工業用洗浄材として様々な用途に広く用いられているが、優れた抗菌性により衛生的に使用、保管でき、実用上きわめて有用である。 The polyvinyl acetal porous material of the present invention has properties such as water absorption, breathability, elasticity, flexibility, etc., so that it can be used as a general household wipe for car washing, bathing, kitchen use, etc. Although it is widely used as a cleaning material in various applications, it can be used and stored hygienically due to its excellent antibacterial properties and is extremely useful in practice.
また、特に海苔製造機の脱水スポンジとして、使用すれば長期間の使用中も多孔質内の細菌の増殖を抑え、海苔への雑菌付着が少なくなり、きわめて有用である。 In particular, when used as a dehydrated sponge in a laver maker, it is extremely useful because it suppresses the growth of bacteria in the porous body even during long-term use and reduces the adhesion of bacteria to the laver.
銀、亜鉛、銅またはそれらの化合物のうちいずれか１種以上を含む無機抗菌剤をポリビニルアセタール樹脂に直接包括、固定化させるためには、ポリビニルアセタール系多孔質体の製造に際して、その製造原液中にこれらの無機抗菌剤を添加する、いわゆるプレミックス法を用いれば良い。ポリビニルアセタール系多孔質体は、ＰＶＡに硫酸等の酸を触媒としてホルムアルデヒド等のアルデヒド類を結合させるアセタール化反応によって製造される。具体的には、ポリビニルアルコール５〜２０％水溶液に無機抗菌剤を添加する。無機抗菌剤はポリビニルアセタール樹脂との親和性が高い成分を主体にしたもので、銀、亜鉛、銅またはそれらの酸化物等それらの金属イオンが徐々に溶出するものならばいずれでも良く、シリカまたはリン酸ジルコニウムを主成分とする担体に担持されたものであることが好ましい。その組成は、シリカまたはリン酸ジルコニウムを６０〜９９％、銀、亜鉛または銅原子として０．５〜１０％含有するものから選択できる。ポリビニルアセタール系多孔質体に均一に分散させるために微粒子粉体状のものが好ましく、粉体のまま直接または、懸濁液として添加できる。無機抗菌剤の添加量は銀、亜鉛または銅原子として、ポリビニルアセタール系多孔質体重量の０．００５〜０．２％の添加量が好ましい。中でも０．０１１〜０．０７２％の範囲が特に好ましい。銀、亜鉛または銅原子として０．００５％未満では、抗菌性が十分に発揮できず、菌やかびの増殖を抑えられないおそれがある。また、０．２％以上添加すると抗菌剤のために多孔質体が硬くなり、柔軟性、弾力性および親水性が損なわれる。 In order to directly embed and fix an inorganic antibacterial agent containing any one or more of silver, zinc, copper or a compound thereof in a polyvinyl acetal resin, in the production of the polyvinyl acetal porous material, What is necessary is just to use what is called a premix method which adds these inorganic antibacterial agents. The polyvinyl acetal porous material is produced by an acetalization reaction in which an aldehyde such as formaldehyde is bound to PVA using an acid such as sulfuric acid as a catalyst. Specifically, an inorganic antibacterial agent is added to a 5-20% aqueous solution of polyvinyl alcohol. The inorganic antibacterial agent is mainly composed of a component having a high affinity with the polyvinyl acetal resin, and may be any one as long as those metal ions such as silver, zinc, copper or oxide thereof are gradually eluted, silica or It is preferably supported on a carrier mainly composed of zirconium phosphate. The composition can be selected from those containing 60-99% silica or zirconium phosphate and 0.5-10% as silver, zinc or copper atoms. In order to disperse uniformly in the polyvinyl acetal porous material, a fine particle powder is preferable, and it can be added directly as a powder or as a suspension. The addition amount of the inorganic antibacterial agent is preferably 0.005 to 0.2% of the weight of the polyvinyl acetal porous material as silver, zinc or copper atoms. Among these, a range of 0.011 to 0.072% is particularly preferable. If the silver, zinc or copper atom is less than 0.005%, the antibacterial property cannot be sufficiently exerted, and there is a possibility that the growth of bacteria and fungi cannot be suppressed. Further, when 0.2% or more is added, the porous body becomes hard due to the antibacterial agent, and the flexibility, elasticity and hydrophilicity are impaired.
次に、無機抗菌剤を添加したＰＶＡ水溶液に、気孔形成材、アルデヒド類および酸触媒を加えて、混合攪拌し、反応原液とする。気孔形成材としては、反応後水洗により除去できるものならばいずれも使用可能であるが、澱粉類が特に好ましい。アルデヒド類としては、ホルムアルデヒドが好適に用いられ、酸触媒としては、無機酸、有機酸いずれも使用できるが、硫酸が特に好ましい。反応原液は、４０〜９０℃で５〜２４時間反応させる。得られた反応凝固物を水洗して、余剰のアルデヒド類、酸、気孔形成材を除去し、ポリビニルアセタール系多孔質体を得る。この状態で、無機抗菌剤が立体的網目状組織からなるポリビニルアセタール樹脂によって直接均一に包括、固定化されている。 Next, a pore-forming material, aldehydes and an acid catalyst are added to the PVA aqueous solution to which the inorganic antibacterial agent has been added, mixed and stirred to obtain a reaction stock solution. Any material can be used as the pore-forming material as long as it can be removed by washing with water after the reaction. As the aldehyde, formaldehyde is preferably used, and as the acid catalyst, either an inorganic acid or an organic acid can be used, but sulfuric acid is particularly preferable. The reaction stock solution is reacted at 40 to 90 ° C. for 5 to 24 hours. The obtained reaction coagulated product is washed with water to remove excess aldehydes, acids, and pore forming materials, and a polyvinyl acetal porous material is obtained. In this state, the inorganic antibacterial agent is directly and uniformly covered and fixed by the polyvinyl acetal resin having a three-dimensional network structure.
ポリビニルアセタール系多孔質体の優れた吸水性を発揮させるには適度な弾力性と保水性を有することが望ましく、３０％圧縮強度が５ｋＰａ〜２５ｋＰａ、保水率が６００〜１２００％であることが好ましい。ポリビニルアセタール系多孔質体は海苔の製造工程で乾燥前に余剰の水分を除去する海苔製造機用の脱水スポンジに使用されており、その吸水性、柔軟性、弾力性から高品質の海苔の製造に適しているが、海水、海苔等に自然に付着している細菌類がポリビニルアセタール系多孔質体の内部で増殖し、海苔を汚染する恐れがあるが、本発明のポリビニルアセタール系多孔質体を用いれば、多孔質体内に存在する細菌類は無機抗菌剤によって増殖が抑えられ、衛生的な海苔製造に好適に使用することができる。 In order to exhibit the excellent water absorption of the polyvinyl acetal porous body, it is desirable to have appropriate elasticity and water retention, preferably 30% compressive strength is 5 kPa to 25 kPa, and water retention is 600 to 1200%. . Polyvinyl acetal porous materials are used in dehydrated sponges for laver making machines that remove excess water before drying in the laver production process, producing high quality laver from its water absorption, flexibility, and elasticity. However, bacteria that naturally adhere to seawater, seaweed, etc. may grow inside the polyvinyl acetal porous body and contaminate the seaweed, but the polyvinyl acetal porous body of the present invention The growth of bacteria present in the porous body is suppressed by the inorganic antibacterial agent and can be suitably used for sanitary laver production.
以下、本発明の実施例について説明するが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
実施例１
平均重合度１７００の完全鹸化型ＰＶＡ（クラレ（株）製ポバール１１７）の１３％水溶液３５リットルに馬鈴薯澱粉の分散液５リットルを混合、ついでシリカゲルに銀原子として５％含有させた銀系抗菌剤の微粉末品をＰＶＡに対して１、３、５％添加し、分散した。それぞれに、５０％硫酸５リットルと３７％ホルムアルデヒド水溶液５リットルを加え、容器に流し込んで、６０℃にて、１８時間反応させた。反応終了後、容器より取り出し、洗浄して余剰のホルムアルデヒド、硫酸、澱粉等を除去し、銀系抗菌剤包括固定化ポリビニルアセタール系多孔質体を得た。
Example 1
Silver antibacterial agent in which 5 liters of potato starch dispersion is mixed with 35 liters of 13% aqueous solution of fully saponified PVA (Poval 117 manufactured by Kuraray Co., Ltd.) having an average degree of polymerization of 1700, and then 5% of silver atoms are contained in silica gel. Were added to the PVA in an amount of 1, 3, 5% and dispersed. 5 liters of 50% sulfuric acid and 5 liters of 37% formaldehyde aqueous solution were added to each, poured into a container, and reacted at 60 ° C. for 18 hours. After completion of the reaction, the product was taken out from the container and washed to remove excess formaldehyde, sulfuric acid, starch and the like, and a silver-based antibacterial agent-entrapped polyvinyl acetal porous material was obtained.
得られたポリビニルアセタール系多孔質体の物性値を表１に示す。なお、銀原子含有量は多孔質体を灰化後、希硝酸に溶解し、ＩＣＰ−ＭＳにて銀量を測定し、多孔質体重量に対する含有比を求めた。また、走査型電子顕微鏡で観察したところ、いずれも網目状のポリビニルアセタール樹脂表面に一部埋没した銀系抗菌剤が認められた。 Table 1 shows the physical property values of the obtained polyvinyl acetal porous material. In addition, silver atom content melt | dissolved in dilute nitric acid after ashing a porous body, measured silver amount by ICP-MS, and calculated | required the content ratio with respect to a porous body weight. Further, when observed with a scanning electron microscope, silver antibacterial agents partially embedded in the surface of the mesh-like polyvinyl acetal resin were observed.
前記で得られたポリビニルアセタール系多孔質体を２ｃｍ×２ｃｍ×０．５ｃｍに裁断し、大腸菌と黄色ブドウ球菌をそれぞれ１０4 個／ｍｌに調整した寒天培地上に置き、３５℃で２日間培養した後、試験片周囲のハロー（阻止円）を測定した結果を表２に示す。いずれもハローが認められ、抗菌性を有していることが確認できた。 The polyvinyl acetal porous material obtained above was cut into 2 cm × 2 cm × 0.5 cm, placed on an agar medium adjusted to 10 4 cells / ml of Escherichia coli and Staphylococcus aureus, and cultured at 35 ° C. for 2 days. Thereafter, Table 2 shows the results of measuring the halo (blocking circle) around the test piece. In both cases, halo was observed, and it was confirmed that they had antibacterial properties.
次に、２５ｃｍ×２５ｃｍ×２．５ｃｍに裁断した銀系抗菌剤を添加したそれぞれのポリビニルアセタール系多孔質体と銀系抗菌剤を添加していない多孔質体をブランクとして、海苔脱水機に設置し、１０万枚の海苔を生産後、多孔質体を取り外し、海苔由来菌を１０4 個／ｍｌに調整した液をそれぞれ含浸し、２日間室温で放置後、菌数を測定した結果を表３に示す。銀系抗菌剤を添加しない多孔質体では著しく菌数が増加していたが、銀系抗菌剤を添加した多孔質体ではいずれも菌が減少し、生産に供しても抗菌性が維持されていることが確認できた。 Next, each polyvinyl acetal porous material added with a silver antibacterial agent cut to 25 cm x 25 cm x 2.5 cm and a porous material not added with a silver antibacterial agent are installed in a laver dehydrator as a blank. After the production of 100,000 laver, the porous body was removed, and each solution was adjusted to 10 4 cells / ml with the laver-derived bacteria, impregnated with each solution and allowed to stand at room temperature for 2 days. Shown in The number of bacteria increased remarkably in the porous body to which no silver antibacterial agent was added, but the number of bacteria decreased in the porous body to which the silver antibacterial agent was added. It was confirmed that
実施例２
銀系抗菌剤として、表４に示す銀系抗菌剤をＰＶＡに対して３％添加する以外は、実施例１と同様にして、抗菌剤固定化ポリビニルアセタール系多孔質体を製造し、実施例１と同様にハロー試験と海苔由来菌１０4 個／ｍｌを含浸し、４８時間経過後菌数測定を実施した。
Example 2
As a silver antibacterial agent, an antibacterial agent-immobilized polyvinyl acetal porous material was produced in the same manner as in Example 1 except that 3% of the silver antibacterial agent shown in Table 4 was added to PVA. In the same manner as in No. 1, the halo test and 10 4 cells / ml of nori-derived bacteria were impregnated, and the number of bacteria was measured after 48 hours.
表４に示すように本発明例のシリカまたはリン酸ジルコニウムを主成分とする銀系抗菌剤では、抗菌性が確認できたが、シリカまたはリン酸ジルコニウム以外を主成分とする比較例の銀系抗菌剤（アパタイト系又はゼオライト系の担持体に抗菌剤を担持させたもの）では、いずれも多孔質体に含有されている銀量は少なく、抗菌性がほとんど認められなかった。これら比較例の抗菌剤はポリビニルアセタール系多孔質体を製造する際に、酸によって抗菌剤を担持している担持体（アパタイト系又はゼオライト系）が溶解あるいはその担持体とポリビニルアセタール系樹脂との親和性が低く、反応後の洗浄でほとんどが流出したものと考えられる。
これに対し、本発明例では、担持体が酸で溶解することなく、ポリビニルアセタール系樹脂との親和性が高く、ポリビニルアセタール樹脂によって直接包括、固定化されているため、反応後の洗浄によっても抗菌剤の流出は生じにくいからであると考えられる。
As shown in Table 4, the antibacterial property was confirmed in the silver-based antibacterial agent mainly composed of silica or zirconium phosphate of the present invention, but the silver-based comparative example mainly composed of other than silica or zirconium phosphate In any of the antibacterial agents (apatite-type or zeolite-type carriers supported with the antibacterial agent), the amount of silver contained in the porous body was small, and almost no antibacterial property was observed. When the antibacterial agent of these comparative examples is used to produce a polyvinyl acetal porous material, the support (apatite or zeolite) carrying the antibacterial agent is dissolved by an acid or the support and the polyvinyl acetal resin The affinity is low, and it is considered that most of the effluent was washed away after washing.
On the other hand, in the example of the present invention, the carrier is not dissolved with an acid and has a high affinity with the polyvinyl acetal resin, and is directly included and immobilized by the polyvinyl acetal resin. This is probably because antibacterial agents do not easily flow out.
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