WO2024010084A1 - Resin composition for outer layer of antibacterial article, molded body, and antibacterial article - Google Patents
Resin composition for outer layer of antibacterial article, molded body, and antibacterial article Download PDFInfo
- Publication number
- WO2024010084A1 WO2024010084A1 PCT/JP2023/025260 JP2023025260W WO2024010084A1 WO 2024010084 A1 WO2024010084 A1 WO 2024010084A1 JP 2023025260 W JP2023025260 W JP 2023025260W WO 2024010084 A1 WO2024010084 A1 WO 2024010084A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antibacterial
- outer layer
- resin composition
- oxide
- block copolymer
- Prior art date
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 65
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
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- 238000009408 flooring Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229940047650 haemophilus influenzae Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940037467 helicobacter pylori Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940115932 legionella pneumophila Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940115931 listeria monocytogenes Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- BECUBVOEPSAYDH-UHFFFAOYSA-N n-(1h-benzimidazol-2-yl)acetamide Chemical compound C1=CC=C2NC(NC(=O)C)=NC2=C1 BECUBVOEPSAYDH-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- 239000004308 thiabendazole Substances 0.000 description 1
- 229960004546 thiabendazole Drugs 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- RIAJLMJRHLGNMZ-UHFFFAOYSA-N triazanium;trioxomolybdenum;phosphate Chemical compound [NH4+].[NH4+].[NH4+].O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.[O-]P([O-])([O-])=O RIAJLMJRHLGNMZ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229940118696 vibrio cholerae Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental Sciences (AREA)
- Polymers & Plastics (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Medicinal Chemistry (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The purpose of the present invention is to provide a resin composition for an outer layer of an antibacterial article, the resin composition being capable of demonstrating high antibacterial properties without the addition of an additive such as a metal oxide and of being processed into a molded body such as an injection molded article, an extrusion molded article, a film, a fiber, a non-woven fabric, or a foamed body. The present invention is a resin composition for an outer layer of an antibacterial article, the resin composition being characterized by containing a block copolymer which has an antibacterial activity value of at least 2 after 24 hours, wherein the block copolymer includes an aliphatic polyether.
Description
本発明は、抗菌性物品外層用樹脂組成物、成形体、および抗菌性物品に関する。
The present invention relates to a resin composition for an outer layer of an antibacterial article, a molded article, and an antibacterial article.
新型コロナウイルスの感染拡大に伴い、衛生、清潔、健康などに対する社会的関心が高まっている。例えば、住宅の壁紙、家具、水まわりの材料、食品工業における食品の製造、包装などが行われる場所の備品、壁面、天井、床面あるいは病院のトイレ、厨房などで使用される機材、空調機や加湿機などの温暖・湿潤の条件下で使用される機器の部品材料、衣料および一般の家庭用品など、日々の暮らしにおけるあらゆる生活空間に対して抗菌性の要求が強くなってきている。
With the spread of the new coronavirus, social interest in hygiene, cleanliness, health, etc. is increasing. For example, wallpaper, furniture, plumbing materials in houses, fixtures in places where food is manufactured and packaged in the food industry, walls, ceilings, and floors, equipment used in hospital toilets, kitchens, etc., and air conditioners. There is a growing demand for antibacterial properties for all kinds of living spaces in daily life, such as parts and materials for equipment used under warm and humid conditions such as humidifiers and humidifiers, clothing, and general household goods.
このような抗菌性を有する材料としては、例えば、特許文献１のように、酸化チタンや酸化セリウム等からなる金属化合物を樹脂に分散させた材料が報告されている。しかしながら、金属化合物が製品表面にブリードアウトするという問題があった。また、混合する樹脂の靭性が金属化合物によって低下するという問題があった。また、濃い色の発色が難しいという問題があった。
As such a material having antibacterial properties, a material in which a metal compound such as titanium oxide or cerium oxide is dispersed in a resin has been reported, for example, as in Patent Document 1. However, there was a problem that the metal compound bleed out onto the product surface. Further, there was a problem in that the toughness of the resin to be mixed was reduced by the metal compound. Another problem was that it was difficult to develop deep colors.
一方、特許文献２のように、抗菌剤を添加しないで抗菌性を発現する高分子化合物として、アミノ基を有するポリビニルアルコールが報告されていた。
On the other hand, as in Patent Document 2, polyvinyl alcohol having an amino group has been reported as a polymer compound that exhibits antibacterial properties without adding an antibacterial agent.
しかしながら、特許文献２の高分子化合物であるアミノ基を有するポリビニルアルコールは成形加工性に課題があり、新たな材料が求められると考えた。
However, the polymer compound disclosed in Patent Document 2, polyvinyl alcohol having an amino group, has problems in moldability, and we thought that a new material would be required.
本発明は、金属化合物などの抗菌剤を添加しなくてもそれ自身で高い抗菌性を発現することができ、成形体として、射出成形品、押出成形品、フィルム、繊維、不織布及び発泡体に加工することができる、抗菌性物品外層用樹脂組成物を提供することを目的とするものである。
The present invention can exhibit high antibacterial properties by itself without adding antibacterial agents such as metal compounds, and can be used as molded products such as injection molded products, extrusion molded products, films, fibers, nonwoven fabrics, and foams. It is an object of the present invention to provide a resin composition for an outer layer of an antibacterial article that can be processed.
本発明者らは、脂肪族ポリエーテルを含むブロック共重合体が、金属化合物などの添加物を添加しなくてもそれ自身が高い抗菌性を有し、これを含有することで樹脂組成物が抗菌性を発現することを見出した。
The present inventors discovered that a block copolymer containing an aliphatic polyether itself has high antibacterial properties even without the addition of additives such as metal compounds, and that containing this block copolymer improves the resin composition. It was discovered that it exhibits antibacterial properties.
すなわち、本発明は、以下の通りである。
（１）２４時間後の抗菌活性値が２以上であるブロック共重合体を含有し、該ブロック共重合体が脂肪族ポリエーテルを含むブロック共重合体であることを特徴とする抗菌性物品外層用樹脂組成物。
（２）前記脂肪族ポリエーテルを含むブロック共重合体が熱可塑性ポリエステルエラストマーであることを特徴とする（１）に記載の抗菌性物品外層用樹脂組成物。
（３）前記脂肪族ポリエーテルを含むブロック共重合体の脂肪族ポリエーテルの共重合比率が９％以上であることを特徴とする（１）または（２）に記載の抗菌性物品外層用樹脂組成物。
（４）前記脂肪族ポリエーテルがポリ（テトラメチレンオキシド）グリコールもしくはポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物であることを特徴とする（１）または（２）に記載の抗菌性物品外層用樹脂組成物。
（５）（１）または（２）に記載の抗菌性物品外層用樹脂組成物を加工してなる成形体。
（６）（１）または（２）に記載の抗菌性物品外層用樹脂組成物を外層に用いてなる抗菌性物品。 That is, the present invention is as follows.
(1) An antibacterial article outer layer containing a block copolymer having an antibacterial activity value of 2 or more after 24 hours, the block copolymer being a block copolymer containing an aliphatic polyether. Resin composition for use.
(2) The resin composition for an outer layer of an antibacterial article according to (1), wherein the block copolymer containing the aliphatic polyether is a thermoplastic polyester elastomer.
(3) The resin for antibacterial article outer layer according to (1) or (2), wherein the copolymerization ratio of aliphatic polyether in the block copolymer containing aliphatic polyether is 9% or more. Composition.
(4) The resin for antibacterial article outer layer according to (1) or (2), wherein the aliphatic polyether is an ethylene oxide adduct of poly(tetramethylene oxide) glycol or poly(propylene oxide) glycol. Composition.
(5) A molded article obtained by processing the resin composition for an outer layer of an antibacterial article according to (1) or (2).
(6) An antibacterial article using the resin composition for an antibacterial article outer layer according to (1) or (2) as an outer layer.
（１）２４時間後の抗菌活性値が２以上であるブロック共重合体を含有し、該ブロック共重合体が脂肪族ポリエーテルを含むブロック共重合体であることを特徴とする抗菌性物品外層用樹脂組成物。
（２）前記脂肪族ポリエーテルを含むブロック共重合体が熱可塑性ポリエステルエラストマーであることを特徴とする（１）に記載の抗菌性物品外層用樹脂組成物。
（３）前記脂肪族ポリエーテルを含むブロック共重合体の脂肪族ポリエーテルの共重合比率が９％以上であることを特徴とする（１）または（２）に記載の抗菌性物品外層用樹脂組成物。
（４）前記脂肪族ポリエーテルがポリ（テトラメチレンオキシド）グリコールもしくはポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物であることを特徴とする（１）または（２）に記載の抗菌性物品外層用樹脂組成物。
（５）（１）または（２）に記載の抗菌性物品外層用樹脂組成物を加工してなる成形体。
（６）（１）または（２）に記載の抗菌性物品外層用樹脂組成物を外層に用いてなる抗菌性物品。 That is, the present invention is as follows.
(1) An antibacterial article outer layer containing a block copolymer having an antibacterial activity value of 2 or more after 24 hours, the block copolymer being a block copolymer containing an aliphatic polyether. Resin composition for use.
(2) The resin composition for an outer layer of an antibacterial article according to (1), wherein the block copolymer containing the aliphatic polyether is a thermoplastic polyester elastomer.
(3) The resin for antibacterial article outer layer according to (1) or (2), wherein the copolymerization ratio of aliphatic polyether in the block copolymer containing aliphatic polyether is 9% or more. Composition.
(4) The resin for antibacterial article outer layer according to (1) or (2), wherein the aliphatic polyether is an ethylene oxide adduct of poly(tetramethylene oxide) glycol or poly(propylene oxide) glycol. Composition.
(5) A molded article obtained by processing the resin composition for an outer layer of an antibacterial article according to (1) or (2).
(6) An antibacterial article using the resin composition for an antibacterial article outer layer according to (1) or (2) as an outer layer.
本発明によれば、金属化合物のブリードアウトや金属化合物による靭性低下や発色性低下を起こすことなく、高い抗菌性を発現することができ、成形加工性に優れる抗菌性物品外層用樹脂組成物が得られる。
According to the present invention, there is provided a resin composition for an outer layer of an antibacterial article that can exhibit high antibacterial properties without causing bleed-out of metal compounds or deterioration in toughness or color development due to metal compounds, and has excellent moldability. can get.
以下、本発明について詳述する。
Hereinafter, the present invention will be explained in detail.
本発明の抗菌性物品外層用樹脂組成物は、２４時間後の抗菌活性値が２以上であるブロック共重合体を含有する。本発明のブロック共重合体は、後述する抗菌性試験における、２４時間後の抗菌活性値が２以上である。本発明の抗菌性物品外層用樹脂組成物は、２４時間後の抗菌活性値が２以上であるブロック共重合体を含有することにより、抗菌性を有する。
The resin composition for the outer layer of an antibacterial article of the present invention contains a block copolymer having an antibacterial activity value of 2 or more after 24 hours. The block copolymer of the present invention has an antibacterial activity value of 2 or more after 24 hours in the antibacterial test described below. The antibacterial article outer layer resin composition of the present invention has antibacterial properties by containing a block copolymer having an antibacterial activity value of 2 or more after 24 hours.
本発明において、「抗菌性」とは、細菌の増殖を抑える性質を意味する。抗菌性は、後述する２４時間後の抗菌活性値（Ｒ）や２４時間後の生菌数低減率（％）で評価される。
In the present invention, "antibacterial" means the property of suppressing bacterial growth. The antibacterial property is evaluated by the antibacterial activity value (R) after 24 hours and the reduction rate of viable bacteria count (%) after 24 hours, which will be described later.
本発明のブロック共重合体は、脂肪族ポリエーテルを含むブロック共重合体である。脂肪族ポリエーテルを含むブロック共重合体は、脂肪族ポリエーテルを含有することで、細菌の増殖を抑制することができる。また、脂肪族ポリエーテルを含むブロック共重合体であることで、成形加工性に優れる。
The block copolymer of the present invention is a block copolymer containing an aliphatic polyether. A block copolymer containing an aliphatic polyether can suppress the growth of bacteria by containing the aliphatic polyether. Moreover, since it is a block copolymer containing an aliphatic polyether, it has excellent moldability.
［脂肪族ポリエーテル］
脂肪族ポリエーテルの具体例としては、ポリ（エチレンオキシド）グリコール、ポリ（プロピレンオキシド）グリコール、ポリ（トリメチレンオキシド）グリコール、ポリ（テトラメチレンオキシド）グリコール、ポリ（ヘキサメチレンオキシド）グリコール、ポリ（ノナメチレンオキシド）グリコール、エチレンオキシドとプロピレンオキシドの共重合体、テトラメチレンオキシドとヘキサメチレンオキシドの共重合体、テトラメチレンオキシドとノナメチレンオキシドの共重合体、ポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物、およびエチレンオキシドとテトラヒドロフランの共重合体などが挙げられる。これらのなかでも、ポリ（テトラメチレンオキシド）グリコールおよび／またはポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物および／またはエチレンオキシドとテトラヒドロフランの共重合体を含むことが好ましい。中でもポリ（テトラメチレンオキシド）グリコール、ポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物を含むことが好ましい。なお、例えば、ポリ（プロピレンオキシド）グリコールは、ポリプロピレンオキシドあるいはポリプロピレングリコールであり、ポリ（テトラメチレンオキシド）グリコールは、ポリ（テトラメチレンオキシド）あるいはポリテトラメチレンエーテルグリコールである。 [Aliphatic polyether]
Specific examples of aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(trimethylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, and poly(nonamethylene oxide) glycol. methylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, copolymers of tetramethylene oxide and hexamethylene oxide, copolymers of tetramethylene oxide and nonamethylene oxide, ethylene oxide adducts of poly(propylene oxide) glycol, and Examples include copolymers of ethylene oxide and tetrahydrofuran. Among these, it is preferable to include an ethylene oxide adduct of poly(tetramethylene oxide) glycol and/or poly(propylene oxide) glycol and/or a copolymer of ethylene oxide and tetrahydrofuran. Among these, it is preferable to include poly(tetramethylene oxide) glycol and poly(propylene oxide) glycol adduct with ethylene oxide. Note that, for example, poly(propylene oxide) glycol is polypropylene oxide or polypropylene glycol, and poly(tetramethylene oxide) glycol is poly(tetramethylene oxide) or polytetramethylene ether glycol.
脂肪族ポリエーテルの具体例としては、ポリ（エチレンオキシド）グリコール、ポリ（プロピレンオキシド）グリコール、ポリ（トリメチレンオキシド）グリコール、ポリ（テトラメチレンオキシド）グリコール、ポリ（ヘキサメチレンオキシド）グリコール、ポリ（ノナメチレンオキシド）グリコール、エチレンオキシドとプロピレンオキシドの共重合体、テトラメチレンオキシドとヘキサメチレンオキシドの共重合体、テトラメチレンオキシドとノナメチレンオキシドの共重合体、ポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物、およびエチレンオキシドとテトラヒドロフランの共重合体などが挙げられる。これらのなかでも、ポリ（テトラメチレンオキシド）グリコールおよび／またはポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物および／またはエチレンオキシドとテトラヒドロフランの共重合体を含むことが好ましい。中でもポリ（テトラメチレンオキシド）グリコール、ポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物を含むことが好ましい。なお、例えば、ポリ（プロピレンオキシド）グリコールは、ポリプロピレンオキシドあるいはポリプロピレングリコールであり、ポリ（テトラメチレンオキシド）グリコールは、ポリ（テトラメチレンオキシド）あるいはポリテトラメチレンエーテルグリコールである。 [Aliphatic polyether]
Specific examples of aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(trimethylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, and poly(nonamethylene oxide) glycol. methylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, copolymers of tetramethylene oxide and hexamethylene oxide, copolymers of tetramethylene oxide and nonamethylene oxide, ethylene oxide adducts of poly(propylene oxide) glycol, and Examples include copolymers of ethylene oxide and tetrahydrofuran. Among these, it is preferable to include an ethylene oxide adduct of poly(tetramethylene oxide) glycol and/or poly(propylene oxide) glycol and/or a copolymer of ethylene oxide and tetrahydrofuran. Among these, it is preferable to include poly(tetramethylene oxide) glycol and poly(propylene oxide) glycol adduct with ethylene oxide. Note that, for example, poly(propylene oxide) glycol is polypropylene oxide or polypropylene glycol, and poly(tetramethylene oxide) glycol is poly(tetramethylene oxide) or polytetramethylene ether glycol.
また、これらの脂肪族ポリエーテルの数平均分子量としては、共重合された状態において３００～６０００であることが好ましい。数平均分子量は一般的な有機分析で測定することができる。
Further, the number average molecular weight of these aliphatic polyethers is preferably 300 to 6,000 in a copolymerized state. The number average molecular weight can be measured by general organic analysis.
脂肪族ポリエーテルを含むブロック共重合体の脂肪族ポリエーテルの共重合比率は９％以上がより好ましく、２０％以上がより好ましく、２５％以上がより好ましく、３０％以上がより好ましく、３５％以上がより好ましく、４０％以上がより好ましく、４５％以上がより好ましく、５０％以上がより好ましい。
The copolymerization ratio of aliphatic polyether in the block copolymer containing aliphatic polyether is more preferably 9% or more, more preferably 20% or more, more preferably 25% or more, more preferably 30% or more, and 35%. It is more preferably 40% or more, more preferably 45% or more, and even more preferably 50% or more.
なお、ここで脂肪族ポリエーテルを含むブロック共重合体の脂肪族ポリエーテルの共重合比率とは、脂肪族ポリエーテルを含むブロック共重合体の、ジオール成分としての脂肪族ポリエーテル単位の割合である。すなわち、原料の脂肪族ポリエーテルからエステル結合生成による水分子分を控除した量の、脂肪族ポリエーテルを含むブロック共重合体全体の量に対する割合を質量％で表したものである。原料の組成が判っていればそのまま計算して求めることができる。また、脂肪族ポリエーテルを含むブロック共重合体をＮＭＲで構造分析して求めることができる。
Note that the copolymerization ratio of aliphatic polyether in a block copolymer containing an aliphatic polyether is the ratio of aliphatic polyether units as a diol component in a block copolymer containing an aliphatic polyether. be. That is, it is expressed in mass % as the ratio of the amount of the raw material aliphatic polyether minus the water molecule content due to the formation of ester bonds to the total amount of the block copolymer containing the aliphatic polyether. If the composition of the raw material is known, it can be calculated directly. It can also be determined by structurally analyzing a block copolymer containing an aliphatic polyether using NMR.
本発明の脂肪族ポリエーテルを含むブロック共重合体として、熱可塑性ポリエステルエラストマー、熱可塑性ポリアミドエラストマー、熱可塑性ポリウレタンエラストマーが挙げられる。中でも、熱可塑性ポリエステルエラストマー、熱可塑性ポリアミドエラストマーが好ましく、熱可塑性ポリエステルエラストマーがより好ましい。
Examples of the block copolymer containing an aliphatic polyether of the present invention include thermoplastic polyester elastomer, thermoplastic polyamide elastomer, and thermoplastic polyurethane elastomer. Among these, thermoplastic polyester elastomers and thermoplastic polyamide elastomers are preferred, and thermoplastic polyester elastomers are more preferred.
［熱可塑性ポリエステルエラストマー］
本発明に用いられる熱可塑性ポリエステルエラストマーは、高融点結晶性重合体セグメントと低融点重合体セグメントの共重合体である。 [Thermoplastic polyester elastomer]
The thermoplastic polyester elastomer used in the present invention is a copolymer of a high melting point crystalline polymer segment and a low melting point polymer segment.
本発明に用いられる熱可塑性ポリエステルエラストマーは、高融点結晶性重合体セグメントと低融点重合体セグメントの共重合体である。 [Thermoplastic polyester elastomer]
The thermoplastic polyester elastomer used in the present invention is a copolymer of a high melting point crystalline polymer segment and a low melting point polymer segment.
高融点結晶性重合体セグメントは、芳香族ジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成性誘導体から形成されるポリエステルである。
The high melting point crystalline polymer segment is a polyester formed from an aromatic dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative.
前記芳香族ジカルボン酸の具体例としては、テレフタル酸、イソフタル酸、フタル酸、ナフタレン－２，６－ジカルボン酸、ナフタレン－２，７－ジカルボン酸、アントラセンジカルボン酸、ジフェニル－４，４'－ジカルボン酸、ジフェノキシエタンジカルボン酸、４，４'－ジフェニルエーテルジカルボン酸、５－スルホイソフタル酸、および３－スルホイソフタル酸ナトリウムなどが挙げられる。本発明においては、前記芳香族ジカルボン酸を主として用いるが、この芳香族ジカルボン酸の一部を、１，４－シクロヘキサンジカルボン酸、シクロペンタンジカルボン酸、４，４'－ジシクロヘキシルジカルボン酸などの脂環族ジカルボン酸や、アジピン酸、コハク酸、シュウ酸、セバシン酸、ドデカンジオン酸、およびダイマー酸などの脂肪族ジカルボン酸に置換してもよい。さらに、ジカルボン酸のエステル形成性誘導体、たとえば低級アルキルエステル、アリールエステル、炭酸エステル、および酸ハロゲン化物なども同等に用い得る。
Specific examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, and diphenyl-4,4'-dicarboxylic acid. acid, diphenoxyethane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. In the present invention, the aromatic dicarboxylic acid is mainly used, but a part of the aromatic dicarboxylic acid is substituted with alicyclic acid such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid, etc. It may be substituted with aliphatic dicarboxylic acids such as group dicarboxylic acids, adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Furthermore, ester-forming derivatives of dicarboxylic acids, such as lower alkyl esters, aryl esters, carbonic esters, and acid halides, can be equally used.
本発明においては、上記酸成分を２種以上使用することができる。例えばテレフタル酸とイソフタル酸、テレフタル酸とドデカンジオン酸、テレフタル酸とダイマー酸などの組み合わせが挙げられる。
In the present invention, two or more of the above acid components can be used. Examples include combinations of terephthalic acid and isophthalic acid, terephthalic acid and dodecanedioic acid, terephthalic acid and dimer acid, and the like.
次に、高融点結晶性重合体セグメント中のジオールの具体例としては、分子量４００以下のジオール、例えば１，４－ブタンジオール、エチレングリコール、トリメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、デカメチレングリコールなどの脂肪族ジオール、１，１－シクロヘキサンジメタノール、１，４－ジシクロヘキサンジメタノール、トリシクロデカンジメタノールなどの脂環族ジオール、およびキシリレングリコール、ビス（ｐ－ヒドロキシ）ジフェニル、ビス（ｐ－ヒドロキシ）ジフェニルプロパン、２，２'－ビス［４－（２－ヒドロキシエトキシ）フェニル］プロパン、ビス［４－（２－ヒドロキシエトキシ）フェニル］スルホン、１，１－ビス［４－（２－ヒドロキシエトキシ）フェニル］シクロヘキサン、４，４'－ジヒドロキシ－ｐ－ターフェニル、および４，４'－ジヒドロキシ－ｐ－クオーターフェニルなどの芳香族ジオールが好ましく、かかるジオールは、エステル形成性誘導体、例えばアセチル体、アルカリ金属塩などの形でも用い得る。これらのジカルボン酸、その誘導体、ジオール成分およびその誘導体は、２種以上併用してもよい。
Next, specific examples of diols in the high melting point crystalline polymer segment include diols with a molecular weight of 400 or less, such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl Aliphatic diols such as glycol, decamethylene glycol, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecane dimethanol, and xylylene glycol, bis(p-hydroxy ) diphenyl, bis(p-hydroxy)diphenylpropane, 2,2'-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis Aromatic diols such as [4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quarterphenyl are preferred; such diols It can also be used in the form of formable derivatives such as acetyl derivatives and alkali metal salts. Two or more of these dicarboxylic acids, derivatives thereof, diol components, and derivatives thereof may be used in combination.
低融点重合体セグメントは、脂肪族ポリエーテルであるが、脂肪族ポリエステルや脂肪族ポリカーボネートを併用してもよい。脂肪族ポリエステルの具体例として、ポリ（ε－カプロラクトン）、ポリエナントラクトン、ポリカプリロラクトン、ポリブチレンアジペート、等が挙げられる。脂肪族ポリカーボネートは、主として炭素数２～１２の脂肪族ジオール残基からなるものであることが好ましい。これらの脂肪族ジオールとしては、例えば、エチレングリコール、１，３－プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，８－オクタンジオール、２，２－ジメチル－１，３－プロパンジオール、３－メチル－１，５－ペンタンジオール、２，４－ジエチル－１，５－ペンタンジオール、１，９－ノナンジオール、２－メチル－１，８－オクタンジオール、等が挙げられる。
The low melting point polymer segment is an aliphatic polyether, but an aliphatic polyester or an aliphatic polycarbonate may also be used in combination. Specific examples of aliphatic polyesters include poly(ε-caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, and the like. It is preferable that the aliphatic polycarbonate mainly consists of aliphatic diol residues having 2 to 12 carbon atoms. Examples of these aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8- Octanediol, etc. are mentioned.
本発明の脂肪族ポリエーテルを含むブロック共重合体には、目的を損なわない範囲で、必要に応じて、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、界面活性剤、滑剤、染料、顔料、可塑剤、難燃剤等の添加剤が含まれていても構わない。
The block copolymer containing the aliphatic polyether of the present invention may contain antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, surfactants, lubricants, Additives such as dyes, pigments, plasticizers, flame retardants, etc. may be included.
本発明の抗菌性物品外層用樹脂組成物は抗菌剤を含まなくても高い抗菌性を有することを特徴とするので、抗菌剤を含まないか、抗菌剤が１質量％未満であることが好ましいが、抗菌剤が含まれていてもよい。抗菌剤としては、酸化チタン、酸化ジルコニウム、酸化アルミニウム、酸化マンガン、酸化亜鉛、酸化タングステン、酸化セリウム、酸化スズ、酸化バナジウム、酸化ルテニウム、酸化イットリウム、酸化クロム、酸化コバルト、酸化モリブデン、酸化銀、ヨウ化銅、亜酸化銅、チタン酸バリウム、チタン酸カリウム、チタン酸ナトリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸リチウム、チタン酸ベリリウム、リンモリブデン酸アンモニウム、第四級アンモニウム塩化合物、ケイ酸塩あるいはリン酸塩などの無機化合物に銀イオン、銅イオンもしくは亜鉛イオンを担持させた無機系抗菌剤、チアベンダゾール、ベンゾチアゾール、２－メチルカルボニルアミノベンツイミダゾール、ビオゾール、チモール、２，４，５，６－テトラクロロイソフタロニトリル、バイナジン、オキシン銅、アミノ酸に銀イオン、銅イオンもしくは亜鉛イオンを担持させた有機系抗菌剤、キトサン、アミノ酸糖体化合物、ヒノキチオールあるいは天然鉱石、などが挙げられる。
Since the resin composition for the outer layer of an antibacterial article of the present invention is characterized by having high antibacterial properties even without containing an antibacterial agent, it is preferable that it does not contain an antibacterial agent or that the antibacterial agent is less than 1% by mass. However, an antibacterial agent may also be included. Antibacterial agents include titanium oxide, zirconium oxide, aluminum oxide, manganese oxide, zinc oxide, tungsten oxide, cerium oxide, tin oxide, vanadium oxide, ruthenium oxide, yttrium oxide, chromium oxide, cobalt oxide, molybdenum oxide, silver oxide, Copper iodide, cuprous oxide, barium titanate, potassium titanate, sodium titanate, strontium titanate, calcium titanate, magnesium titanate, lithium titanate, beryllium titanate, ammonium phosphomolybdate, quaternary ammonium salts compounds, inorganic antibacterial agents with silver, copper or zinc ions supported on inorganic compounds such as silicates or phosphates, thiabendazole, benzothiazole, 2-methylcarbonylaminobenzimidazole, biosol, thymol, 2, 4,5,6-tetrachloroisophthalonitrile, binazine, copper oxine, organic antibacterial agents with silver, copper or zinc ions supported on amino acids, chitosan, amino acid glycoside compounds, hinokitiol or natural minerals, etc. Can be mentioned.
また、本発明の抗菌性物品外層用樹脂組成物は、本発明の脂肪族ポリエーテルを含むブロック共重合体のみからなっても構わないし、目的を損なわない範囲で、必要に応じて、他の重合体や添加剤、タルク、マイカ、ガラスフレーク、炭酸カルシウム、クレー、硫酸バリウム、ガラスビーズ、ガラス繊維、炭素繊維、セルロースナノファイバーなどの補強材を添加することができる。本発明の抗菌性物品外層用樹脂組成物は、本発明の脂肪族ポリエーテルを含むブロック共重合体を、５０～１００質量％含むことが好ましく、８０～１００質量％含むことがより好ましく、９０～１００質量％含むことがさらに好ましい。
Furthermore, the resin composition for the outer layer of an antibacterial article of the present invention may be composed only of the block copolymer containing the aliphatic polyether of the present invention, or may be composed of other components as necessary to the extent that the purpose is not impaired. Polymers and additives, reinforcing materials such as talc, mica, glass flakes, calcium carbonate, clay, barium sulfate, glass beads, glass fibers, carbon fibers, cellulose nanofibers, etc. can be added. The resin composition for the outer layer of an antibacterial article of the present invention preferably contains 50 to 100% by mass, more preferably 80 to 100% by mass, and more preferably 90 to 100% by mass of the block copolymer containing the aliphatic polyether of the present invention. It is more preferable that the content is from 100% by mass.
本発明の細菌の具体例としては、ピロリ菌、結核菌、黄色ブドウ球菌、表皮ブドウ球菌、Ａ群連鎖球菌、Ｂ群連鎖球菌、らい菌、破傷風菌、炭疽菌、髄膜炎菌、インフルエンザ菌、コレラ菌、ペスト菌、百日咳菌、マイコプラズマ、モラクセラ・カタラーリス、レジオネラ・ニューモフィラ、大腸菌、腸管出血性大腸菌Ｏ１５７、チフス菌、ネズミチフス菌、赤痢菌属細菌、カンピロバクター属細菌、ウェルシュ菌、リステリア・モノサイトゲネス、セレウス菌、ボツリヌス菌、プレジオモナス・シゲロイデス、トレポネーマ・パリドゥム、淋菌、クラミジア・トラコマチス、アクチノマイセス・イスラエリ、ストレプトコッカス・ミュータンス、シテロバクター属、エンテロバクター属、セラチア属、緑膿菌、野兎病菌、ストレプトバチルス・モニリフォルミス、バルトネラ・ヘンセレ、等が挙げられる。
Specific examples of the bacteria of the present invention include Helicobacter pylori, Mycobacterium tuberculosis, Staphylococcus aureus, Staphylococcus epidermidis, Group A Streptococcus, Group B Streptococcus, Mycobacterium leprae, Clostridium tetani, Bacillus anthrax, Neisseria meningitidis, and Haemophilus influenzae. , Vibrio cholerae, Yersinia pestis, Bordetella pertussis, Mycoplasma, Moraxella catarrhalis, Legionella pneumophila, Escherichia coli, Enterohemorrhagic Escherichia coli O157, Salmonella typhi, Salmonella typhimurium, Shigella, Campylobacter, Clostridium perfringens, Listeria mono Cytogenes, Bacillus cereus, Clostridium botulinum, Plesiomonas shigelloides, Treponema pallidum, Neisseria gonorrhoeae, Chlamydia trachomatis, Actinomyces israelii, Streptococcus mutans, Cyterobacter sp., Enterobacter sp., Serratia sp., Pseudomonas aeruginosa, Hare Examples include pathogenic bacteria, Streptobacillus moniliformis, Bartonella hensele, and the like.
本発明の成形体は、本発明の抗菌性物品外層用樹脂組成物を加工してなる。本発明の成形体の具体的な態様は、射出成形品、押出成形品、フィルム、繊維、不織布及び発泡体等である。
The molded article of the present invention is obtained by processing the resin composition for an outer layer of an antibacterial article of the present invention. Specific embodiments of the molded product of the present invention include injection molded products, extrusion molded products, films, fibers, nonwoven fabrics, and foams.
本発明の抗菌性物品外層用樹脂組成物は、抗菌性を付与させたい物品の外層に好ましく用いられる。すなわち、抗菌性を有する物品を提供する方法であって、前記方法は物品の外層を提供する工程を含み、前記外層が本発明の抗菌性物品外層用樹脂組成物を含むことは好ましい。ここで外層とは、２層以上が重なってできている成形体の表層部、もしくは単層成形体の露出面であり、例えば、インモールド成形体のフィルム層、２色成形品の人が触れられる層、コーティングしていないマスクの露出面等があげられる。
The resin composition for the outer layer of an antibacterial article of the present invention is preferably used for the outer layer of an article to which it is desired to impart antibacterial properties. That is, it is a method for providing an article having antibacterial properties, and the method includes a step of providing an outer layer of the article, and it is preferable that the outer layer contains the resin composition for an antibacterial article outer layer of the present invention. The outer layer here refers to the surface layer of a molded product made of two or more overlapping layers, or the exposed surface of a single-layer molded product, such as the film layer of an in-mold molded product, or the exposed surface of a two-color molded product that is touched by a person. This includes layers covered by the coating, exposed surfaces of uncoated masks, etc.
また、物品の表面に抗菌性を付与するための、本発明の抗菌性樹脂組成物の物品の外層への使用は好ましい。
Furthermore, it is preferable to use the antibacterial resin composition of the present invention in the outer layer of an article in order to impart antibacterial properties to the surface of the article.
本発明の抗菌性物品外層用樹脂組成物の用途としては、壁紙、床材、カーテン、衣類、ごみ箱、食品包装材、絆創膏、マスク、包帯、食器、家具、玩具、浴室部材、トイレ部材、キッチン部材、家電、フィルター（空気清浄器）、寝具（毛布、布団、シーツ）、座席用シート（カーシート、列車シート、航空機シート、家庭用チェアシート）、つり革、手すり、スポンジ（清掃用、食器洗い、ろ過材）、おむつ、清掃用具、汚染拡散防止材、自動車内装材、等が挙げられる。
Applications of the resin composition for the outer layer of antibacterial articles of the present invention include wallpaper, flooring, curtains, clothing, trash cans, food packaging, adhesive plasters, masks, bandages, tableware, furniture, toys, bathroom parts, toilet parts, and kitchens. Components, home appliances, filters (air purifiers), bedding (blankets, futons, sheets), seats (car seats, train seats, aircraft seats, household chair seats), straps, handrails, sponges (for cleaning, dishwashing) , filter materials), diapers, cleaning tools, pollution diffusion prevention materials, automobile interior materials, etc.
以下に実施例によって本発明の効果を説明する。なお、実施例中の％及び部とは、断りのない場合、すべて質量基準である。表中の“Ｅ”を用いた生菌数は、“Ｅ”の前に仮数部、後に指数部を示す指数表記（Ｅ表記）である。また、実施例中に示される物性は次のように測定した。
The effects of the present invention will be explained below with reference to Examples. Note that all % and parts in the examples are based on mass unless otherwise specified. The number of viable bacteria using "E" in the table is an exponential notation (E notation) in which the mantissa part is before the "E" and the exponent part is after. Further, the physical properties shown in the examples were measured as follows.
［熱可塑性ポリエステルエラストマー（Ａ－１）］
テレフタル酸２７０．０部、１，４－ブタンジオール２３４．０部およびテトラブチルチタネート０．１部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．１部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、７００ｍｍＨｇの減圧下でエステル化反応を開始した。その後、徐々に昇温するとともに、さらに１，４－ブタンジオール５９．０部を連続的に追加添加した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート１．８部、安定剤として“ＩＲＧＡＮＯＸ”１３３０（ＢＡＳＦ社製）１．０部をエステル化缶に添加し、一方、数平均分子量１４００のポリ（テトラメチレンオキシド）グリコール６８６．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が６８％の熱可塑性ポリエステルエラストマー（Ａ－１）を得た。 [Thermoplastic polyester elastomer (A-1)]
Esterification of 270.0 parts of terephthalic acid, 234.0 parts of 1,4-butanediol, 0.1 part of tetrabutyl titanate, and 0.1 part of mono-n-butyl-monohydroxytin oxide using a rectification column and a stirrer. The mixture was charged into a can, and the esterification reaction was started at 160° C. and under a reduced pressure of 700 mmHg. Thereafter, while gradually increasing the temperature, 59.0 parts of 1,4-butanediol was continuously added. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 1.8 parts of tetrabutyl titanate as a polycondensation catalyst and 1.0 part of "IRGANOX" 1330 (manufactured by BASF) as a stabilizer were added to the esterification can, while polyester having a number average molecular weight of 1400 was added. After charging 686.0 parts of (tetramethylene oxide) glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-1) having a copolymerization ratio of the aliphatic polyether component of 68%.
テレフタル酸２７０．０部、１，４－ブタンジオール２３４．０部およびテトラブチルチタネート０．１部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．１部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、７００ｍｍＨｇの減圧下でエステル化反応を開始した。その後、徐々に昇温するとともに、さらに１，４－ブタンジオール５９．０部を連続的に追加添加した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート１．８部、安定剤として“ＩＲＧＡＮＯＸ”１３３０（ＢＡＳＦ社製）１．０部をエステル化缶に添加し、一方、数平均分子量１４００のポリ（テトラメチレンオキシド）グリコール６８６．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が６８％の熱可塑性ポリエステルエラストマー（Ａ－１）を得た。 [Thermoplastic polyester elastomer (A-1)]
Esterification of 270.0 parts of terephthalic acid, 234.0 parts of 1,4-butanediol, 0.1 part of tetrabutyl titanate, and 0.1 part of mono-n-butyl-monohydroxytin oxide using a rectification column and a stirrer. The mixture was charged into a can, and the esterification reaction was started at 160° C. and under a reduced pressure of 700 mmHg. Thereafter, while gradually increasing the temperature, 59.0 parts of 1,4-butanediol was continuously added. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 1.8 parts of tetrabutyl titanate as a polycondensation catalyst and 1.0 part of "IRGANOX" 1330 (manufactured by BASF) as a stabilizer were added to the esterification can, while polyester having a number average molecular weight of 1400 was added. After charging 686.0 parts of (tetramethylene oxide) glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-1) having a copolymerization ratio of the aliphatic polyether component of 68%.
［熱可塑性ポリエステルエラストマー（Ａ－２）］
結晶性芳香族ポリエステルからなる高融点結晶性重合体セグメントとなるテレフタル酸ジメチル３１２部およびイソフタル酸ジメチル９１部、脂肪族ポリエーテル単位からなる低融点重合体セグメントとなる数平均分子量２１５０のポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物５３７部、さらに１，４－ブタンジオール１６７部、チタンテトラブトキシド４部をヘリカルリボン型撹拌翼を備えた反応容器に仕込み、１９０～２２５℃で３時間加熱してメタノールを系外に留出した。反応混合物に“ＩＲＧＡＮＯＸ”１０９８および１０１９（ＢＡＳＦ社製）各２部を添加した後、２４３℃に昇温し、次いで５０分かけて系内の圧力を０．２ｍｍＨｇの減圧とし、その条件下で３時間重合を行い、脂肪族ポリエーテル成分の共重合比率が５５％の熱可塑性ポリエステルエラストマー（Ａ－２）を得た
［熱可塑性ポリエステルエラストマー（Ａ－３）］
テレフタル酸３４０．０部、イソフタル酸１００部、１，４－ブタンジオール量２９６．０部およびテトラブチルチタネート０．３部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．１部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、５００ｍｍＨｇの減圧下でエステル化反応を開始した。その後、徐々に昇温するとともに、さらに１，４－ブタンジオール７４．０部を連続的に追加添加した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート１．５部、安定剤として“ＩＲＧＡＮＯＸ”１０９８（ＢＡＳＦ社製）０．５部をエステル化缶に添加し、一方、数平均分子量１４００のポリテトラメチレングリコール４９５．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が４７％の熱可塑性ポリエステルエラストマー（Ａ－３）を得た。 [Thermoplastic polyester elastomer (A-2)]
312 parts of dimethyl terephthalate and 91 parts of dimethyl isophthalate to form a high melting point crystalline polymer segment consisting of a crystalline aromatic polyester, and poly(propylene with a number average molecular weight of 2150 to form a low melting point polymer segment consisting of an aliphatic polyether unit). 537 parts of ethylene oxide adduct of glycol, 167 parts of 1,4-butanediol, and 4 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon stirring blade, and heated at 190 to 225°C for 3 hours to dissolve methanol. was distilled out of the system. After adding 2 parts each of "IRGANOX" 1098 and 1019 (manufactured by BASF) to the reaction mixture, the temperature was raised to 243°C, and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes. Polymerization was carried out for 3 hours to obtain a thermoplastic polyester elastomer (A-2) with a copolymerization ratio of the aliphatic polyether component of 55% [Thermoplastic polyester elastomer (A-3)]
340.0 parts of terephthalic acid, 100 parts of isophthalic acid, 296.0 parts of 1,4-butanediol, 0.3 part of tetrabutyl titanate, and 0.1 part of mono-n-butyl-monohydroxytin oxide were added to a rectification column, The mixture was charged into an esterification tank equipped with a stirrer, and the esterification reaction was started at 160° C. and under reduced pressure of 500 mmHg. Thereafter, while gradually increasing the temperature, 74.0 parts of 1,4-butanediol was continuously added. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 1.5 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF) as a stabilizer were added to the esterification can. After charging 495.0 parts of tetramethylene glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-3) having a copolymerization ratio of the aliphatic polyether component of 47%.
結晶性芳香族ポリエステルからなる高融点結晶性重合体セグメントとなるテレフタル酸ジメチル３１２部およびイソフタル酸ジメチル９１部、脂肪族ポリエーテル単位からなる低融点重合体セグメントとなる数平均分子量２１５０のポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物５３７部、さらに１，４－ブタンジオール１６７部、チタンテトラブトキシド４部をヘリカルリボン型撹拌翼を備えた反応容器に仕込み、１９０～２２５℃で３時間加熱してメタノールを系外に留出した。反応混合物に“ＩＲＧＡＮＯＸ”１０９８および１０１９（ＢＡＳＦ社製）各２部を添加した後、２４３℃に昇温し、次いで５０分かけて系内の圧力を０．２ｍｍＨｇの減圧とし、その条件下で３時間重合を行い、脂肪族ポリエーテル成分の共重合比率が５５％の熱可塑性ポリエステルエラストマー（Ａ－２）を得た
［熱可塑性ポリエステルエラストマー（Ａ－３）］
テレフタル酸３４０．０部、イソフタル酸１００部、１，４－ブタンジオール量２９６．０部およびテトラブチルチタネート０．３部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．１部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、５００ｍｍＨｇの減圧下でエステル化反応を開始した。その後、徐々に昇温するとともに、さらに１，４－ブタンジオール７４．０部を連続的に追加添加した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート１．５部、安定剤として“ＩＲＧＡＮＯＸ”１０９８（ＢＡＳＦ社製）０．５部をエステル化缶に添加し、一方、数平均分子量１４００のポリテトラメチレングリコール４９５．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が４７％の熱可塑性ポリエステルエラストマー（Ａ－３）を得た。 [Thermoplastic polyester elastomer (A-2)]
312 parts of dimethyl terephthalate and 91 parts of dimethyl isophthalate to form a high melting point crystalline polymer segment consisting of a crystalline aromatic polyester, and poly(propylene with a number average molecular weight of 2150 to form a low melting point polymer segment consisting of an aliphatic polyether unit). 537 parts of ethylene oxide adduct of glycol, 167 parts of 1,4-butanediol, and 4 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon stirring blade, and heated at 190 to 225°C for 3 hours to dissolve methanol. was distilled out of the system. After adding 2 parts each of "IRGANOX" 1098 and 1019 (manufactured by BASF) to the reaction mixture, the temperature was raised to 243°C, and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes. Polymerization was carried out for 3 hours to obtain a thermoplastic polyester elastomer (A-2) with a copolymerization ratio of the aliphatic polyether component of 55% [Thermoplastic polyester elastomer (A-3)]
340.0 parts of terephthalic acid, 100 parts of isophthalic acid, 296.0 parts of 1,4-butanediol, 0.3 part of tetrabutyl titanate, and 0.1 part of mono-n-butyl-monohydroxytin oxide were added to a rectification column, The mixture was charged into an esterification tank equipped with a stirrer, and the esterification reaction was started at 160° C. and under reduced pressure of 500 mmHg. Thereafter, while gradually increasing the temperature, 74.0 parts of 1,4-butanediol was continuously added. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 1.5 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF) as a stabilizer were added to the esterification can. After charging 495.0 parts of tetramethylene glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-3) having a copolymerization ratio of the aliphatic polyether component of 47%.
［熱可塑性ポリエステルエラストマー（Ａ－４）］
テレフタル酸５０１．０部、１，４－ブタンジオール量３２６．０部およびテトラブチルチタネート０．３部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．２部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、６５０ｍｍＨｇの減圧下でエステル化反応を開始した。その後、徐々に昇温するとともに、さらに１，４－ブタンジオール８１．０部を連続的に追加添加しながら、反応途中から減圧度を５００ｍｍＨｇに変更した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート２．０部、安定剤として“ＩＲＧＡＮＯＸ”１０９８（ＢＡＳＦ社製）０．５部をエステル化缶に添加し、一方、数平均分子量１４００のポリテトラメチレングリコール３５４．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が３５％の熱可塑性ポリエステルエラストマー（Ａ－４）を得た。 [Thermoplastic polyester elastomer (A-4)]
501.0 parts of terephthalic acid, 326.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.2 parts of mono-n-butyl-monohydroxytin oxide were mixed into an ester having a rectification column and a stirrer. The esterification reaction was started at 160° C. under reduced pressure of 650 mmHg. Thereafter, while gradually increasing the temperature and continuously adding 81.0 parts of 1,4-butanediol, the degree of vacuum was changed to 500 mmHg midway through the reaction. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 2.0 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF) as a stabilizer were added to the esterification can. After charging 354.0 parts of tetramethylene glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-4) having a copolymerization ratio of the aliphatic polyether component of 35%.
テレフタル酸５０１．０部、１，４－ブタンジオール量３２６．０部およびテトラブチルチタネート０．３部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．２部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、６５０ｍｍＨｇの減圧下でエステル化反応を開始した。その後、徐々に昇温するとともに、さらに１，４－ブタンジオール８１．０部を連続的に追加添加しながら、反応途中から減圧度を５００ｍｍＨｇに変更した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート２．０部、安定剤として“ＩＲＧＡＮＯＸ”１０９８（ＢＡＳＦ社製）０．５部をエステル化缶に添加し、一方、数平均分子量１４００のポリテトラメチレングリコール３５４．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が３５％の熱可塑性ポリエステルエラストマー（Ａ－４）を得た。 [Thermoplastic polyester elastomer (A-4)]
501.0 parts of terephthalic acid, 326.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.2 parts of mono-n-butyl-monohydroxytin oxide were mixed into an ester having a rectification column and a stirrer. The esterification reaction was started at 160° C. under reduced pressure of 650 mmHg. Thereafter, while gradually increasing the temperature and continuously adding 81.0 parts of 1,4-butanediol, the degree of vacuum was changed to 500 mmHg midway through the reaction. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 2.0 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF) as a stabilizer were added to the esterification can. After charging 354.0 parts of tetramethylene glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-4) having a copolymerization ratio of the aliphatic polyether component of 35%.
［熱可塑性ポリエステルエラストマー（Ａ－５）］
テレフタル酸７００．０部、１，４－ブタンジオール量７５９．０部およびテトラブチルチタネート０．３部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．１部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、５００ｍｍＨｇの減圧下でエステル化反応を開始した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート１．５部、安定剤として“ＩＲＧＡＮＯＸ”１３３０（ＢＡＳＦ社製）０．５部をエステル化缶に添加し、一方、数平均分子量１０００のポリテトラメチレングリコール８０．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が８％の熱可塑性ポリエステルエラストマー（Ａ－５）を得た。 [Thermoplastic polyester elastomer (A-5)]
700.0 parts of terephthalic acid, 759.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.1 part of mono-n-butyl-monohydroxytin oxide were added to an ester having a rectification column and a stirrer. The esterification reaction was started at 160° C. and under a reduced pressure of 500 mmHg. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 1.5 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1330 (manufactured by BASF) as a stabilizer were added to the esterification can. After charging 80.0 parts of tetramethylene glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-5) having a copolymerization ratio of the aliphatic polyether component of 8%.
テレフタル酸７００．０部、１，４－ブタンジオール量７５９．０部およびテトラブチルチタネート０．３部、モノｎ－ブチル－モノヒドロキシスズオキサイド０．１部を精留塔、撹拌機を有するエステル化缶に仕込み、１６０℃、５００ｍｍＨｇの減圧下でエステル化反応を開始した。反応を開始してから３時間４０分後に透明な反応生成物を得て、反応を終了させた。エステル化反応終了後、重縮合触媒としてテトラブチルチタネート１．５部、安定剤として“ＩＲＧＡＮＯＸ”１３３０（ＢＡＳＦ社製）０．５部をエステル化缶に添加し、一方、数平均分子量１０００のポリテトラメチレングリコール８０．０部を重縮合缶に仕込んだ後、上記のエステル化反応生成物をエステル化缶から重縮合缶へ移行した。そして、重縮合缶内の反応系を撹拌重合させながら、常圧から１ｍｍＨｇ以下の高真空度まで１時間かけて徐々に減圧系にし、同時に２４５℃に昇温して、２４５℃，１ｍｍＨｇ以下の条件下で３時間３０分重縮合せしめ、脂肪族ポリエーテル成分の共重合比率が８％の熱可塑性ポリエステルエラストマー（Ａ－５）を得た。 [Thermoplastic polyester elastomer (A-5)]
700.0 parts of terephthalic acid, 759.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.1 part of mono-n-butyl-monohydroxytin oxide were added to an ester having a rectification column and a stirrer. The esterification reaction was started at 160° C. and under a reduced pressure of 500 mmHg. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction was completed, 1.5 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1330 (manufactured by BASF) as a stabilizer were added to the esterification can. After charging 80.0 parts of tetramethylene glycol into the polycondensation can, the above esterification reaction product was transferred from the esterification can to the polycondensation can. Then, while stirring and polymerizing the reaction system in the polycondensation reactor, the pressure was gradually reduced from normal pressure to a high degree of vacuum of 1 mmHg or less over 1 hour, and at the same time the temperature was raised to 245°C. Polycondensation was carried out under these conditions for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-5) having a copolymerization ratio of the aliphatic polyether component of 8%.
［ＰＢＴ樹脂（Ｂ）］
トレコンＴＭ１１００Ｓ（東レ（株）社製）。テレフタル酸と１，４－ブタンジオールの重合体。 [PBT resin (B)]
Torrecon TM 1100S (manufactured by Toray Industries, Inc.). A polymer of terephthalic acid and 1,4-butanediol.
トレコンＴＭ１１００Ｓ（東レ（株）社製）。テレフタル酸と１，４－ブタンジオールの重合体。 [PBT resin (B)]
Torrecon TM 1100S (manufactured by Toray Industries, Inc.). A polymer of terephthalic acid and 1,4-butanediol.
［試験片の成形］
日精樹脂工業（株）製の射出成形機ＮＥＸ－１０００を用いて射出成形を行い、ペレットから８０ｘ８０ｘ２ｍｍの角板状の試験片を得た。射出成形が行えていることから、射出成形品、押出成形品、フィルム、繊維、不織布及び発泡体に加工することができる。 [Formation of test piece]
Injection molding was performed using an injection molding machine NEX-1000 manufactured by Nissei Jushi Kogyo Co., Ltd., and a rectangular plate-shaped test piece of 80 x 80 x 2 mm was obtained from the pellet. Since injection molding is possible, it can be processed into injection molded products, extrusion molded products, films, fibers, nonwoven fabrics, and foams.
日精樹脂工業（株）製の射出成形機ＮＥＸ－１０００を用いて射出成形を行い、ペレットから８０ｘ８０ｘ２ｍｍの角板状の試験片を得た。射出成形が行えていることから、射出成形品、押出成形品、フィルム、繊維、不織布及び発泡体に加工することができる。 [Formation of test piece]
Injection molding was performed using an injection molding machine NEX-1000 manufactured by Nissei Jushi Kogyo Co., Ltd., and a rectangular plate-shaped test piece of 80 x 80 x 2 mm was obtained from the pellet. Since injection molding is possible, it can be processed into injection molded products, extrusion molded products, films, fibers, nonwoven fabrics, and foams.
[抗菌性試験］
抗菌活性の測定は，基本的にＪＩＳＺ２８０１：２０１２抗菌加工製品抗菌性試験に準じて行った。 [Antibacterial test]
The antibacterial activity was basically measured in accordance with JISZ2801:2012 Antibacterial Processed Product Antibacterial Property Test.
抗菌活性の測定は，基本的にＪＩＳＺ２８０１：２０１２抗菌加工製品抗菌性試験に準じて行った。 [Antibacterial test]
The antibacterial activity was basically measured in accordance with JISZ2801:2012 Antibacterial Processed Product Antibacterial Property Test.
細菌は大腸菌と黄色ブドウ球菌を用いた。５ｃｍ角に切断した試験片上に、既定の菌液量１００μｌを滴下して，上からカバーフィルム（４ｃｍ角）をかぶせて細菌液を均等に広げた。３５度で２４時間静置したのちに，洗い出し液１０ｍｌを添加し、ピペッティングにて細菌をＳＣＤＬＰ培地で洗い出した。混釈平板培養法を用いて、洗い出し液中の生菌数（ＣＦＵ／ｃｍ２）を寒天培地中のコロニー数により測定した。生菌数の検出限界は０．６３（ＣＦＵ／ｃｍ２）である。
The bacteria used were Escherichia coli and Staphylococcus aureus. A predetermined amount of 100 μl of the bacterial solution was dropped onto a test piece cut into 5 cm square pieces, and a cover film (4 cm square) was placed on top to spread the bacterial solution evenly. After standing at 35 degrees for 24 hours, 10 ml of washing solution was added, and bacteria were washed out with SCDLP medium by pipetting. Using the pour plate culture method, the number of viable bacteria (CFU/cm 2 ) in the washout solution was determined by the number of colonies in the agar medium. The detection limit for the number of viable bacteria is 0.63 (CFU/cm 2 ).
［抗菌活性値及び生菌数低減率］
２４時間後の抗菌活性値（Ｒ）及び２４時間後の生菌数低減率（％）は、接種直後（０時間）の生菌数をＵ０、２４時間後の生菌数をＵ２４とし、下記の式により求めた。
２４時間後の抗菌活性値（Ｒ）＝ｌｇ１０（Ｕ０）－ｌｇ１０（Ｕ２４）
２４時間後の生菌数低減率（％）＝[（Ｕ０－Ｕ２４）×１００]／Ｕ０。 [Antibacterial activity value and viable bacteria count reduction rate]
The antibacterial activity value (R) after 24 hours and the reduction rate of viable bacteria count after 24 hours (%) are calculated using the number of viable bacteria immediately after inoculation (0 hours) as U 0 and the number of viable bacteria after 24 hours as U 24 . , was calculated using the following formula.
Antibacterial activity value after 24 hours (R) = lg10 (U 0 ) - lg10 (U 24 )
Viable cell count reduction rate (%) after 24 hours = [(U 0 - U 24 ) x 100]/U 0.
２４時間後の抗菌活性値（Ｒ）及び２４時間後の生菌数低減率（％）は、接種直後（０時間）の生菌数をＵ０、２４時間後の生菌数をＵ２４とし、下記の式により求めた。
２４時間後の抗菌活性値（Ｒ）＝ｌｇ１０（Ｕ０）－ｌｇ１０（Ｕ２４）
２４時間後の生菌数低減率（％）＝[（Ｕ０－Ｕ２４）×１００]／Ｕ０。 [Antibacterial activity value and viable bacteria count reduction rate]
The antibacterial activity value (R) after 24 hours and the reduction rate of viable bacteria count after 24 hours (%) are calculated using the number of viable bacteria immediately after inoculation (0 hours) as U 0 and the number of viable bacteria after 24 hours as U 24 . , was calculated using the following formula.
Antibacterial activity value after 24 hours (R) = lg10 (U 0 ) - lg10 (U 24 )
Viable cell count reduction rate (%) after 24 hours = [(U 0 - U 24 ) x 100]/U 0.
［実施例１、２］
上記熱可塑性ポリエステルエラストマ（Ａ－１）を用いて評価を行った。 [Example 1, 2]
Evaluation was performed using the above thermoplastic polyester elastomer (A-1).
上記熱可塑性ポリエステルエラストマ（Ａ－１）を用いて評価を行った。 [Example 1, 2]
Evaluation was performed using the above thermoplastic polyester elastomer (A-1).
［実施例３、４］
上記熱可塑性ポリエステルエラストマ（Ａ－２）を用いて評価を行った。 [Examples 3 and 4]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-2).
上記熱可塑性ポリエステルエラストマ（Ａ－２）を用いて評価を行った。 [Examples 3 and 4]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-2).
［実施例５、６］
上記熱可塑性ポリエステルエラストマ（Ａ－３）を用いて評価を行った。 [Example 5, 6]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-3).
上記熱可塑性ポリエステルエラストマ（Ａ－３）を用いて評価を行った。 [Example 5, 6]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-3).
［実施例７、８］
上記熱可塑性ポリエステルエラストマ（Ａ－４）を用いて評価を行った。 [Example 7, 8]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-4).
上記熱可塑性ポリエステルエラストマ（Ａ－４）を用いて評価を行った。 [Example 7, 8]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-4).
［比較例１、２］
上記ＰＢＴ樹脂（Ｂ）を用いて評価を行った。 [Comparative Examples 1 and 2]
Evaluation was performed using the above PBT resin (B).
上記ＰＢＴ樹脂（Ｂ）を用いて評価を行った。 [Comparative Examples 1 and 2]
Evaluation was performed using the above PBT resin (B).
［比較例３、４］
上記熱可塑性ポリエステルエラストマ（Ａ－５）を用いて評価を行った。 [Comparative Examples 3 and 4]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-5).
上記熱可塑性ポリエステルエラストマ（Ａ－５）を用いて評価を行った。 [Comparative Examples 3 and 4]
Evaluation was conducted using the above thermoplastic polyester elastomer (A-5).
実施例および比較例の材料、脂肪族ポリエーテル成分の比率、０時間と２４時間の生菌数、２４時間後の抗菌活性値と２４時間後の生菌数低減率を表１に示す。
Table 1 shows the materials of Examples and Comparative Examples, the ratio of the aliphatic polyether component, the number of viable bacteria at 0 and 24 hours, the antibacterial activity value after 24 hours, and the rate of reduction in the number of viable bacteria after 24 hours.
実施例１～８より、脂肪族ポリエーテル成分を含有する熱可塑性ポリエステルエラストマー（Ａ－１）、（Ａ－２）、（Ａ－３）、（Ａ－４）では生菌数低減効果が大きいことがわかる。
From Examples 1 to 8, thermoplastic polyester elastomers (A-1), (A-2), (A-3), and (A-4) containing an aliphatic polyether component have a large effect of reducing the number of viable bacteria. I understand that.
また、比較例１～４より、脂肪族ポリエーテル成分を含有しないＰＢＴ樹脂（Ｂ）と熱可塑性ポリエステルエラストマ（Ａ－５）では２４時間後の生菌数が０時間の生菌数より多いこと、また抗菌活性値が２未満から、低減効果がないことがわかる。比較例１～３は低減効果がないため、２４時間後の抗菌活性値と２４時間後の生菌数低減率は０とした。
In addition, from Comparative Examples 1 to 4, the number of viable bacteria after 24 hours was greater than the number of viable bacteria at 0 hours for PBT resin (B) that does not contain an aliphatic polyether component and thermoplastic polyester elastomer (A-5). , and an antibacterial activity value of less than 2 indicates that there is no reduction effect. Since Comparative Examples 1 to 3 had no reduction effect, the antibacterial activity value after 24 hours and the reduction rate of viable bacteria count after 24 hours were set to 0.
Claims (6)
- ２４時間後の抗菌活性値が２以上であるブロック共重合体を含有し、該ブロック共重合体が脂肪族ポリエーテルを含むブロック共重合体であることを特徴とする抗菌性物品外層用樹脂組成物。 A resin composition for an outer layer of an antibacterial article, comprising a block copolymer having an antibacterial activity value of 2 or more after 24 hours, the block copolymer being a block copolymer containing an aliphatic polyether. thing.
- 前記脂肪族ポリエーテルを含むブロック共重合体が熱可塑性ポリエステルエラストマーであることを特徴とする請求項１に記載の抗菌性物品外層用樹脂組成物。 The resin composition for an outer layer of an antibacterial article according to claim 1, wherein the block copolymer containing the aliphatic polyether is a thermoplastic polyester elastomer.
- 前記脂肪族ポリエーテルを含むブロック共重合体の脂肪族ポリエーテルの共重合比率が９％以上であることを特徴とする請求項１または２に記載の抗菌性物品外層用樹脂組成物。 The resin composition for an outer layer of an antibacterial article according to claim 1 or 2, wherein the block copolymer containing the aliphatic polyether has a copolymerization ratio of the aliphatic polyether of 9% or more.
- 前記脂肪族ポリエーテルがポリ（テトラメチレンオキシド）グリコールもしくはポリ（プロピレンオキシド）グリコールのエチレンオキシド付加物であることを特徴とする請求項１または２に記載の抗菌性物品外層用樹脂組成物。 The resin composition for an outer layer of an antibacterial article according to claim 1 or 2, wherein the aliphatic polyether is an ethylene oxide adduct of poly(tetramethylene oxide) glycol or poly(propylene oxide) glycol.
- 請求項１または２に記載の抗菌性物品外層用樹脂組成物を加工してなる成形体。 A molded article obtained by processing the resin composition for an outer layer of an antibacterial article according to claim 1 or 2.
- 請求項１または２に記載の抗菌性物品外層用樹脂組成物を外層に用いてなる抗菌性物品。
An antibacterial article comprising the resin composition for an outer layer of an antibacterial article according to claim 1 or 2 as an outer layer.
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| JP2022-110173 | 2022-07-08 | ||
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004190017A (en) * | 2002-11-28 | 2004-07-08 | Du Pont Toray Co Ltd | Thermoplastic elastomer resin composition and molding |
| JP2004352790A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Plasticizer-containing resin composition and molding |
| JP7183477B1 (en) * | 2021-01-22 | 2022-12-05 | 東レ・デュポン株式会社 | Resin composition for outer layer of antiviral article, molded article, antiviral article |
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- 2023-07-07 WO PCT/JP2023/025260 patent/WO2024010084A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004190017A (en) * | 2002-11-28 | 2004-07-08 | Du Pont Toray Co Ltd | Thermoplastic elastomer resin composition and molding |
| JP2004352790A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Plasticizer-containing resin composition and molding |
| JP7183477B1 (en) * | 2021-01-22 | 2022-12-05 | 東レ・デュポン株式会社 | Resin composition for outer layer of antiviral article, molded article, antiviral article |
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