JPWO2014102980A1 - Deodorant antibacterial composition and deodorant antibacterial fabric - Google Patents

Deodorant antibacterial composition and deodorant antibacterial fabric Download PDF

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JPWO2014102980A1
JPWO2014102980A1 JP2014553974A JP2014553974A JPWO2014102980A1 JP WO2014102980 A1 JPWO2014102980 A1 JP WO2014102980A1 JP 2014553974 A JP2014553974 A JP 2014553974A JP 2014553974 A JP2014553974 A JP 2014553974A JP WO2014102980 A1 JPWO2014102980 A1 JP WO2014102980A1
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deodorant
antibacterial
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修一 源中
修一 源中
佳成 宮村
佳成 宮村
行徳 下村
行徳 下村
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Suminoe Textile Co Ltd
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    • A—HUMAN NECESSITIES
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    • D06M13/005—Compositions containing perfumes; Compositions containing deodorants
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Abstract

繰り返し洗濯後であっても優れた消臭性能を発揮できると共に、抗菌性能にも優れ、かつ貯蔵安定性が良好な消臭抗菌組成物を提供する。本発明に係る消臭抗菌組成物は、アミン化合物と、無機系消臭剤と、金属リン酸塩からなる第１塩と、無機系抗菌剤と、スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の第２塩と、バインダー樹脂と、を含有することを特徴とする。Provided is a deodorizing and antibacterial composition that can exhibit excellent deodorizing performance even after repeated washing, has excellent antibacterial performance, and has good storage stability. The deodorant antibacterial composition according to the present invention is from the group consisting of an amine compound, an inorganic deodorant, a first salt composed of a metal phosphate, an inorganic antibacterial agent, a sulfonate and a carboxylate. It contains at least one selected second salt and a binder resin.

Description

本発明は、布帛等に付与することにより、繰り返し洗濯後であっても優れた消臭性能を確保できると共に、抗菌性能にも優れ、かつ貯蔵安定性が良好な消臭抗菌組成物、及び繰り返し洗濯後でも消臭性能に優れると共に抗菌性能にも優れた消臭抗菌布帛に関する。   The present invention provides a deodorizing antibacterial composition having excellent deodorizing performance even after repeated washing, excellent antibacterial performance, and good storage stability by being applied to a fabric or the like, and repeated The present invention relates to a deodorizing and antibacterial fabric that is excellent in deodorizing performance even after washing and also has excellent antibacterial performance.

現代人にとって生活臭の問題は大きな関心事となってきている。住宅のみならず、自動車、電車、旅客機の室内の様々な臭いに対して消臭を行うことが強く要求されるようになってきている。   The problem of life odor has become a major concern for modern people. There is a strong demand to deodorize various odors not only in houses but also in automobiles, trains, and passenger aircraft.

本出願人は、このような要求に応えるべく、アミン化合物と、無機多孔質物質と、金属酸化物と、水酸化金属と、アニオン系界面活性剤と、ノニオン系界面活性剤とを含む消臭組成物を準備し、該消臭組成物を布帛の少なくとも一部に付着させることを提案している（特許文献１参照）。アミン化合物と、無機多孔質物質と、金属酸化物と、水酸化金属とを含む消臭組成物が布帛に付着しているので、様々な臭気に対して優れた消臭性能が得られる。   In order to meet such a demand, the present applicant has deodorized containing an amine compound, an inorganic porous material, a metal oxide, a metal hydroxide, an anionic surfactant, and a nonionic surfactant. It has been proposed to prepare a composition and attach the deodorant composition to at least a part of the fabric (see Patent Document 1). Since the deodorizing composition containing an amine compound, an inorganic porous material, a metal oxide, and a metal hydroxide is attached to the fabric, excellent deodorizing performance against various odors can be obtained.

特開２００９−２８５１６４号公報JP 2009-285164 A

しかしながら、上記従来技術では、繰り返し洗濯後の消臭性能は、洗濯前の初期と比較して低下することから、改善が望まれていた。   However, in the above prior art, since the deodorizing performance after repeated washing is reduced compared to the initial stage before washing, improvement has been desired.

また、消臭剤成分として金属リン酸塩を含有せしめた場合、消臭組成物液の粘度が顕著に増大してしまい、これにより長期保管後にゲル化したり、凝集したりする等、貯蔵安定性が悪いという問題を抱えていた。   In addition, when a metal phosphate is included as a deodorant component, the viscosity of the deodorant composition liquid increases remarkably, which causes storage stability such as gelation or aggregation after long-term storage. Had the problem of being bad.

一方、近年、布帛等には、消臭性能を備えていることに加えて、抗菌性能も有していることが求められることが多くなりつつある。例えば、靴用内装材、靴のインソール等では、特に菌が繁殖しやすい環境にあるので、抗菌性能も備えていることは、非常に有用である。   On the other hand, in recent years, fabrics and the like are increasingly required to have antibacterial performance in addition to having deodorization performance. For example, in an interior material for shoes, an insole of shoes, and the like, it is particularly useful to have antibacterial performance because it is in an environment where bacteria can easily propagate.

本発明は、かかる技術的背景に鑑みてなされたものであって、繰り返し洗濯後であっても優れた消臭性能を発揮できると共に、抗菌性能にも優れ、かつ貯蔵安定性が良好な消臭抗菌組成物、及び、繰り返し洗濯後であっても優れた消臭性能を備えると共に抗菌性能にも優れた消臭抗菌布帛を提供することを目的とする。   The present invention has been made in view of such technical background, and can exhibit excellent deodorizing performance even after repeated washing, has excellent antibacterial performance, and has excellent storage stability. It is an object of the present invention to provide an antibacterial composition and a deodorized antibacterial fabric that has excellent deodorizing performance even after repeated washing and also has excellent antibacterial performance.

前記目的を達成するために、本発明は以下の手段を提供する。   In order to achieve the above object, the present invention provides the following means.

［１］アミン化合物と、
無機系消臭剤と、
金属リン酸塩からなる第１塩と、
無機系抗菌剤と、
スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の第２塩と、
バインダー樹脂と、を含有することを特徴とする消臭抗菌組成物。[1] an amine compound;
An inorganic deodorant,
A first salt comprising a metal phosphate;
An inorganic antibacterial agent,
At least one second salt selected from the group consisting of sulfonates and carboxylates;
A deodorizing antibacterial composition comprising a binder resin.

［２］前記第２塩として、アルファオレフィンスルホン酸塩及びポリカルボン酸塩からなる群より選択される少なくとも１種の塩が用いられている前項１に記載の消臭抗菌組成物。   [2] The deodorant antibacterial composition according to item 1, wherein at least one salt selected from the group consisting of an alpha olefin sulfonate and a polycarboxylate is used as the second salt.

［３］前記無機系消臭剤は、無機多孔質物質、水酸化金属および金属酸化物である前項１または２に記載の消臭抗菌組成物。   [3] The deodorizing antibacterial composition according to item 1 or 2, wherein the inorganic deodorant is an inorganic porous material, a metal hydroxide, and a metal oxide.

［４］さらにノニオン系界面活性剤を含有する前項１〜３のいずれか１項に記載の消臭抗菌組成物。   [4] The deodorizing antibacterial composition according to any one of items 1 to 3, further comprising a nonionic surfactant.

［５］前記バインダー樹脂１００質量部に対し、前記第２塩を０．４質量部〜４０質量部含有し、前記金属リン酸塩からなる第１塩を８質量部〜８０質量部含有する前項１〜４のいずれか１項に記載の消臭抗菌組成物。   [5] The previous item containing 0.4 to 40 parts by mass of the second salt and 8 to 80 parts by mass of the first salt composed of the metal phosphate with respect to 100 parts by mass of the binder resin. The deodorizing antibacterial composition of any one of 1-4.

［６］前記組成物中の固形分濃度が１５質量％〜３５質量％である前項１〜５のいずれか１項に記載の消臭抗菌組成物。   [6] The deodorizing antibacterial composition according to any one of items 1 to 5, wherein the solid content concentration in the composition is 15% by mass to 35% by mass.

［７］布帛の少なくとも一部に、前項１〜６のいずれか１項に記載の消臭抗菌組成物が固着されていることを特徴とする消臭抗菌布帛。   [7] A deodorant antibacterial fabric, wherein the deodorant antibacterial composition according to any one of items 1 to 6 is fixed to at least a part of the fabric.

［８］肌着用生地、服地、壁紙、椅子張り地、車両用内装材、カーテン、カーペット、靴用内装材又は靴のインソールとして用いられる前項７に記載の消臭抗菌布帛。   [8] The deodorant antibacterial fabric according to item 7, which is used as an underwear fabric, clothes, wallpaper, chair upholstery, vehicle interior material, curtain, carpet, shoe interior material or shoe insole.

［１］の発明では、アミン化合物と、無機系消臭剤とを含む組成物であるので、優れた消臭性能が得られる。また、消臭抗菌組成物は、金属リン酸塩（第１塩）を含有するので、繰り返し洗濯後の消臭性能を格段に向上させることができる。更に、組成物は無機系抗菌剤を含有するので、十分な抗菌性能が得られる。更に、金属リン酸塩（第１塩）を含有するものの、スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の第２塩を含有するので、組成物の液安定性を格段に高めることができ、組成物を長期間貯蔵後に布帛等に加工を行っても、消臭性能及び抗菌性能に優れた消臭抗菌布帛等を安定して製造できる。また、組成物は、バインダー樹脂を含有するので、本消臭抗菌組成物を布帛等に固着せしめたときに前記各成分が布帛等から離脱することが防止される。   In the invention of [1], since it is a composition containing an amine compound and an inorganic deodorant, excellent deodorizing performance can be obtained. Moreover, since the deodorizing antibacterial composition contains a metal phosphate (first salt), the deodorizing performance after repeated washing can be remarkably improved. Furthermore, since the composition contains an inorganic antibacterial agent, sufficient antibacterial performance can be obtained. Furthermore, although it contains a metal phosphate (first salt), it contains at least one second salt selected from the group consisting of sulfonates and carboxylates, so that the liquid stability of the composition is markedly improved. Even when the composition is processed into a fabric after long-term storage, a deodorized and antibacterial fabric excellent in deodorizing performance and antibacterial performance can be stably produced. Moreover, since the composition contains a binder resin, the components are prevented from being detached from the fabric or the like when the deodorant antibacterial composition is fixed to the fabric or the like.

［２］の発明では、前記第２塩として、アルファオレフィンスルホン酸塩及びポリカルボン酸塩からなる群より選択される少なくとも１種の塩が用いられているから、組成物の液安定性をさらに高めることができる。   In the invention of [2], at least one salt selected from the group consisting of an alpha olefin sulfonate and a polycarboxylate is used as the second salt, so that the liquid stability of the composition is further improved. Can be increased.

［３］の発明では、無機系消臭剤として、無機多孔質物質、水酸化金属および金属酸化物が用いられているから、様々な臭気に対してより優れた消臭性能が得られる。   In the invention [3], an inorganic porous substance, a metal hydroxide and a metal oxide are used as the inorganic deodorant, so that more excellent deodorization performance against various odors can be obtained.

［４］の発明では、さらにノニオン系界面活性剤を含有するので、組成物の液安定性をより向上させることができる。   In the invention of [4], since a nonionic surfactant is further contained, the liquid stability of the composition can be further improved.

［５］の発明では、バインダー樹脂１００質量部に対し、第２塩を０．４質量部〜４０質量部含有し、金属リン酸塩からなる第１塩を８質量部〜８０質量部含有するから、繰り返し洗濯後の消臭性能をさらに向上させることができると共に、消臭抗菌組成物の液安定性をさらに高めることができる。   In invention of [5], 0.4 mass part-40 mass parts of 2nd salts are contained with respect to 100 mass parts of binder resin, and 8 mass parts-80 mass parts of 1st salts which consist of metal phosphates are contained. Therefore, the deodorizing performance after repeated washing can be further improved, and the liquid stability of the deodorizing antibacterial composition can be further improved.

［６］の発明では、組成物中の固形分濃度が１５質量％〜３５質量％であるから、消臭抗菌組成物の長期間貯蔵安定性をより向上させることができると共に、布帛等に加工する時の消臭抗菌組成物の希釈液中における含有成分（消臭成分、抗菌成分等）の沈降を十分に抑制できる。   In the invention of [6], since the solid content concentration in the composition is 15% by mass to 35% by mass, the long-term storage stability of the deodorant antibacterial composition can be further improved and processed into a fabric or the like. The sedimentation of the components (deodorant component, antibacterial component, etc.) in the diluted solution of the deodorant antibacterial composition can be sufficiently suppressed.

［７］の発明では、繰り返し洗濯後であっても優れた消臭性能を備えると共に、優れた抗菌性能を有した消臭抗菌布帛が提供される。   In the invention of [7], a deodorizing and antibacterial fabric having excellent deodorizing performance even after repeated washing and having excellent antibacterial performance is provided.

［８］の発明では、繰り返し洗濯後であっても優れた消臭性能を備えると共に、優れた抗菌性能を有した、肌着用生地、服地、壁紙、椅子張り地、車両用内装材、カーテン、カーペット、靴用内装材、靴のインソールが提供される。   [8] In the invention of [8], underwear, fabric, wallpaper, chair upholstery, vehicle interior material, curtain, having excellent deodorizing performance even after repeated washing and having excellent antibacterial performance, Carpets, shoe interior materials and shoe insoles are provided.

本発明の消臭抗菌布帛の一実施形態を示す斜視図である。It is a perspective view which shows one Embodiment of the deodorizing antibacterial fabric of this invention. 本発明の消臭抗菌布帛の他の実施形態を示す斜視図である。It is a perspective view which shows other embodiment of the deodorizing antibacterial fabric of this invention.

本発明に係る消臭抗菌組成物は、アミン化合物と、無機系消臭剤と、金属リン酸塩（第１塩）と、無機系抗菌剤と、スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の第２塩と、バインダー樹脂と、を含有する。   The deodorizing antibacterial composition according to the present invention is from the group consisting of an amine compound, an inorganic deodorant, a metal phosphate (first salt), an inorganic antibacterial agent, a sulfonate, and a carboxylate. It contains at least one selected second salt and a binder resin.

前記アミン化合物としては、ヒドラジン誘導体、或いは、ポリアミン化合物を担持した無機ケイ素化合物等が挙げられる。   Examples of the amine compound include a hydrazine derivative or an inorganic silicon compound carrying a polyamine compound.

前記ヒドラジン誘導体としては、例えば、ヒドラジン系化合物と長鎖の脂肪族系化合物とを反応させたもの、あるいはヒドラジン系化合物と芳香族系化合物とを反応させたもの等が挙げられる。中でも、ヒドラジン及びセミカルバジドからなる群より選ばれる１種または２種の化合物と、炭素数８〜１６のモノカルボン酸、ジカルボン酸、芳香族モノカルボン酸、および芳香族ジカルボン酸からなる群より選ばれる１種または２種以上の化合物との反応生成物や、ヒドラジン及びセミカルバジドからなる群より選ばれる１種または２種の化合物と炭素数８〜１６のモノグリシジル誘導体及びジグリシジル誘導体からなる群より選ばれる１種または２種以上の化合物との反応生成物が好適である。   Examples of the hydrazine derivative include those obtained by reacting a hydrazine compound and a long-chain aliphatic compound, or those obtained by reacting a hydrazine compound and an aromatic compound. Among them, one or two compounds selected from the group consisting of hydrazine and semicarbazide, and a group consisting of monocarboxylic acid having 8 to 16 carbon atoms, dicarboxylic acid, aromatic monocarboxylic acid, and aromatic dicarboxylic acid are selected. A reaction product with one or more compounds, or one or two compounds selected from the group consisting of hydrazine and semicarbazide, and a group consisting of monoglycidyl derivatives and diglycidyl derivatives having 8 to 16 carbon atoms. Reaction products with one or more compounds are preferred.

このようなヒドラジン誘導体を用いることによりアルデヒド類に対して化学反応を起こし優れた吸着作用を発揮し悪臭除去性能を確保することができる。前記反応生成物としては、具体的には、セバシン酸ジヒドラジド、ドデカンニ酸ジヒドラジド、イソフタル酸ジヒドラジド等を挙げられる。なお、このようなヒドラジン誘導体の水に対する溶解度は２５℃において５ｇ／Ｌ以下であるのが望ましい。水に対する溶解度がこの範囲内であれば、洗濯等によって水と接触することがあっても、ヒドラジン誘導体がこの水に溶解して流出してしまうことが防止される。   By using such a hydrazine derivative, it is possible to cause a chemical reaction with aldehydes, exhibit an excellent adsorption action, and ensure a malodor removal performance. Specific examples of the reaction product include sebacic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and the like. The solubility of such a hydrazine derivative in water is desirably 5 g / L or less at 25 ° C. If the solubility in water is within this range, the hydrazine derivative is prevented from dissolving and flowing out even if it comes into contact with water by washing or the like.

また、ポリアミン化合物を担持した無機ケイ素化合物としては、特に限定されるものではないが、例えばポリアミン化合物を担持した多孔質二酸化ケイ素、ポリアミン化合物を担持したケイ酸アルミニウム等が挙げられる。   The inorganic silicon compound carrying the polyamine compound is not particularly limited, and examples thereof include porous silicon dioxide carrying the polyamine compound, aluminum silicate carrying the polyamine compound, and the like.

前記ポリアミン化合物としては、特に限定されるものではないが、例えば脂肪族ポリアミン、芳香族ポリアミン、脂環式ポリアミン等が挙げられる。具体的には、例えば、ジエチレントリアミン、テトラエチレンペンタミン等が挙げられる。前記ポリアミン化合物は、特にアルデヒドガスの消臭に有効で、また、無機ケイ素化合物は塩基性ガスの消臭に有効である。   Although it does not specifically limit as said polyamine compound, For example, an aliphatic polyamine, an aromatic polyamine, an alicyclic polyamine etc. are mentioned. Specific examples include diethylenetriamine and tetraethylenepentamine. The polyamine compound is particularly effective for deodorizing aldehyde gas, and the inorganic silicon compound is effective for deodorizing basic gas.

前記無機系消臭剤としては、特に限定されるものではないが、無機多孔質物質、水酸化金属および金属酸化物を併用するのが好ましい。無機多孔質物質、水酸化金属および金属酸化物を併用することにより、様々な臭気を効果的に消臭することができる。   The inorganic deodorant is not particularly limited, but it is preferable to use an inorganic porous material, a metal hydroxide and a metal oxide in combination. Various odors can be effectively deodorized by using an inorganic porous material, a metal hydroxide and a metal oxide in combination.

前記無機多孔質物質は、多孔質故に表面積が大きく、悪臭の吸着能力の優れたものとなる。前記無機多孔質物質としては、例えば、多孔質シリカ、活性炭、ゼオライト、シリカゲル、麦飯石等が挙げられる。中でも、酢酸やアンモニアガス等に対して優れた吸着能を有するゼオライトを用いるのが好ましい。また、ゼオライトは、白色であり繊維に担持させた場合に活性炭よりも布帛の色彩に影響が少ないので、好ましい。ゼオライトは、ケイ素とアルミニウムが酸素を介して三次元的に結合した骨格構造をしている。この骨格中には分子レベルの穴（細孔）が開き、水や有機分子など様々な分子を骨格中に取り込むことから、吸着剤として非常に有用なものである。   Since the inorganic porous material is porous, it has a large surface area and an excellent malodor adsorption ability. Examples of the inorganic porous material include porous silica, activated carbon, zeolite, silica gel, and barley stone. Among them, it is preferable to use a zeolite having an excellent adsorption ability for acetic acid, ammonia gas, and the like. Zeolite is preferred because it is white and has less influence on the color of the fabric than activated carbon when supported on fibers. Zeolite has a skeletal structure in which silicon and aluminum are three-dimensionally bonded through oxygen. In this skeleton, molecular-level holes (pores) are opened, and various molecules such as water and organic molecules are taken into the skeleton, so that it is very useful as an adsorbent.

前記ゼオライトには、種々のものが存在し、中でも人工ゼオライトのＭＦＩ型ゼオライトは、結晶構造に由来する２種類の細孔が三次元的につながっていることから、吸着性能が向上して、消臭性能をより向上させることができる。前記ゼオライトとしてＭＦＩ型ゼオライトを用いた場合には、アンモニア、トリメチルアミン等の塩基性ガスに優れた消臭性能を発揮し、アルデヒド類や１−ノネン等の微量な中性ガスの吸着（消臭）にも優れた効果を発揮する。   There are various types of zeolite. Among them, the artificial zeolite MFI-type zeolite has two types of pores derived from the crystal structure that are three-dimensionally connected to each other. Odor performance can be further improved. When MFI-type zeolite is used as the zeolite, it exhibits excellent deodorizing performance for basic gases such as ammonia and trimethylamine, and adsorbs trace amounts of neutral gases such as aldehydes and 1-nonene (deodorization). Also has an excellent effect.

前記水酸化金属としては、例えば、水酸化ジルコニウム、水酸化マグネシウム、水酸化アルミニウム、水酸化第一鉄、水酸化銅等が挙げられるが、特にこれら例示のものに限定されるものではない。前記水酸化金属は、酢酸等の酸性ガスの分解（消臭）に優れた効果を発揮する。   Examples of the metal hydroxide include zirconium hydroxide, magnesium hydroxide, aluminum hydroxide, ferrous hydroxide, copper hydroxide and the like, but are not particularly limited to these examples. The said metal hydroxide exhibits the effect excellent in decomposition | disassembly (deodorization) of acidic gas, such as an acetic acid.

前記金属酸化物としては、例えば、酸化銅、アルミナ、酸化チタン、酸化亜鉛、酸化鉄、酸化ジルコニウム等が挙げられるが、特にこれら例示のものに限定されるものではない。前記金属酸化物は、アンモニア、トリメチルアミン等の塩基性ガスの分解（消臭）に優れた効果を発揮する。   Examples of the metal oxide include, but are not limited to, copper oxide, alumina, titanium oxide, zinc oxide, iron oxide, zirconium oxide, and the like. The metal oxide exhibits an excellent effect in the decomposition (deodorization) of basic gases such as ammonia and trimethylamine.

前記金属リン酸塩（第１塩）としては、特に限定されるものではないが、トリポリリン酸アルミニウム、リン酸ジルコニウム、リン酸チタン、リン酸錫およびリン酸セリウムからなる群より選ばれる少なくとも１種の金属リン酸塩を用いるのが好ましい。前記金属リン酸塩を消臭抗菌組成物中に含有せしめていることにより、該消臭抗菌組成物を付与せしめた布帛等の繰り返し洗濯後の消臭性能を格段に向上させることができる（消臭性能についての洗濯耐久性を向上させることができる）。   The metal phosphate (first salt) is not particularly limited, but is at least one selected from the group consisting of aluminum tripolyphosphate, zirconium phosphate, titanium phosphate, tin phosphate and cerium phosphate. The metal phosphate is preferably used. By including the metal phosphate in the deodorant antibacterial composition, the deodorization performance after repeated washing of the fabric or the like to which the deodorant antibacterial composition is applied can be remarkably improved (extinguishment). It can improve washing durability for odor performance).

前記無機系抗菌剤としては、特に限定されるものではないが、例えば、銀担持ゼオライト等の銀担持無機多孔質物質、亜鉛担持ゼオライト等の亜鉛担持無機多孔質物質などが挙げられる。ここで、無機系抗菌剤用の担持体としての無機多孔質物質の（ゼオライト以外の）具体例としては、シリカゲル、アルミナゲル等が挙げられる。   The inorganic antibacterial agent is not particularly limited, and examples thereof include silver-carrying inorganic porous materials such as silver-carrying zeolite and zinc-carrying inorganic porous materials such as zinc-carrying zeolite. Here, specific examples of inorganic porous materials (other than zeolite) as a carrier for an inorganic antibacterial agent include silica gel and alumina gel.

本発明において、前記第２塩としては、スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の塩を用いる。   In the present invention, as the second salt, at least one salt selected from the group consisting of sulfonate and carboxylate is used.

前記スルホン酸塩としては、特に限定されるものではないが、アルファオレフィンスルホン酸塩を用いるのが好ましい。前記アルファオレフィンスルホン酸塩としては、特に限定されないが、例えば、アルファオレフィンスルホン酸ナトリウム等が挙げられる。   The sulfonate is not particularly limited, but an alpha olefin sulfonate is preferably used. Although it does not specifically limit as said alpha olefin sulfonate, For example, alpha olefin sulfonate sodium etc. are mentioned.

前記カルボン酸塩としては、特に限定されるものではないが、ポリカルボン酸塩を用いるのが好ましい。前記ポリカルボン酸塩としては、特に限定されないが、例えば、メトキシポリエチレングリコールとアクリル酸とのエステル化合物と、クロトン酸との共重合物、スチレングリコールとアリルアルコールとのエーテル化合物と、フマル酸との共重合物等が挙げられる。   Although it does not specifically limit as said carboxylate, It is preferable to use polycarboxylate. The polycarboxylate is not particularly limited. For example, a copolymer of an ester compound of methoxypolyethylene glycol and acrylic acid and a crotonic acid, an ether compound of styrene glycol and allyl alcohol, and fumaric acid. Examples include copolymers.

前記バインダー樹脂としては、特に限定されるものではないが、例えば、自己架橋型アクリル樹脂、メタアクリル樹脂、ウレタン樹脂、シリコン樹脂、グリオキザ−ル樹脂、酢酸ビニル樹脂、塩化ビニリデン樹脂、ブタジエン樹脂、メラミン樹脂、エポキシ樹脂、アクリル−シリコン共重合体樹脂、エチレン−酢酸ビニル共重合体樹脂、イソブチレン無水マレイン酸共重合体樹脂、エチレン−スチレン−アクリレート−メタアクリレ−ト共重合体樹脂等が挙げられる。また、これらの樹脂を２種類以上併用してバインダー樹脂として用いてもよい。   The binder resin is not particularly limited. For example, self-crosslinking acrylic resin, methacrylic resin, urethane resin, silicon resin, glyoxal resin, vinyl acetate resin, vinylidene chloride resin, butadiene resin, melamine Resins, epoxy resins, acrylic-silicone copolymer resins, ethylene-vinyl acetate copolymer resins, isobutylene maleic anhydride copolymer resins, ethylene-styrene-acrylate-methacrylate copolymer resins, and the like. Two or more of these resins may be used in combination as a binder resin.

本発明の消臭抗菌組成物は、さらにノニオン系界面活性剤を含有するのが好ましい。前記ノニオン系界面活性剤としては、特に限定されるものではないが、例えば、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ソルビタン脂肪酸エステル等が挙げられる。   The deodorant antibacterial composition of the present invention preferably further contains a nonionic surfactant. Although it does not specifically limit as said nonionic surfactant, For example, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, sorbitan fatty acid ester, etc. are mentioned.

前記消臭抗菌組成物において、前記アミン化合物、前記無機多孔質物質、前記水酸化金属、前記金属酸化物、前記金属リン酸塩、前記無機系抗菌剤等は、通常、溶媒に溶解せず溶媒に分散されているが、これら分散質の粒径としては、平均粒径が１０ｎｍ〜１００μｍであるのが好ましい。平均粒径が１０ｎｍ〜１００μｍであることで、布帛に担持したとき、ざらつき感を受けることなく、風合も良好な消臭抗菌布帛を得ることができる。中でも、分散質の平均粒径は１０ｎｍ〜１０μｍであるのが好ましく、１０ｎｍ〜５μｍであるのが特に好ましい。   In the deodorizing antibacterial composition, the amine compound, the inorganic porous material, the metal hydroxide, the metal oxide, the metal phosphate, the inorganic antibacterial agent, etc. are usually not dissolved in the solvent. The average particle size of these dispersoids is preferably 10 nm to 100 μm. When the average particle size is 10 nm to 100 μm, a deodorized antibacterial fabric having a good texture can be obtained without feeling rough when it is carried on the fabric. Especially, it is preferable that the average particle diameter of a dispersoid is 10 nm-10 micrometers, and it is especially preferable that it is 10 nm-5 micrometers.

前記消臭抗菌組成物中の固形分濃度は、１５質量％〜３５質量％に設定されるのが好ましい。１５質量％以上であることで布帛等へ加工する時の消臭抗菌組成物の希釈液中の含有成分の沈降を十分に抑制することができると共に、３５質量％以下であることで消臭抗菌組成物液の長期間貯蔵安定性をさらに向上させることができる。   The solid content concentration in the deodorant antibacterial composition is preferably set to 15% by mass to 35% by mass. When it is 15% by mass or more, it is possible to sufficiently suppress sedimentation of the components contained in the diluted liquid of the deodorant antibacterial composition when it is processed into a fabric or the like, and when it is 35% by mass or less, the deodorant antibacterial The long-term storage stability of the composition liquid can be further improved.

前記消臭抗菌組成物において、前記各成分の含有比率は特に限定されないが、前記アミン化合物は、前記バインダー樹脂１００質量部に対し、４質量部〜４０質量部の範囲に設定されるのが好ましい。   In the deodorant antibacterial composition, the content ratio of each component is not particularly limited, but the amine compound is preferably set in a range of 4 to 40 parts by mass with respect to 100 parts by mass of the binder resin. .

前記無機系消臭剤は、前記バインダー樹脂１００質量部に対し、１０質量部〜１００質量部の範囲に設定されるのが好ましい。   The inorganic deodorant is preferably set in a range of 10 to 100 parts by mass with respect to 100 parts by mass of the binder resin.

前記金属リン酸塩（第１塩）は、前記バインダー樹脂１００質量部に対し、８質量部〜８０質量部の範囲に設定されるのが好ましい。８質量部以上であることで、繰り返し洗濯後の消臭性能をより向上させることができると共に、８０質量部以下であることで、長期間貯蔵安定性をより向上させることができる。   The metal phosphate (first salt) is preferably set in the range of 8 to 80 parts by mass with respect to 100 parts by mass of the binder resin. By being 8 parts by mass or more, the deodorizing performance after repeated washing can be further improved, and by being 80 parts by mass or less, long-term storage stability can be further improved.

前記無機系抗菌剤は、前記バインダー樹脂１００質量部に対し、１質量部〜１０質量部の範囲に設定されるのが好ましい。１質量部以上であることで十分な抗菌性能を付与できると共に１０質量部以下であることで、長期間貯蔵安定性をさらに向上させることができる。   The inorganic antibacterial agent is preferably set in a range of 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the binder resin. When it is 1 part by mass or more, sufficient antibacterial performance can be imparted, and when it is 10 parts by mass or less, long-term storage stability can be further improved.

前記第２塩（スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の塩）は、前記バインダー樹脂１００質量部に対し、０．４質量部〜４０質量部の範囲に設定されるのが好ましい。０．４質量部以上であることで、金属リン酸塩を含有しているにもかかわらず、液の貯蔵安定性を向上させることができると共に、４０質量部以下であることで、液の粘度上昇、ゲル化を抑制し、長期間貯蔵安定性を向上させることができる。   The second salt (at least one salt selected from the group consisting of sulfonate and carboxylate) is set in a range of 0.4 to 40 parts by mass with respect to 100 parts by mass of the binder resin. It is preferable. Although it is 0.4 parts by mass or more, the storage stability of the liquid can be improved in spite of containing the metal phosphate, and the viscosity of the liquid is 40 parts by mass or less. The rise and gelation can be suppressed and long-term storage stability can be improved.

前記ノニオン系界面活性剤は、前記バインダー樹脂１００質量部に対し、０．８質量部〜４０質量部の範囲に設定されるのが好ましい。   The nonionic surfactant is preferably set in the range of 0.8 to 40 parts by mass with respect to 100 parts by mass of the binder resin.

前記消臭抗菌組成物の布帛への担持量（固着量）は、２ｇ／ｍ2〜５０ｇ／ｍ2（乾燥重量；固形分）とするのが好ましい。２ｇ／ｍ2以上であることで十分な消臭抗菌性能を得ることができると共に、５０ｇ／ｍ2以下であることで徒にコストを増大することを回避できる（また５０ｇ／ｍ2を超えても大きな消臭性能の向上はない）。The amount of the deodorant antibacterial composition supported on the fabric (fixed amount) is preferably 2 g / m 2 to 50 g / m 2 (dry weight; solid content). Sufficient deodorant antibacterial performance can be obtained when it is 2 g / m 2 or more, and it can be avoided that the cost is increased when it is 50 g / m 2 or less (also exceeding 50 g / m 2). There is no significant improvement in deodorizing performance).

前記消臭抗菌組成物の塗布液の作成方法としては、特に限定されるものではないが、例えば、前記アミン化合物と、前記無機系消臭剤と、前記金属リン酸塩と、前記無機系抗菌剤と、前記第２塩と、前記ノニオン系界面活性剤と、前記バインダー樹脂と、を水に分散させた水分散液からなる塗布液を作製する。この時、アミン化合物と、無機系消臭剤と、金属リン酸塩と、無機系抗菌剤と、第２塩と、ノニオン系界面活性剤と、バインダー樹脂を可能な限り水に十分に分散させることが好ましい。また、予め先に、アミン化合物と、無機系消臭剤と、金属リン酸塩と、無機系抗菌剤と、第２塩と、ノニオン系界面活性剤と、を水に分散させておいてから、次にバインダー樹脂を分散させるのが、これらをより均一に分散させる点でより好ましい。   A method for preparing the coating liquid for the deodorant antibacterial composition is not particularly limited. For example, the amine compound, the inorganic deodorant, the metal phosphate, and the inorganic antibacterial A coating solution is prepared which comprises an aqueous dispersion in which an agent, the second salt, the nonionic surfactant, and the binder resin are dispersed in water. At this time, the amine compound, the inorganic deodorant, the metal phosphate, the inorganic antibacterial agent, the second salt, the nonionic surfactant, and the binder resin are sufficiently dispersed in water as much as possible. It is preferable. In addition, an amine compound, an inorganic deodorant, a metal phosphate, an inorganic antibacterial agent, a second salt, and a nonionic surfactant are dispersed in water in advance. Then, it is more preferable to disperse the binder resin from the viewpoint of dispersing them more uniformly.

なお、前記消臭抗菌組成物の塗布液には、分散剤、増粘剤等の各種添加剤を添加してもよい。   In addition, you may add various additives, such as a dispersing agent and a thickener, to the coating liquid of the said deodorant antibacterial composition.

こうして得られる消臭抗菌組成物からなる塗布液を、肌着用生地、服地、壁紙、椅子張り地、車両用内装材、カーテン、カーペット、靴用内装材、靴のインソール等の布帛に塗布する。塗布する手法としては、特に限定されるものではないが、例えば、スプレー法、浸漬法、コーティング法、パディング法等が挙げられる。塗布する時期は、例えばカーペットの場合、パイル糸、基布、バッキング層それぞれ単体の状態で塗布してもよいし、基布にパイル糸を植設した表皮層の形態で塗布液を塗布してもよいし、接着層を介して表皮層とバッキング層と接着一体化した形態で塗布してもよい。また、消臭抗菌組成物を目止め層の処理液に混入し、スプレーやローラーコーティングで塗布して消臭抗菌機能のある目止め層としてもよい。また、カーテンの場合は、縫製したあとスプレー法等で塗布しても良いし、生地の状態で浸漬法、コーティング法、パディング法等で塗付し乾燥してもよい。   The coating liquid comprising the deodorant antibacterial composition thus obtained is applied to fabrics such as underwear fabrics, clothing, wallpaper, chair upholstery, vehicle interior materials, curtains, carpets, shoe interior materials, shoe insoles and the like. The method for applying is not particularly limited, and examples thereof include a spray method, a dipping method, a coating method, and a padding method. For example, in the case of carpet, the pile yarn, the base fabric, and the backing layer may be applied in a single state, or the coating liquid may be applied in the form of a skin layer in which the pile yarn is planted on the base fabric. Alternatively, it may be applied in a form in which the skin layer and the backing layer are bonded and integrated through the adhesive layer. Moreover, it is good also as a sealing layer with a deodorizing antibacterial function by mixing a deodorizing antibacterial composition into the processing liquid of a sealing layer, and apply | coating with a spray or roller coating. In the case of a curtain, it may be applied by a spraying method after sewing, or may be applied and dried by a dipping method, a coating method, a padding method or the like in a fabric state.

上記のようにして塗布液を付与した後に乾燥を行うが、乾燥手法としては、加熱処理する方法が、乾燥効率向上の観点から好ましい。加熱処理温度は、１００℃〜１８０℃とするのが好ましい。このような温度での加熱処理によって、消臭抗菌組成物の固着性をより高め、消臭性能の持続耐久性および抗菌性能の持続耐久性をさらに向上させることができる。   Drying is carried out after applying the coating solution as described above. As a drying method, a method of heat treatment is preferable from the viewpoint of improving the drying efficiency. The heat treatment temperature is preferably 100 ° C to 180 ° C. By heat treatment at such a temperature, the fixing property of the deodorant antibacterial composition can be further improved, and the durability of deodorant performance and the durability of antibacterial performance can be further improved.

本発明の消臭抗菌布帛は、布帛の少なくとも一部に上記消臭抗菌組成物が固着されてなるものである。   The deodorant antibacterial fabric of the present invention is obtained by fixing the deodorant antibacterial composition to at least a part of the fabric.

本発明の消臭抗菌布帛としては、特に限定されるものではないが、例えば、肌着用生地、服地、壁紙、椅子張り地、車両用内装材、カーテン、カーペット、靴用内装材、靴のインソール（図１参照）等の布帛の他、織物、編物、不織布、モケット等の布帛等が挙げられる。   The deodorant antibacterial fabric of the present invention is not particularly limited. For example, skin-wearing fabric, clothing, wallpaper, chair upholstery, vehicle interior material, curtain, carpet, shoe interior material, shoe insole In addition to fabrics such as (see FIG. 1), fabrics such as woven fabrics, knitted fabrics, non-woven fabrics, and moquettes can be used.

前記消臭抗菌布帛を構成する繊維としては、特に限定されるものではないが、例えば、ポリエステル繊維、ポリアミド繊維、ポリプロピレン繊維、アクリル繊維、レーヨン繊維等が好適に用いられ、その他、麻、綿、羊毛等の天然繊維等も用いられる。   The fiber constituting the deodorant antibacterial fabric is not particularly limited. For example, polyester fiber, polyamide fiber, polypropylene fiber, acrylic fiber, rayon fiber and the like are preferably used. Natural fibers such as wool are also used.

次に、本発明の具体的実施例について説明するが、本発明はこれら実施例のものに特に限定されるものではない。   Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

＜実施例１＞
ヒドラジド化合物（セバシン酸ジヒドラジド；平均粒径１μｍ）２質量部、トリポリリン酸アルミニウム（平均粒径２μｍ）３質量部、ゼオライト（平均粒径５μｍ）３質量部、水酸化ジルコニウム（平均粒径１μｍ）１質量部、酸化亜鉛（平均粒径１５μｍ）２質量部、銀担持無機多孔質物質（銀担持ゼオライト；平均粒径２０μｍ）２質量部、アルファオレフィンスルホン酸ナトリウム０．５質量部、ポリオキシアルキレンアルキルエーテル１質量部を水７３質量部に混合して撹拌することにより十分に分散させた後、さらにウレタン系樹脂１２．５質量部を混合して撹拌機で撹拌を行うことによって分散液（消臭抗菌組成物液）を得た。<Example 1>
Hydrazide compound (sebacate dihydrazide; average particle size 1 μm) 2 parts by mass, aluminum tripolyphosphate (average particle size 2 μm) 3 parts by mass, zeolite (average particle size 5 μm) 3 parts by mass, zirconium hydroxide (average particle size 1 μm) 1 2 parts by mass of zinc oxide (average particle size 15 μm), 2 parts by mass of silver-supporting inorganic porous material (silver-supported zeolite; average particle size 20 μm), 0.5 part by mass of sodium alpha olefin sulfonate, polyoxyalkylene alkyl After mixing 1 part by mass of ether with 73 parts by mass of water and stirring sufficiently, 12.5 parts by mass of a urethane resin is further mixed and stirred with a stirrer to obtain a dispersion (deodorant). An antibacterial composition liquid) was obtained.

次に、ポリエステル製のステッチボンド不織布（目付：１４０ｇ／ｍ2）を前記分散液に５秒間浸漬した後、取り出してマングルで絞り、１３０℃で１５分間乾燥させることにより、図２に示す消臭抗菌布帛を得た。Next, a polyester stitch-bonded nonwoven fabric (weight per unit: 140 g / m 2 ) was immersed in the dispersion for 5 seconds, then taken out, squeezed with mangles, and dried at 130 ° C. for 15 minutes to remove the deodorant shown in FIG. An antibacterial fabric was obtained.

前記消臭抗菌布帛における消臭抗菌組成物の固形分塗布量は５．４ｇ／ｍ2であった。前記消臭抗菌布帛における各成分の付着量（乾燥状態）は、カルボジヒドラジド：０．４ｇ／ｍ2、トリポリリン酸アルミニウム：０．６ｇ／ｍ2、ゼオライト：０．６ｇ／ｍ2、水酸化ジルコニウム：０．２ｇ／ｍ2、酸化亜鉛：０．４ｇ／ｍ2、銀担持無機多孔質物質（銀担持ゼオライト）：０．４ｇ／ｍ2、アルファオレフィンスルホン酸ナトリウム：０．１ｇ／ｍ2、ポリオキシアルキレンアルキルエーテル：０．２ｇ／ｍ2、ウレタン系樹脂：２．５ｇ／ｍ2であった。The solid content application amount of the deodorant antibacterial composition in the deodorant antibacterial fabric was 5.4 g / m 2 . The adhering amount (dry state) of each component in the deodorant antibacterial fabric was as follows: carbodihydrazide: 0.4 g / m 2 , aluminum tripolyphosphate: 0.6 g / m 2 , zeolite: 0.6 g / m 2 , zirconium hydroxide : 0.2 g / m 2 , zinc oxide: 0.4 g / m 2 , silver-supporting inorganic porous material (silver-supported zeolite): 0.4 g / m 2 , sodium alpha olefin sulfonate: 0.1 g / m 2 , Polyoxyalkylene alkyl ether: 0.2 g / m 2 and urethane resin: 2.5 g / m 2 .

＜実施例２〜８、比較例１〜８＞
配合組成（配合物、配合比率等）を表１、２に示す組成とした以外は、実施例１と同様にして、消臭抗菌布帛を得た。<Examples 2-8, Comparative Examples 1-8>
A deodorized antibacterial fabric was obtained in the same manner as in Example 1 except that the composition (formulation, blending ratio, etc.) was changed to the composition shown in Tables 1 and 2.

Figure 2014102980
Figure 2014102980

Figure 2014102980
Figure 2014102980

上記のようにして得られた各消臭抗菌組成物液（分散液）の貯蔵安定性を下記評価法に基づいて評価した。この結果を表１、２に示す。   The storage stability of each deodorant antibacterial composition liquid (dispersion liquid) obtained as described above was evaluated based on the following evaluation method. The results are shown in Tables 1 and 2.

＜消臭抗菌組成物液の貯蔵安定性評価法＞
消臭抗菌組成物液を４５℃の恒温槽内で７日間静置させた後、取り出した消臭抗菌組成物液を目視し、下記判定基準に基づいて評価した。
（判定基準）
「○」…含有成分の固化、沈降、水との分離のいずれの現象も認められなかった
「×」…含有成分の固化、沈降、水との分離のうち少なくとも１以上の現象が認められた。<Storage stability evaluation method of deodorant antibacterial composition liquid>
The deodorized antibacterial composition liquid was allowed to stand in a 45 ° C. constant temperature bath for 7 days, and then the taken out deodorized antibacterial composition liquid was visually observed and evaluated based on the following criteria.
(Criteria)
“○”: none of the solidification, sedimentation and separation of water was observed. “×”: at least one phenomenon of solidification, sedimentation and separation of water was observed. .

また、上記のようにして得られた各消臭抗菌布帛について下記評価法に基づいて性能評価を行った。これらの結果を表１、２に示す。   Moreover, performance evaluation was performed based on the following evaluation method about each deodorant antibacterial fabric obtained as mentioned above. These results are shown in Tables 1 and 2.

＜摩擦試験法＞
ＪＩＳ Ｌ０８４９に準拠して摩擦試験機II型を用いて消臭抗菌布帛に対し摩擦試験（摩擦回数：３０往復）を行い、下記判定基準に基づいて評価した。
「○」…消臭抗菌組成物（成分）の脱離が認められなかった
「△」…消臭抗菌組成物（成分）の脱離が少し認められた
「×」…消臭抗菌組成物（成分）の脱離が比較的多く認められた。<Friction test method>
The deodorant antibacterial fabric was subjected to a friction test (friction frequency: 30 reciprocations) using a friction tester type II in accordance with JIS L0849, and evaluated based on the following criteria.
“◯”: Desorption of the deodorant antibacterial composition (component) was not observed “△”: Desorption of the deodorant antibacterial composition (component) was slightly observed “X”: Deodorant antibacterial composition ( A relatively large amount of component) was observed.

＜消臭性能評価法＞
消臭抗菌布帛の試験片（１０ｃｍ×１０ｃｍ）を内容量３Ｌの袋内に入れた後、袋内において濃度が２００ｐｐｍとなるようにアンモニアガスを注入し、２０分間経過後にアンモニアガスの残存濃度を測定し、この測定値よりアンモニアガスを除去した総量を算出し、これよりアンモニアガスの除去率（消臭率）（％）を算出した。
「○」…除去率が８０％以上である
「△」…除去率が６０％以上８０％未満である
「×」…除去率が６０％未満である。<Deodorization performance evaluation method>
After putting a test piece (10 cm × 10 cm) of the deodorant antibacterial cloth into a bag having a capacity of 3 L, ammonia gas is injected so that the concentration becomes 200 ppm in the bag, and after 20 minutes, the residual concentration of ammonia gas is measured. The total amount from which ammonia gas was removed was calculated from the measured value, and the ammonia gas removal rate (deodorization rate) (%) was calculated therefrom.
“◯”: The removal rate is 80% or more “Δ”: The removal rate is 60% or more and less than 80% “X”: The removal rate is less than 60%.

＜抗菌性能評価法＞
ＪＩＳ Ｌ１９０２−２００８（繊維製品の抗菌性試験方法及び抗菌効果）に準拠して試験を行った。対象試験菌は、黄色ブドウ球菌である。静菌活性値は、下記算出式により算出し、下記判定基準に基づいて評価した。
静菌活性値＝（Ｍｂ−Ｍａ）−（Ｍｃ−Ｍｏ）
Ｍｂ：無加工標準布帛の１８時間培養後の３検体の静菌数の常用対数値の平均値
Ｍａ：無加工標準布帛の試験菌接種直後の３検体の静菌数の常用対数値の平均値
Ｍｃ：抗菌加工布帛の１８時間培養後の３検体の静菌数の常用対数値の平均値
Ｍｏ：抗菌加工布帛の試験菌接種直後の３検体の静菌数の常用対数値の平均値
（判定基準）
「○」…静菌活性値が２．２以上
「×」…静菌活性値が２．２未満。<Antimicrobial performance evaluation method>
The test was conducted in accordance with JIS L1902-2008 (antibacterial test method and antibacterial effect of textile products). The target test bacterium is S. aureus. The bacteriostatic activity value was calculated by the following calculation formula and evaluated based on the following criteria.
Bacteriostatic activity value = (Mb-Ma)-(Mc-Mo)
Mb: Average value of common logarithm of bacteriostatic number of 3 specimens after 18 hours culture of unprocessed standard fabric Ma: Average value of common logarithm of bacteriostatic number of 3 specimens immediately after inoculation of test bacteria of unprocessed standard fabric Mc: Average value of common logarithmic values of the number of bacteriostatics of three samples after 18 hours of culturing antibacterial fabrics Mo: Average value of common logarithm values of the number of bacteriostatics of three samples immediately after inoculation of test bacteria on antibacterial fabrics Standard)
“◯”: The bacteriostatic activity value is 2.2 or more.

なお、上記消臭性能評価法および抗菌性能評価法に供する布帛としては、前記実施例１〜８及び比較例１〜８の各消臭抗菌布帛に対して、ＳＥＫマーク繊維製品の洗濯マニュアル（ＪＥＣ３２６ 平成２４年４月１日改定、一般社団法人繊維評価技術協議会）に準拠して洗濯を行った後の布帛（洗濯済み布帛）を用いるものとした。即ち、前記洗濯において、洗濯機は、ＪＩＳ Ｌ０２１７の洗い方１０３に規定するＪＩＳ Ｃ９６０６の規格に適合する遠心式絞り装置付きの標準洗濯容量、標準水量の洗濯機を使用し、洗剤は、「ＪＡＦＥＴ標準配合洗剤」を使用した。このようにして洗濯した後の布帛を、上記消臭性能評価および抗菌性能評価に供した。   In addition, as a cloth used for the said deodorant performance evaluation method and antibacterial performance evaluation method, the washing manual (JEC326) of a SEK mark fiber product is used with respect to each deodorant antibacterial fabric of the said Examples 1-8 and Comparative Examples 1-8. The cloth (washed cloth) after being washed according to the revision on April 1, 2012, in accordance with the Japan Fiber Evaluation Technology Council) was used. That is, in the washing, the washing machine uses a washing machine having a standard washing capacity and a standard water amount with a centrifugal squeezing device conforming to the JIS C9606 standard stipulated in the washing method 103 of JIS L0217. A “standard detergent” was used. The fabric after washing in this way was subjected to the above deodorant performance evaluation and antibacterial performance evaluation.

表から明らかなように、本発明に係る実施例１〜８の消臭抗菌組成物は、長期にわたってゲル化、凝集物発生がなくて貯蔵安定性に優れており、従って本発明の消臭抗菌組成物液は、長期間貯蔵後に布帛に加工を行っても、消臭性能及び抗菌性能に優れた消臭抗菌布帛を安定して提供できる。また、本発明に係る実施例１〜８の消臭抗菌布帛は、摩擦試験を行っても消臭抗菌組成物が離脱することがないし、消臭性能及び抗菌性能のいずれにも優れていた。   As is clear from the table, the deodorant antibacterial compositions of Examples 1 to 8 according to the present invention are excellent in storage stability without gelation and aggregate formation over a long period of time. The composition liquid can stably provide a deodorized antibacterial fabric excellent in deodorizing performance and antibacterial performance even when the fabric is processed after long-term storage. Moreover, the deodorant antibacterial fabrics of Examples 1 to 8 according to the present invention did not release the deodorant antibacterial composition even when a friction test was performed, and were excellent in both the deodorant performance and the antibacterial performance.

本発明に係る消臭抗菌組成物は、例えば、布帛等に付与固着されて、布帛等に優れた消臭性能及び抗菌性能を具備させるのに用いられるが、特にこのような用途に限定されるものではない。   The deodorant antibacterial composition according to the present invention is applied and fixed to, for example, a fabric and used to provide the fabric with excellent deodorant performance and antibacterial performance, but is particularly limited to such applications. It is not a thing.

本発明に係る消臭抗菌布帛は、特に限定されるものではないが、例えば、肌着用生地、服地、壁紙、椅子張り地、車両用内装材、カーテン、カーペット、靴用内装材、靴のインソール等として好適に使用される。   Although the deodorant antibacterial fabric according to the present invention is not particularly limited, for example, underwear fabric, clothing, wallpaper, chair upholstery, vehicle interior material, curtain, carpet, shoe interior material, shoe insole Etc. are preferably used.

１…消臭抗菌布帛 1. Deodorant antibacterial fabric

＜抗菌性能評価法＞
ＪＩＳ Ｌ１９０２−２００８（繊維製品の抗菌性試験方法及び抗菌効果）に準拠して試験を行った。対象試験菌は、黄色ブドウ球菌である。静菌活性値は、下記算出式により算出し、下記判定基準に基づいて評価した。
静菌活性値＝（Ｍｂ−Ｍａ）−（Ｍｃ−Ｍｏ）
Ｍｂ：無加工標準布帛の１８時間培養後の３検体の生菌数の常用対数値の平均値
Ｍａ：無加工標準布帛の試験菌接種直後の３検体の生菌数の常用対数値の平均値
Ｍｃ：抗菌加工布帛の１８時間培養後の３検体の生菌数の常用対数値の平均値
Ｍｏ：抗菌加工布帛の試験菌接種直後の３検体の生菌数の常用対数値の平均値
（判定基準）
「○」…静菌活性値が２．２以上
「×」…静菌活性値が２．２未満。
<Antimicrobial performance evaluation method>
The test was conducted in accordance with JIS L1902-2008 (antibacterial test method and antibacterial effect of textile products). The target test bacterium is S. aureus. The bacteriostatic activity value was calculated by the following calculation formula and evaluated based on the following criteria.
Bacteriostatic activity value = (Mb-Ma)-(Mc-Mo)
Mb: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culturing unprocessed standard fabric Ma: Average value of common logarithm of the number of viable bacteria of 3 specimens immediately after inoculation of test bacteria Mc: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours culture of antibacterial processed fabric Mo: Average value of common logarithm of the number of viable bacteria of 3 specimens immediately after inoculation of test bacteria on antibacterial processed fabric (determination Standard)
“◯”: The bacteriostatic activity value is 2.2 or more.

Claims (8)

アミン化合物と、
無機系消臭剤と、
金属リン酸塩からなる第１塩と、
無機系抗菌剤と、
スルホン酸塩及びカルボン酸塩からなる群より選択される少なくとも１種の第２塩と、
バインダー樹脂と、を含有することを特徴とする消臭抗菌組成物。An amine compound;
An inorganic deodorant,
A first salt comprising a metal phosphate;
An inorganic antibacterial agent,
At least one second salt selected from the group consisting of sulfonates and carboxylates;
A deodorizing antibacterial composition comprising a binder resin. 前記第２塩として、アルファオレフィンスルホン酸塩及びポリカルボン酸塩からなる群より選択される少なくとも１種の塩が用いられている請求項１に記載の消臭抗菌組成物。   The deodorizing antibacterial composition according to claim 1, wherein at least one salt selected from the group consisting of an alpha olefin sulfonate and a polycarboxylate is used as the second salt. 前記無機系消臭剤は、無機多孔質物質、水酸化金属および金属酸化物である請求項１または２に記載の消臭抗菌組成物。   The deodorant antibacterial composition according to claim 1 or 2, wherein the inorganic deodorant is an inorganic porous material, a metal hydroxide, and a metal oxide. さらにノニオン系界面活性剤を含有する請求項１〜３のいずれか１項に記載の消臭抗菌組成物。   Furthermore, the deodorizing antibacterial composition of any one of Claims 1-3 containing a nonionic surfactant. 前記バインダー樹脂１００質量部に対し、前記第２塩を０．４質量部〜４０質量部含有し、前記金属リン酸塩からなる第１塩を８質量部〜８０質量部含有する請求項１〜４のいずれか１項に記載の消臭抗菌組成物。   The 1st salt which contains 0.4 mass part-40 mass parts of said 2nd salt with respect to 100 mass parts of said binder resins, and contains 8 mass parts-80 mass parts of 1st salts which consist of the said metal phosphate. 5. The deodorizing antibacterial composition according to any one of 4 above. 前記組成物中の固形分濃度が１５質量％〜３５質量％である請求項１〜５のいずれか１項に記載の消臭抗菌組成物。   The deodorant antibacterial composition according to any one of claims 1 to 5, wherein a solid content concentration in the composition is 15% by mass to 35% by mass. 布帛の少なくとも一部に、請求項１〜６のいずれか１項に記載の消臭抗菌組成物が固着されていることを特徴とする消臭抗菌布帛。   A deodorant antibacterial fabric, wherein the deodorant antibacterial composition according to any one of claims 1 to 6 is fixed to at least a part of the fabric. 肌着用生地、服地、壁紙、椅子張り地、車両用内装材、カーテン、カーペット、靴用内装材又は靴のインソールとして用いられる請求項７に記載の消臭抗菌布帛。   8. The deodorant antibacterial fabric according to claim 7, which is used as an underwear fabric, clothes, wallpaper, chair upholstery, vehicle interior material, curtain, carpet, shoe interior material or shoe insole.
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