TWI803493B - Particulate deodorant for fiber - Google Patents
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- TWI803493B TWI803493B TW107117228A TW107117228A TWI803493B TW I803493 B TWI803493 B TW I803493B TW 107117228 A TW107117228 A TW 107117228A TW 107117228 A TW107117228 A TW 107117228A TW I803493 B TWI803493 B TW I803493B
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Abstract
Description
發明領域field of invention
本發明係有關於一種微粒子狀纖維用除臭劑,屬於除臭劑之技術領域及纖維之技術領域。The invention relates to a deodorant for microparticle fibers, and belongs to the technical field of deodorants and fibers.
發明背景Background of the invention
近年來追求更舒適之居住環境當中,市場上出現除臭墊、除臭窗簾、除臭濾網、以及具備有對汗臭、老人臭等的除臭機能之衣物、寢具等「除臭性製品」。 專利文獻1中,為了獲得酸/鹼成份皆能除臭、對汗臭等惡臭的除臭性高、反覆洗滌亦不易使除臭性降低、用於具有吸水性之纖維的除臭劑,揭示一種使用了含有膨潤石、矽酸鋁、黏結劑樹脂、改質聚矽氧化合物、氧化鋅及水之液體的除臭系統。In the pursuit of a more comfortable living environment in recent years, deodorant mats, deodorizing curtains, deodorizing filters, and clothes and bedding with deodorizing functions against sweat and old people have appeared on the market. products". In Patent Document 1, in order to obtain a deodorant that can deodorize both acid and alkali components, has high deodorization performance against malodors such as sweat odor, and is not easy to reduce the deodorization performance after repeated washing, and is used for fibers with water absorption, it is disclosed A deodorizing system using a liquid containing bentonite, aluminum silicate, binder resin, modified polysiloxane, zinc oxide and water.
專利文獻2及3中,作為直接使纖維中含有抗菌劑或除臭劑之方法,揭示了一種以聚合物二元醇及二異氰酸酯作為起始物之聚胺甲酸酯所構成之彈性絲,其為含有金屬磷酸鹽及4級銨鹽系抗菌劑之聚胺甲酸酯彈性絲。 先行技術文獻 專利文獻In Patent Documents 2 and 3, as a method of directly adding an antibacterial agent or a deodorant to the fiber, an elastic yarn made of polyurethane starting from polymer diol and diisocyanate is disclosed. It is polyurethane elastic yarn containing metal phosphate and 4th grade ammonium salt antibacterial agent. Prior Art Documents Patent Documents
[專利文獻1]日本專利特開2015-171449號公報 [專利文獻2]日本專利特許第5413360號公報 [專利文獻3]日本專利特許第5870928號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-171449 [Patent Document 2] Japanese Patent No. 5413360 [Patent Document 3] Japanese Patent No. 5870928
發明概要 發明欲解決之課題Outline of the Invention Problems to be Solved by the Invention
然而,專利文獻1所揭示之除臭系統是利用後續加工之方法,雖能獲得具有暫時性的除臭性機能之製品,但用於使機能劑附著之黏結劑會產生損及質地、或加工步驟變長而導致的生產性降低或洗滌耐久性降低的問題。 又,專利文獻2及3所揭示之除臭劑是混入纖維,會有被埋住的部份難以獲得除臭效果,欲得到充分效果則需增加添加量,然而增加添加量會產生凝集或大粒子容易混入,紡線時容易發生線斷裂等缺點。 本發明是以提供一種具有良好紡線性,對於三甲基胺、氨等鹼性氣體之除臭性能高,特別是對氨除臭性能優異之除臭劑為課題。 用以解決課題之手段However, the deodorant system disclosed in Patent Document 1 utilizes post-processing methods. Although products with temporary deodorant functions can be obtained, the binder used to attach the functional agent will cause damage to the texture or processing. There is a problem of lower productivity due to longer steps or lower washing durability. Also, the deodorants disclosed in Patent Documents 2 and 3 are mixed with fibers, and it is difficult to obtain a deodorizing effect in the buried part. In order to obtain a sufficient effect, it is necessary to increase the amount of addition. However, increasing the amount of addition will cause aggregation or large Particles are easy to mix in, and the thread is prone to breakage when spinning. The object of the present invention is to provide a deodorant with good spinnability and high deodorizing performance against basic gases such as trimethylamine and ammonia, especially excellent deodorizing performance against ammonia. means to solve problems
用以解決前述課題之具體手段係如下述。 1. 一種纖維用除臭劑,包含α磷酸鋯及/或α磷酸鈦,在粒徑方面,中值粒徑為0.2~0.7μm、且最大粒徑5.0μm以下、D10徑0.1μm以上。Specific means for solving the aforementioned problems are as follows. 1. A deodorant for fibers, comprising α-zirconium phosphate and/or α-titanium phosphate, having a median particle size of 0.2-0.7 μm, a maximum particle size of 5.0 μm or less, and a D10 diameter of 0.1 μm or more.
2.如上述1.之纖維用除臭劑,其中前述α磷酸鋯是以下式(1)表示: Zr1-x Hfx Ha (PO4 )b ・nH2 O (1) 式(1)中,a及b為滿足3b-a=4之正數,b為2.0<b≦2.1,x為0≦x≦0.2之正數,n為0≦n≦2.0之正數。2. The deodorant agent for fibers according to the above 1., wherein the aforementioned α-zirconium phosphate is represented by the following formula (1): Zr 1-x Hf x H a (PO 4 ) b ·nH 2 O (1) Formula (1) Among them, a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, x is a positive number of 0≦x≦0.2, and n is a positive number of 0≦n≦2.0.
3.如上述1.之纖維用除臭劑,其中前述α磷酸鈦是以下式(2)表示: TiHa (PO4 )b ・nH2 O (2) 式(2)中,a及b為滿足3b-a=4之正數,b為2.0<b≦2.1,n為0≦n≦2.0之正數。3. The deodorant for fibers according to the above 1., wherein the α-titanium phosphate is represented by the following formula (2): TiH a (PO 4 ) b・nH 2 O (2) In the formula (2), a and b are A positive number satisfying 3b-a=4, b is a positive number of 2.0<b≦2.1, and n is a positive number of 0≦n≦2.0.
4.如上述1.~3.中任一項之纖維用除臭劑,其中α磷酸鋯及α磷酸鈦之水分含有率為1.0重量%以下。4. The deodorant for fibers according to any one of 1. to 3. above, wherein the moisture content of α-zirconium phosphate and α-titanium phosphate is 1.0% by weight or less.
5.如上述1.~4.中任一項之纖維用除臭劑,其中α磷酸鋯及α磷酸鈦是在水溶液中合成而成。5. The deodorant for fibers according to any one of 1. to 4. above, wherein α-zirconium phosphate and α-titanium phosphate are synthesized in an aqueous solution.
6.如上述1.~5.中任一項之纖維用除臭劑,其為纖維混入用。6. The deodorant for fibers according to any one of 1. to 5. above, which is for mixing with fibers.
7.一種除臭纖維,包含有如上述1.~6.中任一項之纖維用除臭劑。7. A deodorant fiber comprising the deodorant for fiber according to any one of 1. to 6. above.
8.如上述7.之除臭纖維,前述纖維是選自於由聚酯、聚胺甲酸酯、耐綸、人造絲、丙烯酸樹脂、維尼綸及聚丙烯所構成群組中之至少1種。 發明效果8. The deodorant fiber according to 7. above, wherein the fiber is at least one selected from the group consisting of polyester, polyurethane, nylon, rayon, acrylic resin, vinylon, and polypropylene . Invention effect
依據本發明,能提供一種具有良好紡線性,對於三甲基胺、氨等鹼性氣體之除臭性能高,特別是對氨除臭性能優異之除臭劑。According to the present invention, it is possible to provide a deodorant having good spinnability, high deodorizing performance against basic gases such as trimethylamine and ammonia, especially excellent deodorizing performance against ammonia.
用以實施發明之形態form for carrying out the invention
本發明係有關於一種包含α磷酸鋯及/或α磷酸鈦的纖維混入用除臭劑,在粒徑方面,中值粒徑為0.2~0.7μm、且最大粒徑5.0μm以下、D10徑0.1μm以上。 以下,將詳細說明本發明之實施態樣。 此外,「%」若無特別敘述時則意指「重量%」,「份」為「重量份」,「ppm」意指「重量ppm」。又,本實施態樣中,標示數值範圍之「下限~上限」的敘述是表示「下限以上,上限以下」,「上限~下限」的敘述是表示「上限以下,下限以上」。亦即,表示包含上限及下限之數值範圍。此外,本實施態樣中,後述之較佳態樣的2者以上的組合亦屬於較佳態樣。The present invention relates to a fiber-incorporating deodorant containing α-zirconium phosphate and/or α-titanium phosphate. In terms of particle size, the median particle size is 0.2 to 0.7 μm, the maximum particle size is 5.0 μm or less, and the D10 diameter is 0.1 μm or more. Hereinafter, embodiments of the present invention will be described in detail. In addition, unless otherwise stated, "%" means "% by weight", "part" means "part by weight", and "ppm" means "ppm by weight". In addition, in this embodiment, the description of "lower limit~upper limit" indicating the numerical range means "above the lower limit and below the upper limit", and the description of "upper limit~lower limit" means "below the upper limit and above the lower limit". That is, a numerical range including an upper limit and a lower limit is indicated. Moreover, in this embodiment, the combination of 2 or more of the preferable aspects mentioned later also belongs to a preferable aspect.
1.除臭劑之粒徑 本實施態樣所使用的除臭劑是由α磷酸鋯及/或α磷酸鈦所構成,其粒徑為中值粒徑0.2~0.7μm、且最大粒徑5.0μm以下、D10徑0.1μm以上。1. Particle size of deodorant The deodorant used in this embodiment is composed of α-zirconium phosphate and/or α-titanium phosphate, and its particle size is 0.2-0.7 μm in median size and 5.0 μm in maximum size µm or less, D10 diameter 0.1 µm or more.
本實施態樣所使用的除臭劑之粒徑之調製方法並無特別限定,為了獲得目的之粒度分布,是以在水溶液中合成為佳。若在水溶液中合成,合成時容易均勻,易於獲得峰值集中(sharp)的粒度分佈。另一方面,粒徑若以粉碎方式來調製,會有微粉與大粒子混入造成粒度分佈的幅度變廣,易成為紡線時線斷裂的原因,故屬不佳。The preparation method of the particle size of the deodorant used in this embodiment is not particularly limited, and it is preferable to synthesize it in an aqueous solution in order to obtain the target particle size distribution. If it is synthesized in an aqueous solution, it is easy to be uniform during the synthesis, and it is easy to obtain a particle size distribution with sharp peaks. On the other hand, if the particle size is adjusted by pulverization, the range of particle size distribution will be widened due to the mixing of fine powder and large particles, which will easily become the cause of thread breakage during spinning, so it is not good.
另外,本實施態樣之粒徑,是以雷射繞射粒度分佈計進行測定,將結果以體積基準來解析而得之值。In addition, the particle diameter of this embodiment is a value obtained by measuring with a laser diffraction particle size distribution meter and analyzing the result on a volume basis.
本實施態樣所使用的除臭劑之中值粒徑為0.2~0.7μm。較佳為0.2~0.6μm。即便中值粒徑在1μm左右時對於紡線性造成問題不大,然而在將等量的除臭劑混入纖維之際,粒徑越細微則粒子數越多,容易表現出除臭效果。又,中值粒徑在0.2μm以上時,粒子變得不易凝集,紡線變得容易,能抑制紡線時的線斷裂。The median particle size of the deodorant used in this embodiment is 0.2-0.7 μm. Preferably it is 0.2-0.6 μm. Even if the median particle size is around 1 μm, there is not much problem with the spinliness. However, when the same amount of deodorant is mixed into the fiber, the finer the particle size, the more the number of particles, and it is easy to show the deodorant effect. In addition, when the median diameter is 0.2 μm or more, the particles are less likely to aggregate, spinning becomes easier, and yarn breakage during spinning can be suppressed.
本實施態樣所使用的除臭劑之最大粒徑為5.0μm以下。較佳為4.0μm以下,更佳為3.0μm以下。若最大徑為5.0μm以下,能抑制紡線時的線斷裂,故屬較佳。又,下限值是以0.7μm以上為佳。The deodorant used in this embodiment has a maximum particle size of 5.0 μm or less. Preferably it is 4.0 μm or less, more preferably 3.0 μm or less. When the maximum diameter is 5.0 μm or less, it is preferable because the yarn breakage during spinning can be suppressed. In addition, the lower limit value is preferably 0.7 μm or more.
本實施態樣所使用的除臭劑之D10徑為0.1μm以上。較佳為0.15μm以上,更佳為0.2μm以上。若D10徑為0.1μm以上時,粒子變得不易凝集,紡線變得容易,亦能抑制線斷裂。又,D10徑之較佳上限值為0.4μm以下。D10徑若為0.4μm以下,則容易獲得中值粒徑為0.7μm以下之粒子。The D10 diameter of the deodorant used in this embodiment is 0.1 μm or more. It is preferably at least 0.15 μm, more preferably at least 0.2 μm. When the D10 diameter is 0.1 μm or more, the particles are less likely to aggregate, spinning becomes easier, and yarn breakage can also be suppressed. Also, the preferable upper limit of the D10 diameter is 0.4 μm or less. When the D10 diameter is 0.4 μm or less, it is easy to obtain particles having a median diameter of 0.7 μm or less.
2.除臭劑之種類 本實施態樣是由具有前述特定粒徑之α磷酸鋯及/或α磷酸鈦所構成之纖維用除臭劑。 以下,將說明α磷酸鋯及α磷酸鈦。2. Types of deodorants This embodiment is a deodorant for fibers composed of α-zirconium phosphate and/or α-titanium phosphate having the aforementioned specific particle size. Hereinafter, α-zirconium phosphate and α-titanium phosphate will be described.
2-1.α磷酸鋯 作為本實施態樣所使用的α磷酸鋯,只要是具有前述粒徑者,則可使用各種的化合物。 作為本實施態樣中較適宜使用的α磷酸鋯,可舉例如下述式(1)所示之化合物,且是每單位重量的理論陽離子交換容量為6.7meq/g。由除臭性能之觀點來看,下述式(1)所示之化合物的陽離子交換量是以6.0meq/g以上為佳,以6.4meq/g以上為較佳。 Zr1-x Hfx Ha (PO4 )b ・nH2 O (1) 式(1)當中,a及b為滿足3b-a=4之正數,b為2.0<b≦2.1,x為0≦x≦0.2之正數,n為0≦n≦2.0之正數。2-1. Alpha zirconium phosphate As the alpha zirconium phosphate used in this embodiment, as long as it has the particle size mentioned above, various compounds can be used. As the α-zirconium phosphate suitably used in this embodiment, the compound represented by the following formula (1) can be mentioned, and the theoretical cation exchange capacity per unit weight is 6.7meq/g. From the viewpoint of deodorizing performance, the cation exchange capacity of the compound represented by the following formula (1) is preferably 6.0 meq/g or more, more preferably 6.4 meq/g or more. Zr 1-x Hf x H a (PO 4 ) b・nH 2 O (1) In formula (1), a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, and x is 0 A positive number of ≦x≦0.2, and n is a positive number of 0≦n≦2.0.
α磷酸鋯之前述式(1)當中,鉿(Hf)是源自於原料鋯化合物之物。式(1)的x為0<x<1之正數。本實施態樣中,以0<x≦0.2為佳,較佳為0.005≦x≦0.1,更佳為0.005≦x<0.03。本實施態樣中,鉿的含量若變多,離子交換性能會提昇,然而鉿存在有具放射性之同位素,故使用於電子零件時,是以將x值抑制為佳。 式(1)的n是以0.2以下為佳,較佳為0.1以下,更佳為0.05以下。藉由將n的值設為2.0以下,在紡線時的樹脂熔融之際,結晶水會變得容易脫離,能防止發泡或線斷裂。In the aforementioned formula (1) of α-zirconium phosphate, hafnium (Hf) is derived from a raw material zirconium compound. x in formula (1) is a positive number of 0<x<1. In this embodiment, 0<x≦0.2 is preferable, more preferably 0.005≦x≦0.1, more preferably 0.005≦x<0.03. In this embodiment, if the content of hafnium increases, the ion exchange performance will be improved. However, hafnium has radioactive isotopes, so when used in electronic parts, it is better to suppress the value of x. n in formula (1) is preferably at most 0.2, more preferably at most 0.1, more preferably at most 0.05. By setting the value of n to 2.0 or less, when the resin is melted during yarn spinning, water of crystallization is easily desorbed, and foaming and yarn breakage can be prevented.
關於本實施態樣所使用的α磷酸鋯之製造方法,能應用習知技術,對於原料或設備等不設限制。例如,可舉出日本特許第5545328號公報及日本特許第5821258號公報所記載的方法等。 作為α磷酸鋯之製造方法,在水溶液中使原料化合物進行反應之方法因為能容易獲得均勻的粒子,故屬較佳。 例如,可舉出將鋯化合物之水溶液與含有磷酸及/或其鹽〔以下稱為「磷酸(鹽)」〕之水溶液混合使沈澱物生成,並經過熟成使其結晶化之方法等。With regard to the production method of the α-zirconium phosphate used in this embodiment, known techniques can be applied, and there is no limitation on raw materials or equipment. For example, the methods described in Japanese Patent No. 5545328 and Japanese Patent No. 5821258, etc. are mentioned. As a method for producing α-zirconium phosphate, a method of reacting raw material compounds in an aqueous solution is preferable because uniform particles can be easily obtained. For example, a method of mixing an aqueous solution of a zirconium compound with an aqueous solution containing phosphoric acid and/or its salt (hereinafter referred to as "phosphoric acid (salt)") to form a precipitate, followed by aging to crystallize it, etc.
作為製造原料之鋯化合物,可舉出硝酸鋯、醋酸鋯、硫酸鋯、碳酸鋯、鹼式硫酸鋯、硫酸氧鋯、及氧氯化鋯等,較佳為硝酸鋯、醋酸鋯、硫酸鋯、碳酸鋯、鹼式硫酸鋯、硫酸氧鋯及氧氯化鋯,若考慮反應性與經濟性等,更佳為氧氯化鋯。Zirconium compounds as raw materials for production include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconyl sulfate, and zirconium oxychloride, etc., preferably zirconium nitrate, zirconium acetate, zirconium sulfate, Zirconium carbonate, zirconium basic sulfate, zirconyl sulfate, and zirconium oxychloride are more preferably zirconium oxychloride in consideration of reactivity and economy.
作為製造原料的磷酸(鹽),可舉出磷酸、磷酸鈉、磷酸鉀及磷酸銨等,以磷酸為佳,較佳為重量濃度為75%~85%左右的高濃度磷酸。 關於磷酸(鹽)的反應比例,是以相對於鋯化合物的進料的莫耳比率來計算,為2以上,以2.05以上為佳,較佳為2.1以上。 磷酸(鹽)的反應比例相對於鋯化合物即使是大量過剩亦可,然而考慮到上清液之導電度,以上述莫耳比率來計算,為3以下,以2.9以下為佳,較佳為2.6以下。Phosphoric acid (salt) as a raw material for production includes phosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate, etc. Phosphoric acid is preferred, preferably high-concentration phosphoric acid with a weight concentration of about 75% to 85%. The reaction ratio of phosphoric acid (salt) is calculated as a molar ratio relative to the charge of the zirconium compound, and is 2 or more, preferably 2.05 or more, more preferably 2.1 or more. The reaction ratio of phosphoric acid (salt) may be a large excess relative to the zirconium compound. However, considering the conductivity of the supernatant, the above-mentioned molar ratio is 3 or less, preferably 2.9 or less, more preferably 2.6 the following.
α磷酸鋯之製造當中,藉由添加草酸化合物,化合物之製造會變更快,能減少原料浪費並有效率地製造,故屬較佳。 作為此時的草酸化合物,可舉出草酸2水合物、草酸銨及草酸氫銨,以草酸2水合物較佳。 關於草酸的反應比例,是以相對於鋯化合物的莫耳比率來計算,為2.5~3.5,以2.7~3.2為佳,較佳為2.8~3.0。本實施態樣中,若為此比例則α磷酸鋯之製造變得容易,故屬較佳。In the production of α-zirconium phosphate, by adding the oxalic acid compound, the production of the compound will be faster, the waste of raw materials can be reduced and the production can be efficiently produced, so it is preferable. Examples of the oxalic acid compound in this case include oxalic acid dihydrate, ammonium oxalate, and ammonium hydrogen oxalate, and oxalic acid dihydrate is preferred. The reaction ratio of oxalic acid is calculated based on the molar ratio relative to the zirconium compound, and is 2.5-3.5, preferably 2.7-3.2, more preferably 2.8-3.0. In this embodiment, if it is this ratio, since the manufacture of alpha zirconium phosphate becomes easy, it is preferable.
將鋯化合物之水溶液與含有磷酸(鹽)之水溶液混合後,進行熟成,該熟成可在常溫下進行,然而為了加快熟成是以在90℃以上的濕式常壓下進行為佳,此外,在比常壓更高的壓力環境並在超過100℃的條件稱為水熱條件,在此條件下合成亦可。若在水熱條件下製造α磷酸鋯時,從製造成本的觀點來看,在130℃以下進行合成係屬較佳。After mixing the aqueous solution of zirconium compound and the aqueous solution containing phosphoric acid (salt), aging is carried out. The aging can be carried out at normal temperature. However, in order to speed up the aging, it is better to carry out under wet normal pressure above 90°C. In addition, in A pressure environment higher than normal pressure and a condition exceeding 100°C are called hydrothermal conditions, and synthesis is also possible under these conditions. When producing α-zirconium phosphate under hydrothermal conditions, it is preferable to perform the synthesis at 130° C. or lower from the viewpoint of production cost.
關於α磷酸鋯之製造時間,只要是能合成α磷酸鋯之時間,任何的時間皆可。例如,在將磷酸(鹽)與鋯化合物混合並使沈澱生成後,透過熟成能獲得α磷酸鋯。該熟成之時間會因為熟成溫度而有不同。 例如,90℃下之熟成是以4小時以上為佳。此外,即使進行24小時以上的熟成,α磷酸鋯之含有率會有達到界限而無法再上升之傾向。 合成後的α磷酸鋯再經過過濾分離並仔細水洗後,進行乾燥可獲得α磷酸鋯。The production time of α-zirconium phosphate may be any time as long as α-zirconium phosphate can be synthesized. For example, alpha zirconium phosphate can be obtained by aging after mixing phosphoric acid (salt) with a zirconium compound and forming a precipitate. The aging time will vary depending on the aging temperature. For example, aging at 90°C is preferably more than 4 hours. In addition, even if aging is performed for 24 hours or longer, the content of α-zirconium phosphate tends to reach a limit and cannot be further increased. The synthesized α-zirconium phosphate is separated by filtration, carefully washed with water, and then dried to obtain α-zirconium phosphate.
2-2.α磷酸鈦 作為本實施態樣所使用的α磷酸鈦,只要是具有前述粒徑者,則可使用各種的化合物。 作為本實施態樣中較適宜使用的α磷酸鈦,可舉例如下述式(2)所示之化合物,且每單位重量的理論陽離子交換容量為7.7meq/g。由除臭性能之觀點來看,下述式(2)所示之化合物的陽離子交換量是以6.2meq/g以上為佳,6.7meq/g以上為較佳。 TiHa (PO4)b ・nH2 O (2) 式(2)當中,a及b為滿足3b-a=4之正數,b為2.0<b≦2.1, n為0≦n≦2.0之正數。2-2. α-Titanium Phosphate As the α-titanium phosphate used in this embodiment, as long as it has the aforementioned particle size, various compounds can be used. As the α-titanium phosphate suitably used in this embodiment, the compound represented by the following formula (2) can be mentioned, and the theoretical cation exchange capacity per unit weight is 7.7meq/g. From the viewpoint of deodorizing performance, the cation exchange capacity of the compound represented by the following formula (2) is preferably 6.2 meq/g or more, more preferably 6.7 meq/g or more. TiH a (PO 4)b ·nH 2 O (2) Among formula (2), a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, n is a positive number of 0≦n≦2.0 .
α磷酸鈦之前述式(2)中的n是以0.2以下為佳,較佳為0.1以下,更佳為0.05以下。藉由將n的值設為2.0以下,在紡線時的樹脂熔融之際,結晶水會脫離,能防止發泡或線斷裂。n in the aforementioned formula (2) of α-titanium phosphate is preferably 0.2 or less, more preferably 0.1 or less, more preferably 0.05 or less. By setting the value of n to 2.0 or less, when the resin is melted during yarn spinning, water of crystallization is desorbed, and foaming and yarn breakage can be prevented.
α磷酸鈦之製造方法,能應用習知技術,對於原料或設備等不設限制。 作為α磷酸鈦之製造方法,在水溶液中使原料化合物進行反應之方法因為能容易獲得均勻的粒子,故屬較佳。 例如,能採用於鈦化合物之水溶液中加入磷酸使沈澱物生成,並使其結晶化之方式製造。 例如,可舉出將鈦化合物之水溶液與含有磷酸(鹽)之水溶液混合使沈澱物生成,並經過熟成使其結晶化之方法等。The production method of α-titanium phosphate can be applied to conventional techniques, and there is no limitation on raw materials or equipment. As a method for producing α-titanium phosphate, a method of reacting raw material compounds in an aqueous solution is preferable because uniform particles can be easily obtained. For example, it can be produced by adding phosphoric acid to an aqueous solution of a titanium compound to form a precipitate and crystallize it. For example, a method of mixing an aqueous solution of a titanium compound and an aqueous solution containing phosphoric acid (salt) to form a precipitate, followed by aging to crystallize it, and the like.
作為製造原料之鈦化合物,可舉出硫酸鈦等。 作為製造原料的磷酸(鹽),可舉出與前述同樣的化合物。Titanium sulfate etc. are mentioned as a titanium compound of a manufacturing raw material. Examples of the phosphoric acid (salt) as the raw material for production include the same compounds as those described above.
3.除臭劑中的水分含有率 本實施型態所使用的除臭劑之水分含有率是以1.0重量%以下為佳。更佳為0.7重量%以下。藉由將水分含有率設為1.0重量%以下,製作母批料時能防止樹脂之發泡或水解,故屬較佳。3. Moisture content in deodorant The moisture content of the deodorant used in this embodiment is preferably 1.0% by weight or less. More preferably, it is 0.7 weight% or less. By setting the moisture content to 1.0% by weight or less, foaming or hydrolysis of the resin can be prevented when making a master batch, which is preferable.
4.除臭性纖維 本實施態樣為纖維用除臭劑,而作為使用該除臭劑製造除臭性纖維之方法,依循常規方法即可。 例如,可舉出將本實施態樣之除臭劑混入纖維並紡線之方法、或在紡線後之纖維塗布除臭劑溶液之方法等。4. Deodorant fiber This embodiment is a deodorant for fiber, and as a method of producing deodorant fiber using this deodorant, it is sufficient to follow a conventional method. For example, the method of mixing the deodorant of this embodiment into a fiber and spinning it, or the method of coating a deodorant solution on the fiber after spinning, etc. are mentioned.
作為可使用的纖維用樹脂,任一周知之化學纖維皆可使用。作為較佳具體例,可舉例如聚酯、聚胺甲酸酯、耐綸、人造絲、壓克力、維尼綸及聚丙烯等。該等樹脂可為單獨聚合物亦或共聚物。若為共聚物,對於各個共聚合成份之聚合比例並無特別限制。Any known chemical fiber can be used as the usable fiber resin. Preferred specific examples include polyester, polyurethane, nylon, rayon, acrylic, vinylon, and polypropylene. These resins may be single polymers or copolymers. In the case of a copolymer, there is no particular limitation on the polymerization ratio of each copolymerization component.
本實施態樣之除臭劑是以作為纖維混入用除臭劑來使用為佳。 此情況下作為除臭性纖維之具體的製造方法,將本實施態樣之除臭劑混入已熔融之液狀纖維用樹脂或者已溶解之纖維用樹脂溶液,並將其紡線之方法等。The deodorant of this embodiment is preferably used as a deodorant for fiber mixing. In this case, as a specific production method of the deodorant fiber, there is a method in which the deodorant of this embodiment is mixed with molten liquid fiber resin or dissolved fiber resin solution, and the method is spun.
纖維用樹脂所含有的本實施態樣之除臭劑的比例並無特別限定。 一般來說若增加含量就能強力發揮除臭性並長時間持續,然而就算含有特定程度以上的量,除臭效果亦不會有太大差異,或者會有樹脂強度降低之情形,較佳為樹脂每100重量份就有0.1~3.0重量份,更佳為0.5~2.0重量份。The ratio of the deodorant of this embodiment contained in resin for fibers is not specifically limited. Generally speaking, if the content is increased, the deodorant effect can be strongly exerted and lasted for a long time. However, even if the content exceeds a certain level, the deodorizing effect will not be much different, or the resin strength will decrease. It is better to use There are 0.1-3.0 parts by weight per 100 parts by weight of the resin, more preferably 0.5-2.0 parts by weight.
使用了本實施態樣之除臭劑的除臭性纖維,能使用於視除臭性為必需之各種領域,使用於例如內衣、絲襪、襪子、棉被、被套、座墊、被毯、地毯、窗簾、沙發、汽車座墊、空氣濾網及照護用衣服等許多纖維製品。 [實施例]The deodorant fiber using the deodorant of this embodiment can be used in various fields where deodorization is necessary, such as underwear, stockings, socks, quilts, quilt covers, seat cushions, quilt blankets, and carpets , curtains, sofas, car seat cushions, air filters and nursing clothes and many other fiber products. [Example]
其次,根據實施例及比較例具體地說明本發明,然而本發明並不受以下實施例限制。除臭劑之物性及除臭性能是依據下述方法進行測定。Next, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the following examples. The physical properties and deodorizing performance of the deodorant were measured in accordance with the following methods.
(1)粒徑︰中值粒徑、最大粒徑、D10徑 除臭劑之粒徑測定是以(股)堀場製作所製之雷射繞射式粒度分佈測定裝置「LA-950」進行測定,將結果以體積基準進行解析。 測定條件是將相對於水100重量%添加了1.0重量%除臭劑之除臭劑分散液以超音波進行分散,在折射率2.4下進行測定。(1) Particle size: Median particle size, maximum particle size, and D10 diameter The particle size measurement of deodorants is carried out by the laser diffraction particle size distribution measuring device "LA-950" manufactured by Horiba Seisakusho Co., Ltd. The results are parsed on a volumetric basis. The measurement conditions were such that a deodorant dispersion liquid in which 1.0% by weight of a deodorant was added to 100% by weight of water was dispersed with ultrasonic waves, and the measurement was performed at a refractive index of 2.4.
(2)紡線性試驗 製造出相對於聚酯樹脂(Unitika製MA2101M)100重量%添加了10重量%除臭劑之母批料。接著,將該母批料與不含除臭劑之聚酯樹脂顆粒混合,調整成各添加量(重量%)。使用複絲紡線機將其以紡線溫度275℃、紡線速度500m/分鐘進行紡線2小時,使伸度成為280~320%之方式在120℃下進行延伸,獲得含有除臭劑之聚酯纖維。 此時,油劑是使用通常用於聚酯纖維紡線之水溶性油劑(將竹本油脂(股)製DELION6033以水稀釋10倍)。 進行連續紡線2小時,並依據以下判定方法對紡線性進行評價。線斷率越小,紡線性越優異。 ○○︰線斷率為小於3.0% ○︰線斷率為3.0%以上,小於6.0% △︰線斷率為6.0%以上,小於10.0% ╳︰線斷率為10.0%以上 ─︰無法評價(2) Spinning linearity test A master batch in which 10% by weight of a deodorant was added to 100% by weight of a polyester resin (MA2101M manufactured by Unitika) was produced. Next, this master batch was mixed with polyester resin pellets not containing a deodorant, and each addition amount (% by weight) was adjusted. Using a multifilament spinning machine, it was spun at a spinning temperature of 275°C and a spinning speed of 500m/min for 2 hours, and stretched at 120°C so that the elongation became 280-320%, and a deodorant-containing product was obtained. Polyester. At this time, as the oil agent, a water-soluble oil agent (DELION 6033 manufactured by Takemoto Oil & Fat Co., Ltd. was diluted 10 times with water) that is generally used for polyester fiber spinning was used. Continuous spinning was carried out for 2 hours, and the spinning property was evaluated according to the following determination method. The smaller the thread breakage rate, the better the spinnability. ○○: wire breakage rate is less than 3.0% ○: wire breakage rate is more than 3.0% and less than 6.0% △: wire breakage rate is more than 6.0% and less than 10.0% ╳: wire breakage rate is more than 10.0% ─: cannot be evaluated
(3)除臭性試驗1 除臭性試驗是依據除臭加工纖維製品認證基準(制定者︰日本社團法人纖維評價技術協議會之製品認證部,制定日︰平成14年(2002年)9月1日),如下述般以機器試驗進行臭氣成份之除臭性評價。此外,社團法人纖維評價技術協議會依據該機器分析試驗將各臭氣成份的減少率判定為「具有除臭效果」之合格基準標示於表1。 ○檢測管法 1.將上述(2)製作的延伸線作圓筒編織並進行鹼減量處理(於4重量%氫氧化鈉水溶液中煮沸1小時,浴比=1/40)後獲得之物調整成10cm×10cm,放入採氣袋(Tedlar Bag)。 2.注入表1所示之特定量的試驗氣體,將2小時之後的殘存氣體濃度(ppm)用成份對應檢測管(Gastec社製)進行測定,算出殘存氣體濃度之減少率並紀錄作為除臭率。測定是以n=3之平均值求得。此外,氣體填充量為3L,稀釋氣體使用乾燥空氣或氮氣氣體。(3) Deodorization test 1 The deodorization test is based on the certification standard for deodorized processed fiber products (developer: Product Certification Department of Japan Association for Fiber Evaluation Technology Association, date of formulation: September 2002 1 day), as follows, the deodorization evaluation of odor components was carried out by machine test. In addition, the fiber evaluation technology association of the corporate juridical person judges the reduction rate of each odor component as "having a deodorizing effect" based on the machine analysis test, and marks it in Table 1. ○Detection tube method 1. Adjustment of the product obtained by cylindrically braiding the extension thread produced in (2) above and performing alkali weight reduction treatment (boiling in 4% by weight sodium hydroxide aqueous solution for 1 hour, bath ratio = 1/40) into 10cm×10cm and put into a Tedlar Bag. 2. Inject a specific amount of test gas shown in Table 1, measure the residual gas concentration (ppm) after 2 hours with a component-corresponding detection tube (manufactured by Gastec), calculate the reduction rate of the residual gas concentration and record it as deodorization Rate. The determination is obtained by the average value of n=3. In addition, the gas filling volume is 3L, and the dilution gas uses dry air or nitrogen gas.
(4)除臭性試驗2(耐久性試驗) 將上述(3)之1當中經過鹼減量處理之圓筒編織纖維進行洗滌10次後,以上述(3)之2記載的檢測管法進行測定。(4) Deodorization test 2 (durability test) After washing the cylindrical braided fibers subjected to the alkali weight reduction treatment in the above (3) 1 for 10 times, it was measured by the detection tube method described in the above (3) 2 .
(5)水分含有率 水分含有率是將實施例及比較例所獲得之除臭劑在150℃下加熱2小時,藉由[(加熱後重量-加熱前重量)/加熱前重量]計算出。 結果為實施例1~4是0.3重量%,實施例5~12是0.4重量%,比較例1~10是0.3重量%,比較例11~14是0.4重量%。(5) Moisture content The moisture content was calculated by [(weight after heating-weight before heating)/weight before heating] by heating the deodorants obtained in Examples and Comparative Examples at 150°C for 2 hours. As a result, it was 0.3 weight% in Examples 1-4, 0.4 weight% in Examples 5-12, 0.3 weight% in Comparative Examples 1-10, and 0.4 weight% in Comparative Examples 11-14.
[表1]
<實施例1、2> 於2L圓底燒瓶加入去離子水1160mL及35%鹽酸173.4g,並追加含鉿0.18%之氧氯化鋯8水合物20%水溶液288.4g後,將草酸2水合物119.2g溶解於其中。將該溶液一邊仔細攪拌一邊加入75%磷酸134.4g。花2小時將其升溫至98℃,並進行攪拌回流12小時。冷卻後,將獲得的沈澱物仔細水洗洗淨後,在105℃下進行乾燥,獲得磷酸鋯。將其以轉子高速粉碎機(FRITSCH社製,P-14(1997年製)︰16000rpm,網眼80μm)進行粉碎。對於此獲得之磷酸鋯進行測定之結果,確認其為α磷酸鋯。 對於該α磷酸鋯之組成式等進行測定,組成式為︰ Zr0.99 Hf0.01 H2.03 (PO4 )2.01 ・0.05H2 O 中值粒徑0.51μm、最大粒徑2.5μm、D10徑0.22μm。細節標示於表2。<Examples 1 and 2> Add 1160mL of deionized water and 173.4g of 35% hydrochloric acid to a 2L round bottom flask, and add 288.4g of 20% aqueous solution of zirconium oxychloride hexahydrate containing 0.18% of hafnium, and dihydrate the oxalic acid dihydrate 119.2 g dissolved therein. While carefully stirring this solution, 134.4 g of 75% phosphoric acid was added. It was heated to 98°C over 2 hours, and stirred and refluxed for 12 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain zirconium phosphate. This was pulverized with a rotor high-speed pulverizer (manufactured by FRITSCH, P-14 (manufactured in 1997): 16000 rpm, mesh 80 μm). As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate. The compositional formula of the α-zirconium phosphate was measured, and the compositional formula was: Zr 0.99 Hf 0.01 H 2.03 (PO 4 ) 2.01 ·0.05H 2 O with a median particle size of 0.51 μm, a maximum particle size of 2.5 μm, and a D10 diameter of 0.22 μm. Details are indicated in Table 2.
<實施例3、4> 於2L圓底燒瓶加入去離子水1056mL及35%鹽酸185.2g,並追加含鉿0.18%之氧氯化鋯8水合物20%水溶液322.7g後,將草酸2水合物109.2g溶解於其中。將該溶液一邊仔細攪拌一邊加入75%磷酸160.8g。花2小時將其升溫至98℃,並進行攪拌回流12小時。冷卻後,將獲得的沈澱物仔細水洗洗淨後,在105℃下進行乾燥,獲得磷酸鋯。對於此獲得之磷酸鋯進行測定之結果,確認其為α磷酸鋯。 對於該α磷酸鋯之組成式等進行測定,組成式為︰ Zr0.99 Hf0.01 H2.03 (PO4 )2.01 ・0.05H2 O 中值粒徑0.22μm、最大粒徑2.2μm、D10徑0.15μm。細節標示於表2。<Example 3, 4> Add 1056mL of deionized water and 185.2g of 35% hydrochloric acid to a 2L round bottom flask, and add 322.7g of 20% aqueous solution of zirconium oxychloride hexahydrate containing 0.18% of hafnium, and dihydrate oxalic acid 109.2 g were dissolved therein. While carefully stirring this solution, 160.8 g of 75% phosphoric acid was added. It was heated to 98°C over 2 hours, and stirred and refluxed for 12 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain zirconium phosphate. As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate. The compositional formula of the α-zirconium phosphate was measured, and the compositional formula was: Zr 0.99 Hf 0.01 H 2.03 (PO 4 ) 2.01・0.05H 2 O with a median particle size of 0.22 μm, a maximum particle size of 2.2 μm, and a D10 diameter of 0.15 μm. Details are indicated in Table 2.
<實施例5、6> 於500mL圓底燒瓶加入去離子水228.75mL,並加入75%磷酸202.7g。一邊仔細攪拌一邊加入硫酸鈦68.55g,並繼續攪拌10分鐘。其後,花1小時將其升溫至100℃,並進行攪拌回流44小時。冷卻後,將獲得的沈澱物仔細水洗洗淨後,在105℃下進行乾燥,獲得磷酸鈦。對於此獲得之磷酸鈦進行測定之結果,確認其為α磷酸鈦。 對於該α磷酸鈦之組成式等進行測定,組成式為︰ TiH2.02 (PO4 )2.01 ・0.05H2 O 中值粒徑0.56μm、最大粒徑2.6μm、D10徑0.25μm。細節標示於表2。<Examples 5 and 6> 228.75 mL of deionized water and 202.7 g of 75% phosphoric acid were added to a 500 mL round bottom flask. While carefully stirring, 68.55 g of titanium sulfate was added, and stirring was continued for 10 minutes. Thereafter, it was heated up to 100° C. over 1 hour, and stirred and refluxed for 44 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain titanium phosphate. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The compositional formula of the α-titanium phosphate was measured, and the compositional formula was: TiH 2.02 (PO 4 ) 2.01 ·0.05H 2 O with a median particle size of 0.56 μm, a maximum particle size of 2.6 μm, and a D10 size of 0.25 μm. Details are indicated in Table 2.
<實施例7、8> 於500mL圓底燒瓶加入去離子水228.75mL,並加入75%磷酸202.7g。一邊仔細攪拌一邊加入硫酸鈦68.55g,並繼續攪拌10分鐘。其後,花1小時將其升溫至85℃,並進行攪拌回流20小時。冷卻後,將獲得的沈澱物仔細水洗洗淨後,在105℃下進行乾燥,獲得磷酸鈦。對於此獲得之磷酸鈦進行測定之結果,確認其為α磷酸鈦。 對於該α磷酸鈦之組成式等進行測定,組成式為︰ TiH2.02 (PO4 )2.01 ・0.05H2 O 中值粒徑0.21μm、最大粒徑2.2μm、D10徑0.14μm。細節標示於表2。<Examples 7 and 8> 228.75 mL of deionized water and 202.7 g of 75% phosphoric acid were added to a 500 mL round bottom flask. While carefully stirring, 68.55 g of titanium sulfate was added, and stirring was continued for 10 minutes. Thereafter, it was heated up to 85° C. over 1 hour, and stirred and refluxed for 20 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain titanium phosphate. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The compositional formula of the α-titanium phosphate was measured, and the compositional formula was: TiH 2.02 (PO 4 ) 2.01 ·0.05H 2 O with a median particle size of 0.21 μm, a maximum particle size of 2.2 μm, and a D10 size of 0.14 μm. Details are indicated in Table 2.
<實施例9、10> 將實施例1合成之α磷酸鋯與實施例5合成之α磷酸鈦以1︰1混合之物作為除臭劑使用。 該混合物之中值粒徑、最大粒徑、D10徑標示於表2。<Examples 9 and 10> The α-zirconium phosphate synthesized in Example 1 and the α-titanium phosphate synthesized in Example 5 were mixed at a ratio of 1:1 and used as a deodorant. The median diameter, maximum particle diameter, and D10 diameter of the mixture are shown in Table 2.
<實施例11、12> 將實施例3合成之α磷酸鋯與實施例7合成之α磷酸鈦以1︰1混合之物作為除臭劑使用。 該混合物之中值粒徑、最大粒徑、D10徑標示於表2。<Examples 11 and 12> The α-zirconium phosphate synthesized in Example 3 and the α-titanium phosphate synthesized in Example 7 were mixed at a ratio of 1:1 and used as a deodorant. The median diameter, maximum particle diameter, and D10 diameter of the mixture are shown in Table 2.
<比較例1、2> 使用東亞合成(股)公司製之磷酸鋯系除臭劑「Kesmon NS-10」。該製品之細節如表3所示。<Comparative Examples 1 and 2> A zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. was used. Details of the preparation are shown in Table 3.
<比較例3、4> 於500mL圓底燒瓶加入去離子水95mL,並加入75%磷酸1800g。一邊仔細攪拌一邊追加含鉿0.18%之氧氯化鋯8水合物20%水溶液360g後,花1小時升溫至98℃,並進行攪拌回流12小時。 對於此獲得之磷酸鈦進行測定之結果,確認其為α磷酸鈦。中值粒徑0.11μm、最大粒徑1.4μm、D10徑0.05μm。細節標示於表3。<Comparative examples 3 and 4> 95 mL of deionized water and 1800 g of 75% phosphoric acid were added to a 500 mL round bottom flask. After adding 360 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium while carefully stirring, the temperature was raised to 98° C. over 1 hour, and stirred and refluxed for 12 hours. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The median particle size is 0.11 μm, the maximum particle size is 1.4 μm, and the D10 diameter is 0.05 μm. Details are indicated in Table 3.
<比較例5、6> 於2L圓底燒瓶加入去離子水1500mL,並追加含鉿0.18%之氧氯化鋯8水合物20%水溶液210g後,將草酸2水合物240g溶解於其中。將該溶液一邊仔細攪拌一邊加入75%磷酸90g。花2小時將其升溫至98℃,並進行攪拌回流24小時。冷卻後,將獲得的沈澱物仔細水洗洗淨後,在105℃下進行乾燥,獲得磷酸鋯。對於此獲得之磷酸鋯進行測定之結果,確認其為α磷酸鋯。 對於該α磷酸鋯之組成式等進行測定,組成式為︰ Zr0.99 Hf0.01 H2.03 (PO4 )2.01 ・0.05H2 O 中值粒徑2.1μm、最大粒徑10.0μm、D10徑0.81μm。細節標示於表3。<Comparative Examples 5 and 6> 1500 mL of deionized water was added to a 2L round bottom flask, and 210 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% of hafnium was added, and 240 g of oxalic acid dihydrate was dissolved therein. While carefully stirring this solution, 90 g of 75% phosphoric acid was added. It was heated to 98°C over 2 hours and refluxed with stirring for 24 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain zirconium phosphate. As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate. The compositional formula of the α-zirconium phosphate was measured, and the compositional formula was: Zr 0.99 Hf 0.01 H 2.03 (PO 4 ) 2.01・0.05H 2 O with a median particle size of 2.1 μm, a maximum particle size of 10.0 μm, and a D10 diameter of 0.81 μm. Details are indicated in Table 3.
<比較例7、8> 將東亞合成(股)公司製之磷酸鋯系除臭劑「Kesmon NS-10」10%分散於水,投入50重量%的30μm之二氧化鋯粒,使用Disper(特殊機化工業(股)公司製(現.PRIMIX(股)公司),Homodisper,model L(1994年製))在轉數3000rpm下進行2小時濕式粉碎。中值粒徑0.52μm、最大粒徑5.1μm、D10徑0.07μm。細節標示於表3。<Comparative Examples 7 and 8> Disperse 10% of the zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. in water, add 50% by weight of 30 μm zirconia particles, and use Disper (special A Homodisper, model L (manufactured in 1994) manufactured by Kikka Kogyo Co., Ltd. (currently PRIMIX Co., Ltd.) was subjected to wet pulverization at a rotation speed of 3000 rpm for 2 hours. The median particle size is 0.52 μm, the maximum particle size is 5.1 μm, and the D10 diameter is 0.07 μm. Details are indicated in Table 3.
<比較例9、10> 將東亞合成(股)公司製之磷酸鋯系除臭劑「Kesmon NS-10」10%分散於水,投入50重量%的10μm之二氧化鋯粒,使用Disper在轉數3000rpm下進行2小時濕式粉碎。中值粒徑0.2μm、最大粒徑4.5μm、D10徑0.05μm。細節標示於表3。<Comparative Examples 9 and 10> Disperse 10% of the zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. in water, add 50% by weight of 10μm zirconia particles, and use Disper to turn Wet pulverization was carried out at 3000 rpm for 2 hours. The median particle size is 0.2 μm, the maximum particle size is 4.5 μm, and the D10 diameter is 0.05 μm. Details are indicated in Table 3.
<比較例11、12> 於500mL圓底燒瓶加入去離子水228.75mL,並加入75%磷酸202.7g。一邊仔細攪拌一邊加入硫酸鈦68.55g,並繼續攪拌10分鐘。其後,花1小時升溫至100℃,並進行攪拌回流100小時。冷卻後,將獲得的沈澱物仔細水洗洗淨後,在105℃下進行乾燥,獲得磷酸鈦。 對於此獲得之磷酸鈦進行測定之結果,確認其為α磷酸鈦。 對於該α磷酸鈦之組成式等進行測定,組成式為︰ TiH2.02 (PO4 )2.01 ・0.05H2 O 中值粒徑1.05μm、最大粒徑5.8μm、D10徑0.51μm。細節標示於表3。<Comparative examples 11 and 12> 228.75 mL of deionized water and 202.7 g of 75% phosphoric acid were added to a 500 mL round bottom flask. While carefully stirring, 68.55 g of titanium sulfate was added, and stirring was continued for 10 minutes. Thereafter, the temperature was raised to 100° C. over 1 hour, and stirred and refluxed for 100 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain titanium phosphate. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The compositional formula of the α-titanium phosphate was measured, and the compositional formula was: TiH 2.02 (PO 4 ) 2.01 ·0.05H 2 O with a median particle size of 1.05 μm, a maximum particle size of 5.8 μm, and a D10 size of 0.51 μm. Details are indicated in Table 3.
<比較例13、14> 將比較例6所合成之α磷酸鈦10%分散於水,投入50wt%的30μm之二氧化鋯粒,使用Disper在轉數3000rpm下進行2小時濕式粉碎。中值粒徑0.49μm、最大粒徑5.2μm、D10徑0.06μm。細節標示於表3。<Comparative Examples 13 and 14> Disperse 10% of α-titanium phosphate synthesized in Comparative Example 6 in water, add 50wt% of 30 μm zirconia particles, and perform wet pulverization for 2 hours at 3000 rpm using Disper. The median particle size is 0.49 μm, the maximum particle size is 5.2 μm, and the D10 diameter is 0.06 μm. Details are indicated in Table 3.
<比較例15、16> 使用TAYCA(股)公司製之三聚磷酸二氫鋁系除臭劑「K-FRESH 100P」。中值粒徑1.1μm、最大粒徑5.9μm、D10徑0.55μm。細節標示於表3。<Comparative examples 15 and 16> Aluminum dihydrogen tripolyphosphate deodorant "K-FRESH 100P" manufactured by TAYCA Co., Ltd. was used. The median particle size is 1.1 μm, the maximum particle size is 5.9 μm, and the D10 diameter is 0.55 μm. Details are indicated in Table 3.
<參考例> 不添加除臭劑而是直接紡線、圓筒編織並進行除臭評價。<Reference example> The deodorant evaluation was carried out without adding a deodorant, and directly spinning and cylindrical knitting.
實施例所使用的除臭劑有優異紡線性而不須擔心線斷裂。添加了實施例之除臭劑的纖維有優異除臭性能,洗滌後亦維持有除臭性能。 另一方面,比較例所使用的除臭劑在紡線性或除臭性能方面,亦或是兩方面皆表現不佳。而鹼處理導致之減量率在全部樣本當中為13~18重量%。The deodorants used in the examples have excellent spinnability without fear of thread breakage. The fiber added with the deodorant of the example has excellent deodorizing performance and maintains deodorizing performance after washing. On the other hand, the deodorants used in the comparative examples were not good in spinnability, deodorant performance, or both. The weight loss rate caused by alkali treatment was 13-18% by weight in all samples.
[表2] [Table 2]
[表3] [table 3]
產業上之可利用性 本發明之除臭劑屬於微粒子且粒度分佈之寬度狹小,故紡線性優異。又,特別是混入了纖維者對於氨的除臭性能優異,耐洗滌性亦高。Industrial Applicability The deodorant of the present invention is fine particles and has a narrow particle size distribution, so it has excellent spinnability. In addition, especially those mixed with fibers have excellent deodorizing performance against ammonia and have high washing resistance.
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TW200819391A (en) * | 2006-10-27 | 2008-05-01 | Toagosei Co Ltd | Novel lamellar zirconium phosphate |
TW201610248A (en) * | 2014-05-29 | 2016-03-16 | 東麗奧培隆特士股份有限公司 | Deodorant fabric |
WO2016194995A1 (en) * | 2015-06-04 | 2016-12-08 | 東亞合成株式会社 | Ion scavenger for lithium ion secondary cell, liquid electrolyte, separator, and lithium ion secondary cell |
CN106255533A (en) * | 2014-06-20 | 2016-12-21 | 东亚合成株式会社 | Deodorant mask |
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TW200819391A (en) * | 2006-10-27 | 2008-05-01 | Toagosei Co Ltd | Novel lamellar zirconium phosphate |
TW201610248A (en) * | 2014-05-29 | 2016-03-16 | 東麗奧培隆特士股份有限公司 | Deodorant fabric |
CN106255533A (en) * | 2014-06-20 | 2016-12-21 | 东亚合成株式会社 | Deodorant mask |
WO2016194995A1 (en) * | 2015-06-04 | 2016-12-08 | 東亞合成株式会社 | Ion scavenger for lithium ion secondary cell, liquid electrolyte, separator, and lithium ion secondary cell |
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