JP4626330B2 - Thermoplastic resin composition and molded product using the resin composition - Google Patents
Thermoplastic resin composition and molded product using the resin composition Download PDFInfo
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本発明は、優れた抗菌性を有する熱可塑性樹脂組成物および該樹脂組成物を用いて成る成形物に関する。 The present invention relates to a thermoplastic resin composition having excellent antibacterial properties and a molded article formed using the resin composition.
近年、若年層を中心に抗菌・殺菌に対する要求が強まっている。玩具、トイレ用品、まな板、包丁等の台所用品、箸、皿等の食品容器、浴用用品、歯ブラシ等の家庭用品から工業用品に至るまで抗菌性が望まれており、抗菌性成形物が使用されている。 In recent years, there has been an increasing demand for antibacterial and sterilization, especially among young people. Antibacterial properties are desired from toys, toilet articles, kitchen utensils such as cutting boards, kitchen knives, food containers such as chopsticks and dishes, bathing utensils, household items such as toothbrushes to industrial supplies, and antibacterial molded products are used. ing.
また、病院等の医療設備においては黄色ブドウ球菌、大腸菌、緑膿菌等の院内感染が大きな社会的問題となっている。手術室等の特別な部屋だけでなく免疫力の低下した病人等にも安全な衛生的環境を提供するため、壁材、床材、天井材、階段手すり等の材料に抗菌性を求める要求はより強いものとなっている。 In hospitals and other medical facilities, nosocomial infections such as Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa are a major social problem. In order to provide a safe and hygienic environment not only for special rooms such as operating rooms but also for patients with reduced immunity, there is a demand for antibacterial properties for materials such as wall materials, flooring materials, ceiling materials, and stair railings. It has become stronger.
これらの製品に抗菌性を付与するために、熱可塑性樹脂に各種の抗菌剤を添加したり、抗菌剤を含有する合成樹脂塗料を塗布することが行われている。 In order to impart antibacterial properties to these products, various antibacterial agents are added to thermoplastic resins, or synthetic resin paints containing antibacterial agents are applied.
銀などの特定の金属に抗菌作用があることが古くから知られており、これら金属を用いた抗菌剤として、ゼオライト、シリカゲル、ヒドロキシアパタイト等の各種の無機化合物を上記金属で変成した無機系抗菌剤または各種の有機酸の上記金属塩が知られている。 It has long been known that specific metals such as silver have an antibacterial action, and as an antibacterial agent using these metals, inorganic antibacterials in which various inorganic compounds such as zeolite, silica gel and hydroxyapatite are modified with the above metals. Such metal salts of agents or various organic acids are known.
しかし、金属塩の過多や遊離アルカリが存在すると、銀イオン等が反応性に富むため呈色反応を起こす危険があり、特に、熱可塑性樹脂のような添加剤が多い系では変色が著しい欠点もあるため、その用途は限定されたものでしかなかった。そこで、銀イオンの反応性を抑制する為にフッ素皮膜を行う事（例えば特許文献１参照）も試みられたが、満足行くものではなかった。 However, if there is an excess of metal salt or free alkali, there is a risk of causing a color reaction due to the high reactivity of silver ions, etc., especially in systems where there are many additives such as thermoplastic resins, there is also the disadvantage that discoloration is significant. For that reason, its use has been limited. Then, in order to suppress the reactivity of silver ions, an attempt was made to perform a fluorine film (see, for example, Patent Document 1), but it was not satisfactory.
また、有機系の抗菌剤として、ハロゲンや硫黄を含有する有機化合物等が知られているが、これら有機化合物は抗菌性には優れるものの、人体に有害な化合物が多い。また、無機系抗菌剤に比べて耐熱性、安定性に乏しいために、熱可塑性樹脂に添加して加工を行う際に、分解したり製品から逃失して効力を失うばかりでなく、臭気の発生や高分子材料の物性低下等の好ましくない作用をも奏するため、用途が制限されていた。 In addition, organic compounds containing halogen or sulfur are known as organic antibacterial agents, but these organic compounds are excellent in antibacterial properties, but many compounds are harmful to the human body. In addition, since it has poor heat resistance and stability compared to inorganic antibacterial agents, when it is added to a thermoplastic resin and processed, it not only decomposes and loses its effectiveness by losing its product, but also has an odor. The use has been limited because of undesirable effects such as generation and degradation of physical properties of the polymer material.
また、安全性の高い天然由来の抗菌剤として、竹類抽出物を配合したポリ塩化ビニル樹脂またはポリオレフィン樹脂から得られる抗菌・抗藻性成形物が提案（例えば特許文献２参照）されているが、竹類抽出物の抗菌・抗藻効果は小さいので、単独では多量に添加しなければ効果を奏さなくなるばかりでなく、分解する等の耐熱性に欠点があった。 Further, antibacterial and antialgal moldings obtained from polyvinyl chloride resin or polyolefin resin blended with bamboo extract have been proposed as highly safe antibacterial agents derived from nature (see, for example, Patent Document 2). In addition, the antibacterial and antialgal effects of bamboo extracts are small, so if they are not added in a large amount, they will not be effective, and there are drawbacks in heat resistance such as decomposition.
さらに、天然由来としてリグニン化合物と熱可塑性樹脂とを特定の割合で含有させる事により（例えば特許文献３参照）抗菌性を持たせる事が提案されているが、リグニンの耐熱性が悪く十分な抗菌性が得られていないのが現状である。 Furthermore, it has been proposed to provide antibacterial properties by containing a lignin compound and a thermoplastic resin in a specific ratio as a natural origin (see, for example, Patent Document 3), but lignin has poor heat resistance and has sufficient antibacterial properties. It is the present condition that the property is not acquired.
このため、熱可塑性樹脂の加工に耐えられる高い安定性を有し、製品の価値を損なうような着色がなく、しかも、人体に対する安全性の大きい抗菌剤、及びこのような抗菌剤を添加することにより、優れた抗菌性を有する熱可塑性樹脂組成物及び成形物が強く要望されていた。 For this reason, antibacterial agents that have high stability to withstand the processing of thermoplastic resins, have no color that impairs the value of the product, and are highly safe for the human body, and such antibacterial agents should be added Therefore, there has been a strong demand for thermoplastic resin compositions and molded articles having excellent antibacterial properties.
本発明の目的は、優れた抗菌性を有する熱可塑性樹脂組成物および該樹脂組成物を用いて成る成形物を提供することにある。 An object of the present invention is to provide a thermoplastic resin composition having excellent antibacterial properties and a molded product formed using the resin composition.
本発明者等は鋭意検討を重ねた結果、抗菌剤として竹類抽出物と、フライポンタイト型鉱物とを併用する事によって両者が相乗的に作用して優れた抗菌性を示し、しかも、高い耐熱性を有し、製品の価値を損なうような着色がないばかりでなく、人体に対する安全性が大きいことを特徴とする熱可塑性樹脂組成物及び成形物を得た。 As a result of intensive studies, the inventors of the present invention used a bamboo extract as an antibacterial agent and a fly-pontite-type mineral in combination, both of which acted synergistically to exhibit excellent antibacterial properties, and high A thermoplastic resin composition and a molded product having heat resistance and not only coloring that impairs the value of the product but also having high safety to human bodies were obtained.
すなわち本発明の第１の発明は、抗菌剤として孟宗竹抽出物と、下記式（１）で示されるフライポンタイト型鉱物とを含む熱可塑性樹脂組成物である。
（Ｚｎ 3-X Ａｌ X ）（Ｓｉ 2-X Ａｌ X ）Ｏ 5 （ＯＨ） 4 （１）
（式中、Ｘは０．１〜１．７５を表す。）
In other words, the first invention of the present invention is a thermoplastic resin composition containing a Sosoutake extract as an antibacterial agent and a fly-pontite-type mineral represented by the following formula (1) .
(Zn 3-X Al X) (Si 2-X Al X) O 5 (OH) 4 (1)
(In the formula, X represents 0.1 to 1.75.)
第２の発明は、フライポンタイト型鉱物が合成フライポンタイト型鉱物である第１の発明に記載の熱可塑性樹脂組成物である。 2nd invention is a thermoplastic resin composition as described in 1st invention whose fly-pontite type mineral is a synthetic fly-pontite type mineral.
第３の発明は、フライポンタイト型鉱物に含まれる酸化物の３成分組成比が、ＳｉＯ2２５〜６５モル％、ＭＯ（Ｍ＝ＺｎまたはＭｇ）１５〜６０モル％、Ａｌ2Ｏ3２〜５０モル％の範囲である上記発明の熱可塑性樹脂組成物である。 In the third invention, the three-component composition ratio of the oxide contained in the fly-pontite type mineral is SiO 2 25 to 65 mol%, MO (M = Zn or Mg) 15 to 60 mol%, Al 2 O 3 2. It is a thermoplastic resin composition of the said invention which is the range of -50 mol%.
第４の発明は、上記発明の熱可塑性樹脂組成物を成形して得られる成形物である。
4th invention is a molding obtained by shape | molding the thermoplastic resin composition of the said invention .
本発明の熱可塑性樹脂組成物は、抗菌剤として竹類抽出物と、フライポンタイト型鉱物とを含むので、抗菌性と共に成形性に優れる。 Since the thermoplastic resin composition of the present invention contains a bamboo extract and a fly-pontite-type mineral as an antibacterial agent, it is excellent in moldability as well as antibacterial properties.
本発明の熱可塑性樹脂組成物は、フライポンタイト型鉱物が下記式（１）で示されるので、更に抗菌性に優れる。
（Ｚｎ３−ＸＡｌＸ）（Ｓｉ２−ＸＡｌＸ）Ｏ５（ＯＨ）４ （１）
（式中、Ｘは０．１〜１．７５を表す。）
The thermoplastic resin composition of the present invention is further excellent in antibacterial properties because the fly-pontite-type mineral is represented by the following formula (1).
(Zn 3-X Al X) (Si 2-X Al X) O 5 (OH) 4 (1)
(In the formula, X represents 0.1 to 1.75.)
本発明の熱可塑性樹脂組成物は、フライポンタイト型鉱物に含まれる酸化物の３成分組成比が、ＳｉＯ２２５〜６５モル％、ＭＯ（Ｍ＝ＺｎまたはＭｇ）１５〜６０モル％、Ａｌ２Ｏ３２〜５０モル％の範囲なので更に抗菌性に優れる。 In the thermoplastic resin composition of the present invention, the three-component composition ratio of the oxide contained in the fly-pontite-type mineral is 25 to 65 mol% of SiO 2 , 15 to 60 mol% of MO (M = Zn or Mg), Al Since it is in the range of 2 O 3 2 to 50 mol%, it is further excellent in antibacterial properties.
本発明の成形物は、本発明の熱可塑性樹脂組成物を成形して得られるので抗菌性、成形性に優れると共に着色しない。 Since the molded product of the present invention is obtained by molding the thermoplastic resin composition of the present invention, it is excellent in antibacterial properties and moldability and is not colored.
次に、好ましい実施の形態を挙げて本発明を更に詳細に説明する。
本発明において使用される熱可塑性樹脂としては、従来各種の樹脂成形物の製造に使用されている熱可塑性樹脂はいずれも使用することができ、特に制限されない。例えば高密度、低密度または直鎖状低密度ポリエチレン、ポリプロピレン、ポリブテン−１、ポリ−３−メチルペンテン等のα−オレフィン重合体；エチレン−酢酸ビニル共重合体、エチレン−プロピレン共重合体等のポリオレフィン及びこれらの共重合体；ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩素化ポリプロピレン、ポリフッ化ビニリデン、塩化ゴム、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体、塩化ビニル−塩化ビニリデン共重合体、塩化ビニル−塩化ビニリデン−酢酸ビニル三元共重合体、塩化ビニル−アクリル酸エステル共重合体、塩化ビニル−マレイン酸エステル共重合体、塩化ビニル−シクロヘキシルマレイミド共重合体、塩化ビニル−シクロヘキシルマレイミド共重合体等の含ハロゲン樹脂；石油樹脂、クマロン樹脂、ポリスチレン、ポリ酢酸ビニル、アクリル樹脂；スチレン及び／又はα−メチルスチレンと他の単量体（例えば無水マレイン酸、フェニルマレイミド、メタクリル酸メチル、ブタジエン、アクリロニトリル等）との共重合体（例えばＡＳ樹脂、ＡＢＳ樹脂、ＭＢＳ樹脂、耐熱ＡＢＳ樹脂等）；ポリメチルメタクリレート、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール；ポリエチレンテレフタレート、ポリテトラメチレンテレフタレート等の直鎖ポリエステル；ポリフェニレンオキサイド、ポリフェニレンスルフィド、ポリカプロラクタム及びポリヘキサメチレンアジパミド等のポリアミド；ポリカーボネート、分岐ポリカーボネート、ポリアセタール、ポリウレタン、繊維素系樹脂等の熱可塑性合成樹脂及びこれらのブレンド物をあげることができる。更に、イソプレンゴム、ブタジエンゴム、アクリロニトリル−ブタジエン共重合ゴム、スチレン−ブタジエン共重合ゴム等のエラストマーであっても良い。上記高分子材料の中でも、ポリオレフィンが好ましい。
Next, the present invention will be described in more detail with reference to preferred embodiments.
As the thermoplastic resin used in the present invention, any thermoplastic resin conventionally used for producing various resin molded products can be used, and is not particularly limited. For example, α-olefin polymers such as high density, low density or linear low density polyethylene, polypropylene, polybutene-1, poly-3-methylpentene; ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, etc. Polyolefin and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride -Vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer, Such as vinyl chloride-cyclohexylmaleimide copolymer Halogen resin; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin; styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (For example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; linear polyester such as polyethylene terephthalate, polytetramethylene terephthalate; polyphenylene oxide , Polyamides such as polyphenylene sulfide, polycaprolactam and polyhexamethylene adipamide; polycarbonate, branched polycarbonate, polyacetal, polyurethane, fiber It can be mentioned a thermoplastic synthetic resin and blends of such systems resin. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used. Among the polymer materials, polyolefin is preferable.
本発明で使用される抗菌剤は竹類抽出物である。竹類抽出物の原料としてはトウチク属、ホウオウチク属、ナリヒラダケ属、マダケ属、メダケ属、シホウチク属、ササモルファ属、ジュドザサ属等に属する竹類であり、中でも孟宗竹の葉及び茎の表皮が特に好適である。これらの原料から竹類抽出物を得るには、ボールミル等を用いて葉や茎の表皮を粉砕し、ついでエタノール、ｎ−へキサン、エーテル、アセトン等の溶媒で抽出後、溶媒を蒸発させればよい。また、この際必要により、クロマトグラフィーを用いてさらに精製することもできる。
竹類抽出物は、水や有機溶剤等の溶媒に溶解・分散した状態や粉末状態等、形態に限定なく使用できる。
The antibacterial agent used in the present invention is a bamboo extract. Bamboo extracts are bamboos belonging to the genus Tochiku, Houchiku, Narihirada, Madake, Medake, Shibuchiku, Sasamorfa, Judozasa, etc. It is. In order to obtain bamboo extracts from these raw materials, the skin of leaves and stems is pulverized using a ball mill or the like, then extracted with a solvent such as ethanol, n-hexane, ether or acetone, and then the solvent is evaporated. That's fine. At this time, if necessary, it can be further purified using chromatography.
Bamboo extracts can be used in any form, such as dissolved or dispersed in water or an organic solvent, or in powder form.
成形物における抗菌剤の添加量は０．０１〜１５重量％が好ましい。０．０１重量％未満では十分な抗菌性が得られない場合がある。また、抗菌剤が水等の溶媒に分散している場合は１５重量％を超えて添加すると、その水等による発泡や着色によって成形物に不具合が生じる可能性がある。特には０．１〜１重量％が好ましい。 The addition amount of the antibacterial agent in the molded product is preferably 0.01 to 15% by weight. If it is less than 0.01% by weight, sufficient antibacterial properties may not be obtained. In addition, when the antibacterial agent is dispersed in a solvent such as water, if it is added in an amount exceeding 15% by weight, there is a possibility that a defect may occur in the molded product due to foaming or coloring with the water or the like. In particular, 0.1 to 1% by weight is preferable.
また、上記抗菌剤の抗菌相乗剤として、グリセリンと脂肪酸のモノエステルであるモノグリセリドを用いることができる。脂肪酸はＣ２〜Ｃ２０のものが好ましく、Ｃ８〜Ｃ１２が特に好ましい。
また、酢酸、プロピオン酸、クエン酸等の有機酸、グリシン等のアミノ酸、ソルビトール等の糖類、プロタミン等のタンパク質、ヒノキチオール、香辛料抽出物等の天然抗菌剤を用いることができる。
As the antibacterial synergist of the antibacterial agent, monoglyceride which is a monoester of glycerin and fatty acid can be used. The fatty acid is preferably C 2 to C 20 , and particularly preferably C 8 to C 12 .
Further, organic antibacterial agents such as organic acids such as acetic acid, propionic acid and citric acid, amino acids such as glycine, saccharides such as sorbitol, proteins such as protamine, hinokitiol, and spice extract can be used.
本発明において、フライポンタイト（fraiponite）型鉱物はブリード促進剤として使用される。フライポンタイト型鉱物とは、二層構造のフィロケイ酸亜鉛又は含アルミニウムフィロケイ酸亜鉛を主体とし、ＳｉＯ４の四面体層とＺｎＯ６の八面体層とが層状に結合した二層構造を基本骨格とするものであり、ＳｉＯ４の四面体のＳｉの一部がＡｌで置換され、このバレンスに対応して、ＺｎＯ６の八面体のＺｎの一部がＡｌで置換された構造となっている。
フライポンタイト型鉱物には天然物または合成物があるが、どちらも使用できる。粒径が揃い分散性が良好、不純物が少なく、含まれる酸化物の組成比が調節できる点で、合成フライポンタイト型鉱物の方がより好ましく用いられる。
In the present invention, fraiponite type minerals are used as bleed promoters. The fly-pontite-type mineral is mainly composed of a two-layered zinc phyllosilicate or aluminum-containing zinc phyllosilicate, and is basically a two-layer structure in which a tetrahedral layer of SiO 4 and an octahedral layer of ZnO 6 are combined in layers. A part of Si of the tetrahedron of SiO 4 is substituted with Al, and a part of Zn of the octahedron of ZnO 6 is substituted with Al corresponding to this valence. Yes.
There are natural products or synthetic products in the fly-pontite type mineral, but both can be used. Synthetic fly-pontite-type minerals are more preferably used in terms of uniform particle size, good dispersibility, few impurities, and the ability to adjust the composition ratio of the contained oxide.
フライポンタイト型鉱物の基本的な構造は下記式（１）に示される。
（Ｚｎ３−ＸＡｌＸ）（Ｓｉ２−ＸＡｌＸ）Ｏ５（ＯＨ）４ （１）
（式中、Ｘは０．１〜１．７５を表す。０．３〜１．０が好ましい。）
The basic structure of the fly-pontite type mineral is shown in the following formula (1).
(Zn 3-X Al X) (Si 2-X Al X) O 5 (OH) 4 (1)
(In the formula, X represents 0.1 to 1.75, preferably 0.3 to 1.0.)
また、フライポンタイト型鉱物に含まれる酸化物の３成分組成比は、ＳｉＯ２２５〜６５モル％、ＭＯ（Ｍ＝ＺｎまたはＭｇ）１５〜６０モル％、Ａｌ２Ｏ３２〜５０モル％の範囲であるものがより好ましい。 In addition, the three-component composition ratio of the oxide contained in the fly-pontite type mineral is as follows: SiO 2 25 to 65 mol%, MO (M = Zn or Mg) 15 to 60 mol%, Al 2 O 3 2 to 50 mol%. More preferred are those in the range.
成形物におけるフライポンタイト型鉱物の添加量は０．０５〜１０重量％が好ましい。０．０５％重量％未満では十分な抗菌性が得られない場合がある。また、フライポンタイトは吸着水を有しているため、１０重量％を超えて添加するとその水分により成形時発泡等の問題が生じる。特には０．０５〜１重量％が好ましい。 The addition amount of the fly-pontite type mineral in the molded product is preferably 0.05 to 10% by weight. If it is less than 0.05% by weight, sufficient antibacterial properties may not be obtained. In addition, since flypontite has adsorbed water, adding more than 10% by weight causes problems such as foaming during molding due to the moisture. In particular, 0.05 to 1% by weight is preferable.
本発明の熱可塑性樹脂組成物には、顔料又は染料を配合できる。例えばアゾ系、アンスラキノン系、ペリレン系、ペリノン系、キナクリドン系、フタロシアニン系、イソインドリノン系、ジオキサジン系、インダスレン系、キノフタロン系等の有機顔料、酸化亜鉛、酸化チタン、群青、コバルトブルー、カーボンブラック、チタンイエロー等の有色無機顔料、硫酸バリウム、カオリン、タルク等の体質顔料、アンスラキノン系、ペリレン系、ペリノン系、モノアゾ系、メチン系、複素環系、ラクトン系、フタロシアニン系等の油溶性染料、分散染料が使用できる。 A pigment or a dye can be blended in the thermoplastic resin composition of the present invention. For example, organic pigments such as azo, anthraquinone, perylene, perinone, quinacridone, phthalocyanine, isoindolinone, dioxazine, indanthrene, quinophthalone, zinc oxide, titanium oxide, ultramarine, cobalt blue, Colored inorganic pigments such as carbon black and titanium yellow, extender pigments such as barium sulfate, kaolin and talc, oils such as anthraquinone, perylene, perinone, monoazo, methine, heterocyclic, lactone and phthalocyanine Soluble dyes and disperse dyes can be used.
本発明の熱可塑性樹脂組成物には、熱可塑性樹脂や成形物に使用される公知の酸化防止剤、紫外線吸収剤、光安定剤、金属不活性剤等、滑剤の添加剤が配合できる。
酸化防止剤としてはフェノール系、ホスファイト系等が使用できる。フェノール系としては、例えばジエチル[[3,5−ビス（1,1−ジメチルエチル）−４−ヒドロキシフェニル]メチル]ホスフォネート、オクタデシル−３−（3,5−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート等を挙げることができる。ホスファイト系としては、例えばトリス（2,4−ジ−tert−ブチルフェニル）ホスファイト、ビス（2,6−ジ−tert−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト等を挙げることができる。
The thermoplastic resin composition of the present invention can be blended with additives for lubricants such as known antioxidants, ultraviolet absorbers, light stabilizers, metal deactivators and the like used in thermoplastic resins and molded articles.
As the antioxidant, phenol-based, phosphite-based and the like can be used. Examples of phenolic compounds include diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate and the like. Examples of the phosphite system include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, and the like. be able to.
紫外線防止剤としてはベンゾトリアゾール系、トリアジン系等が使用できる。ベンゾトリアゾール系としては、例えば2,2−メチレンビス[４−（1,1,3,3−テトラメチルブチル）−６[（2H−ベンゾトリアゾール−２−イル）フェノール]]、２−（２H−ベンゾトリアゾール−２−イル）−４−（1,1,3,3−テトラメチルブチル）フェノール、２−[５−クロロ（２H）−ベンゾトリアゾール−２−イル]−４−メチル−６−（tert−ブチル）フェノール等を挙げることができる。トリアジン系としては、例えば２−（4,6−ジフェニル−1,3,5−トリアジン−２−イル）−５−[（ヘキシル）オキシ]−フェノール等を挙げることができる。 Benzotriazole-based, triazine-based and the like can be used as the ultraviolet ray preventing agent. Examples of the benzotriazole series include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H- Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- ( tert-butyl) phenol and the like. Examples of the triazine series include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.
光安定剤としてはヒンダードアミン系等が使用できる。ヒンダードアミン系としては、例えばビス（２,２,６,６−テトラメチル−４−ピペリジル）セバケート、ポリ[{６−（1,1,3,3−テトラメチルブチル）アミノ−1,3,5−トリアジン−2,4−ジイル}{（2,2,6,6−テトラメチル−４−ピペリジル）イミノ}ヘキサメチレン{（2,2,6,6−テトラメチル−４−ピペリジル）イミノ}]、ジブチルアミン・1,3,5−トリアジン・N,N−ビス（2,2,6,6−テトラメチル−４−ピペリジル−1,6−ヘキサメチレンジアミン・N−（2,2,6,6−テトラメチル−４−ピペリジル）ブチルアミンの重縮合物等を挙げることができる。 As the light stabilizer, a hindered amine or the like can be used. Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5. -Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] Dibutylamine, 1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, N- (2,2,6, 6-tetramethyl-4-piperidyl) butylamine polycondensate and the like.
金属不活性剤としては、例えば2,3-ビス[[３−[3,5−ジ−tert−ブチル−４−ヒドロキシフェニル]プロピオニル]]プロピオノヒドラジド等を挙げることができる。 Examples of the metal deactivator include 2,3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.
滑剤としては、金属石鹸すなわち高級脂肪酸の金属塩、またはオキシカルボン酸金属塩を用いることができる。ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸バリウム、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸リチウム、ラウリル酸カルシウム、ラウリル酸亜鉛、ラウリル酸マグネシウム、オキシカルボン酸金属塩としてα−ヒドロキシミリスチン酸、α−ヒドロキシパルミチン酸、α−ヒドロキシステアリン酸、α−ヒドロキシエイコサン酸、α−ヒドロキシドコサン酸、α−ヒドロキシテトラエイコサン酸、α−ヒドロキシヘキサエイコサン酸、α−ヒドロキシオクタエイコサン酸、α−ヒドロキシトリアコンタン酸、β−ヒドロキシミリスチン酸、１０−ヒドロキシデカン酸、１５−ヒドロキシペンタデカン酸、１６−ヒドロキシヘキサデカン酸、１２−ヒドロキシステアリン酸、リシノール酸等の金属塩が挙げられる。 As the lubricant, a metal soap, that is, a metal salt of a higher fatty acid or a metal salt of oxycarboxylic acid can be used. Calcium stearate, magnesium stearate, barium stearate, zinc stearate, aluminum stearate, lithium stearate, calcium laurate, zinc laurate, magnesium laurate, α-hydroxymyristic acid, α-hydroxy as metal salt of oxycarboxylic acid Palmitic acid, α-hydroxystearic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaicosanoic acid, α-hydroxy Metal salts such as triacontanoic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid, ricinoleic acid It is below.
また、本発明の熱可塑性樹脂組成物には、公知の無機系および／または有機系の抗菌剤、防黴剤を併用することによって抗菌性をより広範なものとすることもできる。これらの添加剤は、本発明の熱可塑性樹脂組成物を作製する際に粉末のまま添加しても良い。また、あらかじめ添加剤のコンパウンドやマスターバッチを製造し、それを本発明の熱可塑性樹脂組成物に添加しても良い。 Further, the thermoplastic resin composition of the present invention can have a broader antibacterial property by using a known inorganic and / or organic antibacterial agent and antifungal agent together. These additives may be added in powder form when the thermoplastic resin composition of the present invention is produced. Alternatively, an additive compound or masterbatch may be produced in advance and added to the thermoplastic resin composition of the present invention.
本発明の熱可塑性樹脂組成物は、抗菌剤と、フライポンタイト型鉱物と、必要に応じて上記添加剤とを熱可塑性樹脂に加え、エクストルーダー、２軸ニーダー、ロールミル等の混練機を用いて均一に混合し溶融混練して得られる。ペレット状やマーブル状等の所望の形状に成形してもよい。
本発明の熱可塑性樹脂組成物は、抗菌剤とフライポンタイト型鉱物が高濃度であるマスターバッチでも良い。マスターバッチの場合、成形物製造の際に希釈樹脂を添加しマスターバッチ濃度を希釈して成形物を製造する。
The thermoplastic resin composition of the present invention uses an antibacterial agent, a fly-pontite-type mineral, and, if necessary, the above additives to the thermoplastic resin and uses a kneader such as an extruder, a twin-screw kneader, or a roll mill. And uniformly mixed and melt-kneaded. You may shape | mold into desired shapes, such as a pellet form and a marble form.
The thermoplastic resin composition of the present invention may be a masterbatch having a high concentration of antibacterial agent and frypontite mineral. In the case of a master batch, a diluted resin is added during the production of a molded product to dilute the master batch concentration to produce a molded product.
また、本発明の樹脂組成物は、抗菌剤とフライポンタイト型鉱物の濃度が成形物と同じ組成であるコンパウンドでも良い。コンパウンドの場合、そのままの組成で成形物を製造できる。 Further, the resin composition of the present invention may be a compound in which the concentration of the antibacterial agent and the fly-pontite type mineral is the same as that of the molded product. In the case of a compound, a molded product can be produced with the composition as it is.
本発明の成形物としては容器、キャップ、部品等の３次元成形物、フィルム、シート、テープ等の２次元成形物等が挙げられる。これらの成形物は多層構造を有しても良い。 Examples of the molded product of the present invention include three-dimensional molded products such as containers, caps and parts, and two-dimensional molded products such as films, sheets and tapes. These molded products may have a multilayer structure.
３次元成形物は、その成形物に応じて射出成形、押出成形、中空成形、回転成形、粉末成形、真空成形等公知の方法で成形できる。その具体例としては食品、洗剤、医薬品、化粧品、飲料製品等の透明容器及びそのキャップ類が挙げられる。 The three-dimensional molded product can be molded by a known method such as injection molding, extrusion molding, hollow molding, rotational molding, powder molding, or vacuum molding according to the molded product. Specific examples thereof include transparent containers such as foods, detergents, pharmaceuticals, cosmetics and beverage products, and caps thereof.
２次元成形物は、熱可塑性樹脂のフィルム化に用いられるインフレーション加工、多層インフレーション加工、Ｔダイフィルム加工、フラットフィルム法による縦横同時二軸延伸法、または縦横逐次二軸延伸法、チューブラフィルム法等公知の方法で成形される。このようにして得られた２次元成形物は食品包装、繊維包装、雑貨包装、薬品類の包装、テープ、絶縁材料、農業用フィルム、各種シート等通常の熱可塑性樹脂フィルムが用いられる分野と同様の分野で用いられる。 Two-dimensional molded products include inflation processing, multilayer inflation processing, T-die film processing, vertical and horizontal simultaneous biaxial stretching methods using a flat film method, or vertical and horizontal sequential biaxial stretching methods, tubular film methods, etc. It is molded by a known method. The two-dimensional molded product thus obtained is the same as the field in which ordinary thermoplastic resin films are used, such as food packaging, fiber packaging, miscellaneous goods packaging, medicine packaging, tapes, insulating materials, agricultural films, and various sheets. Used in the field of
また、フィルムは各種基材即ちクラフト紙や上質紙などの紙類、プラスチックフィルム類、アルミニウム等の金属箔等と密着させてラミネートとすることが出来る。得られたラミネートは牛乳、酒類等の食品容器、医薬品の包装材料、食品の包装材料、各種シート等の用途がある。 Further, the film can be laminated by adhering to various base materials, that is, papers such as kraft paper and fine paper, plastic films, metal foil such as aluminum, and the like. The obtained laminate has uses for food containers such as milk and alcoholic beverages, pharmaceutical packaging materials, food packaging materials, and various sheets.
以下、本発明について具体的に実施例をもって説明する。以下の記載において、部は重量部を、％は重量％をそれぞれ表す。 Hereinafter, the present invention will be specifically described with reference to examples. In the following description, parts represent parts by weight, and% represents% by weight.
（１）抗菌フィラーの作成
表１に示すように、成分（ア）、成分（イ）をニーダーで均一に混合し、抗菌フィラーを作成した。成分（ア）のみの場合はニーダーを使用せずそのまま用いた。
（２）マスターバッチの製造
[実施例１〜６]
表１に示すように、成分（ア）、成分（イ）から成る抗菌フィラーと、成分（ウ）と、酸化防止剤とを均一混合し、直径３０ｍｍ二軸押出機においてスクリュー回転数２５０ｒｐｍ、吐出量１０Ｋｇ／ｈの条件下で溶融混練し、マスターバッチを製造した。溶融混練の際の温度は、成分（ウ）がＬＤＰＥの場合は設定温度１６０℃、ＰＰの場合は設定温度２４０℃で行った。
(1) Preparation of antibacterial filler As shown in Table 1, the component (a) and the component (b) were uniformly mixed with a kneader to prepare an antibacterial filler. In the case of only component (a), it was used as it was without using a kneader.
(2) Master batch production
[Examples 1 to 6]
As shown in Table 1, the antibacterial filler composed of component (a) and component (a), component (c) and antioxidant are uniformly mixed, and the screw rotation speed is 250 rpm and discharged in a 30 mm diameter twin screw extruder. A master batch was produced by melt-kneading under the condition of an amount of 10 kg / h. The temperature at the time of melt kneading was set at a set temperature of 160 ° C. when the component (c) was LDPE, and at a set temperature of 240 ° C. when PP was used.
[比較例１〜１４]
表１に示すように、成分（ア）、成分（イ）から成る抗菌フィラーと、成分（ウ）と、酸化防止剤とを均一混合し、実施例１と同様にしてマスターバッチを得た。
[Comparative Examples 1-14]
As shown in Table 1, the antibacterial filler composed of the component (a) and the component (a), the component (c) and the antioxidant were mixed uniformly, and a master batch was obtained in the same manner as in Example 1.
表１中、孟宗竹抽出液の有効成分濃度は２０重量％である。
また、フライポンタイトは、下記式（１）に示される合成フライポンタイトであり、
（Ｚｎ３−ＸＡｌＸ）（Ｓｉ２−ＸＡｌＸ）Ｏ５（ＯＨ）４ （１）
（式中、Ｘは０．１〜１．７５を表す。）
３成分組成比はＳｉＯ２６４．４モル％、ＺｎＯ３１．１モル％、Ａｌ２Ｏ３４．５モル％である。
In Table 1, the active ingredient concentration of the Miso bamboo extract is 20% by weight.
Moreover, fly-pontite is a synthetic fly-pontite shown by following formula (1),
(Zn 3-X Al X) (Si 2-X Al X) O 5 (OH) 4 (1)
(In the formula, X represents 0.1 to 1.75.)
The three-component composition ratio is SiO 2 64.4 mol%, ZnO 31.1 mol%, and Al 2 O 3 4.5 mol%.
［評価試験］
得られたマスターバッチについて以下の評価を行い、結果を表２に示した。
マスターバッチを、それぞれ希釈樹脂（ＭＢで用いた樹脂と同じ樹脂を用いた。）で１０倍希釈して混合し、ラボプラストミル（東洋精機社製）にてＴダイを用いてフィルム成形物を得た。
[Evaluation test]
The following evaluation was performed on the obtained master batch, and the results are shown in Table 2.
Each master batch was diluted 10 times with a diluted resin (the same resin as that used in MB) and mixed, and a film molded product was obtained using a T die in a lab plast mill (manufactured by Toyo Seiki Co., Ltd.). Obtained.
ａ．抗菌性評価
各フィルムについて、黄色ブドウ球菌、大腸菌の抗菌性試験（フィルム密着法ＪＩＳ Ｚ２８０１）を行い、菌接種直後から２４時間後の菌数の減少率によって、以下の基準に従い評価した。
○：９９％以上減少（菌は１％以下）
×：９９％未満
a. Antibacterial Evaluation Each film was subjected to an antibacterial test of Staphylococcus aureus and Escherichia coli (film adhesion method JIS Z2801), and evaluated according to the following criteria by the rate of decrease in the number of bacteria 24 hours after the inoculation.
○: Decrease by 99% or more (fungus is 1% or less)
×: Less than 99%
ｂ．色相評価
フィルムを色差計（ＣＯＬＯＲ７ｘ クラボウ社製）で測色し、希釈樹脂のみのフィルム（抗菌剤無添加）との色差を、以下の基準に従い評価した。
○：△Ｅ ５未満
△：△Ｅ ５以上７未満
×：△Ｅ ７以上
b. Hue evaluation The color of the film was measured with a color difference meter (COLOR7x Kurabo Industries Co., Ltd.), and the color difference with a film containing only a diluted resin (no antibacterial agent added) was evaluated according to the following criteria.
○: Less than ΔE 5 Δ: ΔE 5 or more and less than 7 ×: ΔE 7 or more
Claims (4)
（Ｚｎ 3-X Ａｌ X ）（Ｓｉ 2-X Ａｌ X ）Ｏ 5 （ＯＨ） 4 （１）
（式中、Ｘは０．１〜１．７５を表す。） A thermoplastic resin composition comprising a Sosou bamboo extract as an antibacterial agent and a frypontite-type mineral represented by the following formula (1) .
(Zn 3-X Al X) (Si 2-X Al X) O 5 (OH) 4 (1)
(In the formula, X represents 0.1 to 1.75.)
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| JP2004323706A (en) * | 2003-04-25 | 2004-11-18 | Toyo Ink Mfg Co Ltd | Resin composition and molded product obtained by using the same resin composition |
| JP2004359628A (en) * | 2003-06-06 | 2004-12-24 | Toyo Ink Mfg Co Ltd | Method for producing extract of bamboo and bamboo grasses |
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