TW201834743A - Adsorbent for acidic gas, deodorant, and deodorizing product - Google Patents
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發明領域 本發明係有關於由矽酸鈉構成之酸性氣體用吸附劑，較佳為有關於由結晶質矽酸鈉構成之酸性氣體用吸附劑。本發明又有關於提供使用該吸附劑之除臭劑以及紙、纖維、薄膜、塑膠成形品等除臭加工製品，因該吸附劑之加工性優越，即使與樹脂等捏合加工也無樹脂劣化及染色的情形，故使用該吸附劑會發揮優越除臭性能。FIELD OF THE INVENTION The present invention relates to an acid gas adsorbent comprising sodium citrate, and more preferably to an acid gas adsorbent composed of crystalline sodium citrate. Further, the present invention relates to a deodorant using the adsorbent, and a deodorant processed product such as paper, fiber, film, or plastic molded article, which is excellent in processability, and has no resin deterioration even when kneaded with a resin or the like. In the case of dyeing, the use of the adsorbent exerts superior deodorizing performance.
發明背景 近年來，針對日常生活中之臭味的關注日益增加，室內置放型或噴霧型之除臭製品、除臭壁紙、除臭簾及除臭衣物等各式各樣的除臭加工製品被提出。這些除臭製品或除臭加工製品是使用由無機系吸附劑構成之除臭劑予以塗覆或於加工時捏合而發揮除臭性能。 臭味有酸性氣體、鹼性氣體及硫系氣體等，依據構成除臭劑之吸附劑的種類，對這些目標臭味具選擇性，因此必須選定適合產生之臭味的吸附劑來使用。 汗臭、體臭及寵物臭等中所含的醋酸及異戊酸等酸性氣體為與生活緊密連接之應用下產生之不易除臭的一種臭味，因此有增添了除臭性能及安全性之多種吸附劑被提出。BACKGROUND OF THE INVENTION In recent years, attention has been paid to the odor in daily life, and various deodorizing processed products such as deodorizing products, deodorizing wallpapers, deodorizing curtains, and deodorizing clothes, which are built-in or spray-type in the room. Been proposed. These deodorant products or deodorant processed products are coated with a deodorant composed of an inorganic adsorbent or kneaded at the time of processing to exhibit deodorizing performance. The odor includes an acid gas, an alkaline gas, a sulfur-based gas, and the like, and depending on the type of the adsorbent constituting the deodorant, these target odors are selective. Therefore, it is necessary to select an adsorbent suitable for the generated odor. Acidic gases such as acetic acid and isovaleric acid contained in sweat odor, body odor, and pet odor are odors that are not easily deodorized by applications that are closely connected with life, and thus have added deodorizing performance and safety. A variety of adsorbents have been proposed.
以往，已提出使用了各種無機系吸附劑之除臭劑以作為酸性氣體用除臭劑。 例如，專利文獻1揭露了一種酸性成分吸附劑，其特徵為將再水合性氧化鋁粉末成形，接著保持在室溫~120℃的水蒸氣環境下後燒製而獲得氧化鋁載體，然後使以氧化物換算計2~15質量%的氧化鋁金屬鹽受載於該氧化鋁載體而成。專利文獻2揭露了一種作為除臭劑之水合氧化鋯，其可消除肇因於醋酸、異戊酸及丁酸等酸性氣體之惡臭。專利文獻3揭露了一種作為除臭劑之水合氧化鋯，其可消除肇因於醋酸、異戊酸及丁酸等酸性氣體之惡臭。專利文獻4揭露了一種除臭劑，其係含有成分(a)三聚磷酸鋁、成分(b)氧化鋅、成分(c)膨潤石及成分(d)水而成，該除臭劑對含有醋酸等之惡臭具有除臭效果。專利文獻5記載了使用被賦予多種除臭劑之布料的內部裝潢，且揭露了一種作為除臭劑之氧化鋅，其對酸性氣體類的臭味有效。Conventionally, deodorants using various inorganic adsorbents have been proposed as deodorants for acid gases. For example, Patent Document 1 discloses an acidic component adsorbent characterized in that a rehydration alumina powder is formed, followed by being maintained in a water vapor atmosphere at room temperature to 120 ° C, and then fired to obtain an alumina carrier, and then 2 to 15% by mass of an alumina metal salt in an oxide conversion amount is contained in the alumina carrier. Patent Document 2 discloses a hydrated zirconia as a deodorant which can eliminate the odor caused by acid gases such as acetic acid, isovaleric acid and butyric acid. Patent Document 3 discloses a hydrated zirconia as a deodorant which can eliminate the odor caused by acid gases such as acetic acid, isovaleric acid and butyric acid. Patent Document 4 discloses a deodorant comprising a component (a) aluminum tripolyphosphate, a component (b) zinc oxide, a component (c) bentonite, and a component (d) water, and the deodorant pair contains The malodor of acetic acid or the like has a deodorizing effect. Patent Document 5 describes an interior decoration using a cloth to which a plurality of deodorants are applied, and discloses zinc oxide as a deodorant which is effective for an acid gas-based odor.
先前技術文獻 專利文獻 專利文獻1：日本特開平6-190274號公報 專利文獻2：日本特開平10-155884號公報 專利文獻3：日本特開2002-200149號公報 專利文獻4：日本特開2009-90012號公報 專利文獻5：日本特開2014-54754號公報CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document No. 90012: Japanese Laid-Open Patent Publication No. 2014-54754
發明概要 發明欲解決之課題 雖然上述提出之酸性氣體用除臭劑展現吸附酸性氣體的效果，但其吸附容量並不足夠，故加工於紙、纖維及塑膠等基材時，必須要有非常多的加工量。並且因為酸性氣體用除臭劑有許多顯示為鹼性的材料，會使經加工之樹脂基材劣化，以致經常會有物性下降或吸附劑脫落之情形，尤其越是酸性氣體吸附效果優越的鋅化合物或鹼性強的除臭劑，這樣的傾向就越強烈。 因此本發明之課題為提供一種對酸性氣體的吸附性高、且摻合於樹脂等時不易發生樹脂劣化之吸附劑。又，本發明之課題為提供使用該吸附劑而發揮優越除臭性能的除臭劑以及紙、不織布及纖維等除臭加工製品。SUMMARY OF THE INVENTION Problems to be Solved by the Invention Although the deodorant for acid gas proposed above exhibits an effect of adsorbing an acid gas, its adsorption capacity is not sufficient, so it is necessary to process a substrate such as paper, fiber or plastic. The amount of processing. Moreover, since the deodorant for acid gas has many materials which are alkaline, the processed resin substrate is deteriorated, so that the physical property is often lowered or the adsorbent is detached, and in particular, the zinc gas having superior acid gas adsorption effect is superior. The tendency of such a compound or a strong deodorant is stronger. Therefore, an object of the present invention is to provide an adsorbent which has high adsorptivity to an acid gas and which is less likely to cause deterioration of the resin when blended with a resin or the like. Further, an object of the present invention is to provide a deodorant which exhibits superior deodorizing performance using the adsorbent, and a deodorant processed product such as paper, nonwoven fabric and fiber.
用以解決課題之手段 本案發明人發現一種優異的吸附劑，其使用由矽酸鈉構成之酸性氣體用吸附劑而展現極高除臭性能。又發現該吸附劑即使與樹脂摻合也不易引起樹脂劣化，經塗佈該吸附劑或與該吸附劑捏合加工之紙、不織布、纖維、塑膠成形品等未有染色或變色等之外觀瑕疵，且展現高除臭性能。 亦即，本發明表示於下。 ＜1＞一種酸性氣體用吸附劑，係由矽酸鈉構成。 ＜2＞如上述＜1＞之酸性氣體用吸附劑，其中矽酸鈉係以下式(1)表示： Na2 O・mSiO2 ・nH2 O (1) 式(1)中，m及n為正數且為符合m=0.8~4.4、n=0.01~8.0之數值。 ＜3＞如上述＜1＞或＜2＞之酸性氣體用吸附劑，其醋酸氣體化學吸附容量為20mL/g以上。 ＜4＞如上述＜1＞至＜3＞中任一酸性氣體用吸附劑，其經雷射繞射粒度分佈儀測定之平均粒度為0.1μm~20μm。 ＜5＞如上述＜1＞至＜4＞中任一酸性氣體用吸附劑，其中矽酸鈉為結晶質。 ＜6＞一種除臭劑，包含上述＜1＞至＜5＞中任一酸性氣體用吸附劑。 ＜7＞一種除臭加工製品，係將上述＜1＞至＜5＞中任一酸性氣體用吸附劑塗佈於樹脂或與樹脂捏合加工者。Means for Solving the Problem The inventors of the present invention have found an excellent adsorbent which exhibits extremely high deodorizing performance by using an adsorbent for acid gas composed of sodium citrate. Further, it has been found that the adsorbent does not easily cause deterioration of the resin even when it is blended with the resin, and the coating, the non-woven fabric, the fiber, the plastic molded article, and the like which are kneaded with the adsorbent are not stained or discolored, and the like. And exhibits high deodorizing performance. That is, the present invention is shown below. <1> An adsorbent for acid gas, which is composed of sodium citrate. <2> The adsorbent for acid gas according to <1> above, wherein sodium citrate is represented by the following formula (1): Na 2 O, mSiO 2 , nH 2 O (1) In the formula (1), m and n are Positive numbers are in accordance with the values of m=0.8~4.4 and n=0.01~8.0. <3> The adsorbent for an acid gas according to <1> or <2> above, wherein the acetic acid gas chemisorption capacity is 20 mL/g or more. <4> The adsorbent for acid gas according to any one of <1> to <3> above which has an average particle size of 0.1 μm to 20 μm as measured by a laser diffraction particle size distribution analyzer. <5> The adsorbent for an acid gas according to any one of <1> to <4> above, wherein the sodium citrate is crystalline. <6> A deodorant comprising the adsorbent for an acid gas according to any one of <1> to <5> above. <7> A deodorant-processed product which is obtained by applying the adsorbent for any of the above-mentioned <1> to <5> to a resin or kneading with a resin.
發明效果 本發明之酸性氣體用吸附劑(以下僅稱作「吸附劑」)除了對醋酸及異戊酸等之酸性氣體有優越的吸附性，且摻合於樹脂等時不易發生樹脂劣化。吸附劑的色調為白色，可於紙及纖維等製品進行塗佈或捏合加工，從而可提供使用該吸附劑而發揮優越除臭性能的除臭劑以及紙、不織布及纖維等除臭加工製品。EFFECTS OF THE INVENTION The acid gas adsorbent of the present invention (hereinafter simply referred to as "adsorbent") has excellent adsorptivity to an acid gas such as acetic acid or isovaleric acid, and is less likely to cause deterioration of the resin when it is blended with a resin or the like. The color tone of the adsorbent is white, and it can be applied or kneaded in a product such as paper or fiber, thereby providing a deodorant which exhibits superior deodorizing performance using the adsorbent, and a deodorant processed product such as paper, nonwoven fabric, and fiber.
用以實施發明之形態 本發明為一種由矽酸鈉構成之酸性氣體用吸附劑。 以下將詳細說明本發明。此外，除非特定指明，%為質量%，份表示質量份。MODE FOR CARRYING OUT THE INVENTION The present invention is an acid gas adsorbent composed of sodium citrate. The invention will be described in detail below. Further, % is % by mass unless otherwise specified, and parts represent parts by mass.
1.矽酸鈉 本發明之酸性氣體用吸附劑所使用的矽酸鈉(本發明之吸附劑)可以使用各種化合物。 矽酸鈉的具體例可舉為水矽鈉石(Na2 O･4SiO2 ･8H2 O)、二矽酸鈉(Na2 O･Si2 O4 ･nH2 O)、多水矽鈉石(Na2 O･8SiO2 ･11H2 O)、伊利石(ilerite，NaHSi8 O17 ･nH2 O)、麥烴矽鈉石(magadiite，Na2 HSi14 O29 ･nH2 O)及斜水矽鈉石(Na2 HSi2 O41 ･nH2 O)等，較佳為二矽酸鈉。1. Sodium citrate The sodium citrate (the adsorbent of the present invention) used in the adsorbent for acid gas of the present invention can be used in various compounds. Specific examples of sodium citrate include sodium sulphate (Na 2 O, 4 SiO 2 • 8H 2 O), sodium digurate (Na 2 O, Si 2 O 4 • nH 2 O), and sodium sulphate (Na 2 O·8SiO 2 ·11H 2 O), illite (Narite, NaHSi 8 O 17 • nH 2 O), sodium astrorite (magadiite, Na 2 HSi 14 O 29 • nH 2 O) and oblique water Sodium sulphate (Na 2 HSi 2 O 41 · nH 2 O) or the like is preferably sodium dicitrate.
較佳的矽酸鈉為結晶質矽酸鈉，因其吸附酸性氣體的性能優越。 本發明中之結晶質係指於X射線粉末繞射測定下可得到起因於晶體結構之明確繞射峰者。The preferred sodium citrate is crystalline sodium citrate, which is superior in its ability to adsorb acid gases. The crystal form in the present invention means that a clear diffraction peak due to a crystal structure can be obtained by X-ray powder diffraction measurement.
本發明所使用的矽酸鈉宜為下式(1)所示之矽酸鈉。 Na2 O・mSiO2 ・nH2 O (1) 式(1)中，m及n為符合m=0.8~4.4且n=0.01~8.0之數值。m值越大SiO2 濃度越增加，故會變得難溶。m較佳的範圍為1.5~2.6，m未達0.8時水溶性會變高因而耐久性不佳，m超過4.4時吸附力下降。n小於0.01則酸性氣體吸附量下降，n大於8.0時水分在樹脂加工時會造成水解等而使加工性降低。 上述m及n係由螢光X射線分析之測定結果算出元素分析比後的數值。The sodium citrate used in the present invention is preferably sodium citrate represented by the following formula (1). Na 2 O·mSiO 2 ·nH 2 O (1) In the formula (1), m and n are values in which m = 0.8 to 4.4 and n = 0.01 to 8.0. The larger the m value, the more the SiO 2 concentration increases, so that it becomes poorly soluble. The preferred range of m is from 1.5 to 2.6. When m is less than 0.8, the water solubility becomes high and the durability is poor. When m exceeds 4.4, the adsorption force decreases. When n is less than 0.01, the acid gas adsorption amount is lowered, and when n is more than 8.0, moisture is hydrolyzed during resin processing, and workability is lowered. The above m and n are values obtained by calculating the elemental analysis ratio from the measurement results of the fluorescent X-ray analysis.
本發明使用之矽酸鈉的製造方法可應用先前的技術，不限制原料、製法或設備等。 例如，可以下述方法製造：將SiO2 /Na2 O莫耳比為0.8~4.4之矽酸鈉水溶液乾燥，並在500℃~850℃下將乾燥所得固體燒製數分鐘~十幾小時。 此外，對吸附劑而言即使含有少許其他成分亦不牽連除臭性能下降，因此並不會造成問題，但也不會大幅提升除臭性能。The method for producing sodium citrate used in the present invention can be applied to the prior art without restricting raw materials, processes, equipment, and the like. For example, it can be produced by drying an aqueous solution of sodium silicate having a SiO 2 /Na 2 O molar ratio of 0.8 to 4.4, and firing the dried solid at 500 ° C to 850 ° C for several minutes to several ten hours. Further, even if the adsorbent contains a small amount of other components, the deodorizing performance is not impaired, so that it does not cause a problem, but the deodorizing performance is not greatly improved.
本發明之矽酸鈉之醋酸氣體化學吸附容量宜為20mL/g以上。藉由將該化學吸附容量設為20mL/g以上，會有優越的吸附性能，可得到令人滿意的除臭效果。又，上限沒有特別地限制，較佳為200mL/g以下，更佳為100mL/g以下。 本發明之吸附容量係指化合物可除臭、吸收、吸附之特定氣體成分的最大量。 再者，在吸附劑的技術領域中，大多呈現的是以物理吸附及化學吸附兩種吸附機制吸附之吸附容量。在物理吸附的情形下，因吸附力弱的緣故，曾經被吸附的臭味會再釋出；化學吸附則因與臭味反應而不會發生再釋放，故就吸附劑之吸附機制來說以化學吸附為佳。區別除臭劑之化學吸附容量與物理吸附容量的方法為令吸附試驗溫度為高溫來測定吸附容量。由於物理吸附在高溫下變得無法吸附，故將吸附試驗溫度設為40℃以上即可僅區別測定化學吸附容量，本發明中之化學吸附容量也是採用這樣的測定方法。 具體的醋酸氣體化學吸附容量之測定方法如下。 將除臭劑置入難以吸附醋酸氣體且為不透氣材質的乙烯醇系聚合物或聚酯等之試驗袋中後密封，在該經密封的試驗袋中注入醋酸氣體後保存於40℃以上的恆溫器。於剛注入醋酸氣體後與保存一定時間後，測定試驗袋中殘存的醋酸氣體濃度。此時，將一定時間後殘存氣體濃度達到初始氣體濃度的1/10以上之時間點作為吸附性能失效(breakthrough)之點，且以此時殘存氣體濃度與初始氣體濃度的差為吸附劑所吸附及吸收之醋酸氣體量。The acetic acid gas chemisorption capacity of the sodium citrate of the present invention is preferably 20 mL/g or more. By setting the chemical adsorption capacity to 20 mL/g or more, the adsorption performance is excellent, and a satisfactory deodorizing effect can be obtained. Further, the upper limit is not particularly limited, but is preferably 200 mL/g or less, and more preferably 100 mL/g or less. The adsorption capacity of the present invention refers to the maximum amount of a specific gas component which the compound deodorizes, absorbs, and adsorbs. Furthermore, in the technical field of adsorbents, most of the adsorption capacities are adsorbed by two adsorption mechanisms, physical adsorption and chemical adsorption. In the case of physical adsorption, the odor that has been adsorbed will be released again due to the weak adsorption force; the chemical adsorption will not re-release due to the reaction with the odor, so the adsorption mechanism of the adsorbent is Chemical adsorption is preferred. The method of distinguishing the chemical adsorption capacity and the physical adsorption capacity of the deodorant is to measure the adsorption capacity by setting the adsorption test temperature to a high temperature. Since the physical adsorption becomes impossible to adsorb at a high temperature, it is only necessary to distinguish the chemical adsorption capacity by setting the adsorption test temperature to 40 ° C or higher. The chemical adsorption capacity in the present invention is also a measurement method. The specific method for measuring the chemical adsorption capacity of acetic acid gas is as follows. The deodorant is placed in a test bag such as a vinyl alcohol polymer or a polyester which is difficult to adsorb acetic acid gas and is a gas-impermeable material, and then sealed, and acetic acid gas is injected into the sealed test bag, and then stored at 40 ° C or higher. Thermostat. After the acetic acid gas was injected and stored for a certain period of time, the concentration of acetic acid gas remaining in the test bag was measured. At this time, the time point at which the residual gas concentration reaches 1/10 or more of the initial gas concentration after a certain period of time is taken as the point of the breakdown of the adsorption performance, and the difference between the residual gas concentration and the initial gas concentration at this time is adsorbed by the adsorbent. And the amount of acetic acid gas absorbed.
本發明之矽酸鈉為白色粉末，該粉末顏色以Lab表色系統而言較佳為：L值90~99、a值-2~5、b值-2~5。若Lab色彩空間表現在上述範圍之內，則除臭劑可使用於廣泛的用途。The sodium citrate of the present invention is a white powder, and the color of the powder is preferably a Lab color system: an L value of 90 to 99, an a value of -2 to 5, and a b value of -2 to 5. If the Lab color space is within the above range, the deodorant can be used for a wide range of purposes.
本發明之矽酸鈉的粒度以平均粒度計較佳為0.1μm~20μm，更佳為0.5μm~3μm。 將平均粒度設為0.1μm以上則不易凝集而可製成加工性優越的物品；將平均粒度設為10μm以下則可防止在加工為細纖維或薄膜等之過程中斷絲等瑕疵或成形品外觀瑕疵。又，最大粒度較佳為20μm以下，更佳為5μm以下。The particle size of the sodium citrate of the present invention is preferably from 0.1 μm to 20 μm, more preferably from 0.5 μm to 3 μm, in terms of an average particle size. When the average particle size is 0.1 μm or more, it is difficult to aggregate, and an article having excellent workability can be obtained. When the average particle size is 10 μm or less, it is possible to prevent the occurrence of defects such as silk or the appearance of a molded article in the process of processing into a fine fiber or a film. . Further, the maximum particle size is preferably 20 μm or less, more preferably 5 μm or less.
上述平均粒度係表示經雷射繞射粒度分佈儀測定並以體積基準解析測定結果所得之粒度D50值。The above average particle size means a particle size D50 value obtained by a laser diffraction particle size distribution analyzer and analyzing the measurement results on a volume basis.
2.酸性氣體吸附劑及用途 本發明為由前述矽酸鈉構成之酸性氣體用吸附劑。 本發明之酸性氣體為成為惡臭原因之酸性氣體，具體來說係指醋酸、異戊酸及丁酸等。2. Acid gas adsorbent and use The present invention relates to an acid gas adsorbent comprising the above sodium citrate. The acid gas of the present invention is an acid gas which is a cause of malodor, and specifically means acetic acid, isovaleric acid, butyric acid or the like.
本發明之酸性氣體用吸附劑可作為除臭劑而使用於各種用途。 作為除臭劑的使用形態可直接以矽酸鈉粉末或顆粒作為除臭劑來使用，又可作成將矽酸鈉粉末或顆粒置於匣盒等容器內之除臭製品來使用，靜置於室內或室外惡臭發生源的附近可發揮其效果。The acid gas adsorbent of the present invention can be used as a deodorant for various purposes. As a deodorant, the use form can be directly used as a deodorant by using sodium citrate powder or granules, or can be used as a deodorant product in which a sodium citrate powder or granules are placed in a container such as a cassette. It can be used in the vicinity of indoor or outdoor odor generating sources.
再者，本發明之酸性氣體用吸附劑如以下詳述可摻合於纖維、塗料、片材或成形品等中作為用於製造除臭加工製品之原料來利用。 除臭加工製品的用途可列舉除臭纖維、除臭塗料、除臭片材及除臭樹脂成形品等。 將本發明之吸附劑用於製造該等除臭加工製品時，吸附劑的形態可依目的以各種形態使用，例如：在摻合於樹脂等進行混合或捏拌的情形下使用矽酸鈉粉末或顆粒，在基材上塗覆使用的情形下則使用含有矽酸鈉的水系或有機溶劑系懸浮液。 以下就該等用途進行說明。Further, the acid gas adsorbent of the present invention can be used as a raw material for producing a deodorant processed product by blending it into a fiber, a paint, a sheet, a molded article or the like as described in detail below. Examples of the use of the deodorant processed product include deodorant fibers, deodorant paints, deodorant sheets, and deodorant resin molded articles. When the adsorbent of the present invention is used for the production of the deodorant processed articles, the form of the adsorbent can be used in various forms depending on the purpose, for example, sodium citrate powder is used in the case of mixing or kneading in a resin or the like. Alternatively, in the case where the particles are applied to a substrate, an aqueous or organic solvent suspension containing sodium citrate is used. The following uses for these purposes.
2-1.除臭劑 本發明之除臭劑係包含本發明之酸性氣體用吸附劑。 本發明之除臭劑可與其他已知的除臭劑混合作成除臭劑來使用。 與本發明之除臭劑混合之其他除臭劑的具體例有：用以消除如氨及三甲胺等鹼性氣體臭味之鹼性氣體除臭劑。鹼性氣體除臭劑可例示如對水呈不溶性或難溶性之四價金屬磷酸鹽化合物。該四價金屬磷酸鹽化合物的較佳具體例為磷酸鋯、磷酸鈦及磷酸錫等。該等化合物有結晶質物與非晶質物，其中結晶質物具有α型結晶、β型結晶、γ型結晶、鈉超離子導體(NASICON)型結晶等各種結晶系，有氣體吸附性者皆可與本發明之除臭劑混合。 本發明之除臭劑也可與用以消除硫化氫與甲硫醇等硫系氣體臭味之硫性氣體除臭劑混合作成除臭劑。例如可與載持有至少1種以上金屬離子之矽膠、氧化鋅、矽酸銅或矽酸鋅混合，前述至少1種以上金屬離子係選自於由銅、鋅及錳所構成之群組中。以矽膠、氧化鋅、矽酸銅及矽酸鋅而言，比表面積越大者除臭性能越高因此越佳。 此外，本發明之除臭劑也可為使本發明之酸性氣體用吸附劑受載於沸石等載體者。 再者，本發明之除臭劑也可含有其他已知的添加劑。2-1. Deodorant The deodorant of the present invention contains the adsorbent for acid gas of the present invention. The deodorant of the present invention can be used as a deodorant by mixing with other known deodorants. Specific examples of the other deodorant mixed with the deodorant of the present invention include an alkaline gas deodorant for eliminating the odor of an alkaline gas such as ammonia or trimethylamine. The alkaline gas deodorant can be exemplified by a tetravalent metal phosphate compound which is insoluble or poorly soluble in water. Preferable specific examples of the tetravalent metal phosphate compound are zirconium phosphate, titanium phosphate, tin phosphate, and the like. These compounds include crystalline materials and amorphous materials, and the crystalline material has various crystal systems such as α-type crystal, β-form crystal, γ-type crystal, and sodium super-ionic conductor (NASICON) crystal, and both of them have gas adsorption properties. The deodorant of the invention is mixed. The deodorant of the present invention can also be used as a deodorant by mixing with a sulfur gas deodorant for eliminating the odor of sulfur gas such as hydrogen sulfide and methyl mercaptan. For example, it may be mixed with tantalum, zinc oxide, copper ruthenate or zinc antimonate carrying at least one metal ion, and at least one or more metal ions are selected from the group consisting of copper, zinc and manganese. . In the case of tannin extract, zinc oxide, copper ruthenate and zinc niobate, the higher the specific surface area, the higher the deodorizing performance and therefore the better. Further, the deodorant of the present invention may be such that the acid gas adsorbent of the present invention is supported on a carrier such as zeolite. Further, the deodorant of the present invention may also contain other known additives.
2-2.除臭纖維 使用本發明吸附劑的有利用途之一為除臭纖維。 天然纖維及合成纖維任一者皆可作為此狀況下的原料纖維，亦可為短纖維、長纖維及具有芯鞘結構之複合纖維等任一者。使用本發明之吸附劑以賦予纖維除臭性能的方法並無特別地限制，例如：利用後加工將本發明之吸附劑塗佈於纖維時，可藉由以塗佈或浸泡等方法將含有矽酸鈉之水系或有機溶劑系懸浮液附著於纖維表面再除去溶劑而塗敷於纖維表面。另外，也可以混合用以增加對纖維表面之附著力的黏結劑。 含有矽酸鈉之水系懸浮液的pH並沒有特別地限制，然而為了使吸附劑的性能充分發揮，pH較佳為6~10左右。2-2. Deodorizing fiber One of the advantageous uses of the adsorbent of the present invention is a deodorizing fiber. Any of natural fibers and synthetic fibers may be used as the raw material fibers in this case, and may be any of short fibers, long fibers, and composite fibers having a core-sheath structure. The method of using the adsorbent of the present invention to impart deodorizing performance to the fiber is not particularly limited. For example, when the adsorbent of the present invention is applied to a fiber by post-processing, it may be contained by coating or soaking. The sodium or organic solvent suspension of sodium is attached to the surface of the fiber to remove the solvent and applied to the surface of the fiber. In addition, a binder for increasing the adhesion to the surface of the fiber may also be mixed. The pH of the aqueous suspension containing sodium citrate is not particularly limited, but in order to sufficiently exert the performance of the adsorbent, the pH is preferably about 6 to 10.
再者，將本發明吸附劑與溶融之液狀纖維用樹脂或溶解之纖維用樹脂溶液捏合，藉由將其紡絲可獲得經賦予除臭性能之纖維。 任何已知的化學纖維皆可使用能用於此方法的纖維用樹脂。較佳的具體例例如：聚酯、聚醯胺、壓克力、聚丙烯、聚乙烯(polyethylene)、聚乙烯(polyvinyl)、聚亞乙烯(polyvinylidene)、聚胺甲酸酯及聚苯乙烯等。該等樹脂可為均聚物也可為共聚物。為共聚物時，各共聚成分之聚合比例並沒有特別地限制。 本發明吸附劑尤有一大特點是可與聚酯纖維進行捏合加工。一般來說，酸性氣體吸附容量大的氧化鋅或氧化鋁和氧化鎂的複合氧化物等由於鹼性成分等而在與聚酯樹脂捏合下降低了樹脂黏度，經常無法紡絲。反觀本發明吸附劑推測因造成樹脂劣化的鹼性成分是存在於晶體結構的內部，故可於不致聚酯劣化下進行加工。Further, the adsorbent of the present invention is kneaded with a molten resin or a dissolved resin resin solution, and a fiber having a deodorizing property can be obtained by spinning the same. A fiber resin which can be used in this method can be used for any known chemical fiber. Preferred specific examples are, for example, polyester, polyamide, acrylic, polypropylene, polyethylene, polyvinyl, polyvinylidene, polyurethane, polystyrene, etc. . The resins may be homopolymers or copolymers. When it is a copolymer, the polymerization ratio of each copolymerization component is not specifically limited. A particularly characteristic feature of the adsorbent of the present invention is that it can be kneaded with polyester fibers. In general, zinc oxide or a composite oxide of alumina and magnesia having a large acid gas adsorption capacity is reduced in resin viscosity by kneading with a polyester resin due to an alkaline component or the like, and is often unable to be spun. In contrast, the adsorbent of the present invention is presumed to be present in the crystal structure due to the presence of an alkaline component which causes deterioration of the resin, so that it can be processed without deterioration of the polyester.
包含於樹脂中之本發明酸性氣體用吸附劑之比例並沒有特別地限制。一般來說，若是使含量增加則可使除臭性能強力地發揮且可長時間持續，但是由於含有某種程度以上在除臭效果上就不會產生巨大差異，又或者會有樹脂強度下降的情形，因此每100質量份樹脂中本發明酸性氣體用吸附劑含量宜為0.1~10質量份，較佳為0.5~5質量份。 使用了本發明酸性氣體用吸附劑之除臭纖維可以利用於各種需要除臭性能之範疇，例如：可使用於許多纖維製品諸如內衣、絲襪、襪子、被褥、被褥套、坐墊、毛毯、地毯、簾、沙發、汽車椅、空氣過濾器、護理用衣物等。The ratio of the adsorbent for acid gas of the present invention contained in the resin is not particularly limited. In general, if the content is increased, the deodorizing performance can be exerted strongly and can be continued for a long period of time, but since there is a certain degree or more, there is no large difference in the deodorizing effect, or there is a decrease in the resin strength. In this case, the content of the adsorbent for acid gas of the present invention per 100 parts by mass of the resin is preferably 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass. The deodorizing fiber using the adsorbent for acid gas of the present invention can be utilized in various fields requiring deodorizing properties, for example, it can be used for many fiber products such as underwear, stockings, socks, bedding, bedding, cushions, blankets, carpets, Curtains, sofas, car seats, air filters, nursing clothing, etc.
2-3.除臭塗料 使用本發明酸性氣體用吸附劑的其他用途為除臭塗料。 在製造除臭塗料時，成為所用塗料展色劑(vehicle)之主成分的油脂或樹脂沒有特別地限制，可為天然植物油、天然樹脂、半合成樹脂及合成樹脂脂中之任一者，且亦可為熱可塑性樹脂及熱硬化性樹脂中之任一者。可使用的油脂及樹脂為例如：亞麻仁油、桐油、大豆油等乾性油或半乾性油；松香、硝化纖維素、乙基纖維素、醋酸丁酸纖維素、苯甲基纖維素、酚醛清漆(Novolac)型或可溶酚醛(Resol)型酚樹脂、醇酸樹脂、胺基醇酸樹脂、丙烯酸樹脂、氯乙烯、聚矽氧樹脂、氟樹脂、環氧樹脂、胺基甲酸乙酯樹脂(urethane resin)、飽和聚酯樹脂、三聚氰胺樹脂及聚二氯亞乙烯樹脂(polyvinylidene chloride resin)等。2-3. Deodorant paint The other use of the adsorbent for acid gas of the present invention is a deodorant paint. In the production of the deodorant paint, the oil or fat or the resin which is a main component of the paint vehicle to be used is not particularly limited, and may be any of natural vegetable oil, natural resin, semi-synthetic resin and synthetic resin grease, and It may be any of a thermoplastic resin and a thermosetting resin. The fats and oils and resins that can be used are, for example, dry oils or semi-drying oils such as linseed oil, tung oil, and soybean oil; rosin, nitrocellulose, ethyl cellulose, cellulose acetate butyrate, benzyl cellulose, novolac (Novolac) type or Resol type phenol resin, alkyd resin, amino alkyd resin, acrylic resin, vinyl chloride, polyoxyl resin, fluororesin, epoxy resin, urethane resin ( Urethane resin), saturated polyester resin, melamine resin, and polyvinylidene chloride resin.
本發明酸性氣體用吸附劑也可使用於液狀塗料或粉體塗料任一者。再者，使用本發明酸性氣體用吸附劑之除臭塗料組成物可為由任何機制硬化之類型，具體有氧化聚合型、濕氣聚合型、加熱硬化型、觸媒硬化型、紫外線硬化型及多元醇硬化型等。又，除了微粒子氧化鋅及可能會和與微粒子氧化鋅併用之除臭物質產生化學反應者之外，使用於塗料組成物中的顏料、分散劑及其他添加劑並沒有特別地限制。使用本發明酸性氣體用吸附劑之塗料組成物可輕易調配，具體來說，只要使用球磨機、輥磨機、分散機或混合機等一般混合裝置將上述吸附劑或除臭組成物與塗料成分充分地分散及混合即可。The adsorbent for acid gas of the present invention can also be used for any of liquid paints or powder paints. Further, the deodorant coating composition using the adsorbent for acid gas of the present invention may be of any type which is hardened by any mechanism, specifically, an oxidative polymerization type, a moisture polymerization type, a heat curing type, a catalyst hardening type, an ultraviolet curing type, and Polyol hardening type and the like. Further, the pigment, the dispersant and other additives used in the coating composition are not particularly limited, except for the particulate zinc oxide and the chemical reaction which may be caused by the deodorizing substance used together with the fine particle zinc oxide. The coating composition using the adsorbent for acid gas of the present invention can be easily formulated. Specifically, the adsorbent or the deodorant composition and the coating composition are sufficiently used by a general mixing device such as a ball mill, a roll mill, a disperser or a mixer. Disperse and mix.
包含於除臭塗料中之本發明酸性氣體用吸附劑之比例並沒有特別地限制。一般來說，若是使含量增加則可使除臭性能強力地發揮且可長時間持續，但是由於含有某種程度以上在除臭效果上就不會產生巨大差異，又或者被塗面的光澤會消失或產生裂隙，因此每100質量份塗料組成物中本發明酸性氣體用吸附劑含量宜為0.1~20質量份，較佳為0.5~10質量份。 摻合本發明吸附劑的除臭塗料可以利用於各種需要除臭性能之範疇，例如可使用於建築物、車輛、鐵路等的內壁外壁、垃圾焚化廠設施或廚餘容器等。The ratio of the adsorbent for acid gas of the present invention contained in the deodorant paint is not particularly limited. In general, if the content is increased, the deodorizing performance can be exerted strongly and can be continued for a long time, but since there is a certain degree or more, there is no great difference in the deodorizing effect, or the gloss of the coated surface is The content of the acid gas adsorbent of the present invention is preferably 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass per 100 parts by mass of the coating composition. The deodorant paint to which the adsorbent of the present invention is blended can be utilized in various fields requiring deodorizing properties, for example, it can be used for an outer wall of a building, a vehicle, a railway, or the like, a garbage incineration facility or a kitchen waste container.
2-4.除臭片材 本發明酸性氣體用吸附劑的其他用途之一為除臭片材。 成為原料的片材其材質及微構造等並沒有特別地限制。較佳的材質為樹脂、紙等或該等之複合物，且宜為多孔質材質者。片材的較佳具體例有和紙、合成紙、不織布及樹脂膜等，特別佳的片材為由天然紙漿及/或合成紙漿所構成之紙。使用天然紙漿則吸附劑粒子的粉末受挾於微細分叉的纖維之間，優點在於即使不特別使用結合劑也可作為實用的載體，另一方面，合成紙漿的優點在於優越的耐藥品性。使用合成紙漿時因為有時很難經由在纖維間挾塞粉末來載持吸附劑粒子，故也可以在抄紙後的乾燥步驟中將一部分纖維溶融以增加粉末與纖維之間的附著力，或在一部分纖維中混合別的熱硬化性樹脂纖維。 如此將天然紙漿與合成紙漿以適當比例混合使用，可獲得已調整各種特性之紙，一般來說，合成紙漿的比例增多可獲得具有優越的強度、耐水性、耐藥品性及耐油性等之紙，另一方面，天然紙漿的比例增多則可獲得具有優越的吸水性、透氣性、親水性、成形加工性及質地等之紙。2-4. Deodorizing Sheet One of the other uses of the adsorbent for acid gas of the present invention is a deodorizing sheet. The material, the microstructure, and the like of the sheet to be a raw material are not particularly limited. The preferred material is a resin, paper, or the like, or a composite thereof, and is preferably a porous material. Preferred examples of the sheet include paper, synthetic paper, non-woven fabric, and resin film. Particularly preferred sheets are papers composed of natural pulp and/or synthetic pulp. When natural pulp is used, the powder of the adsorbent particles is interposed between the fibers of the finely divided fork. The advantage is that it can be used as a practical carrier even without using a binder in particular. On the other hand, synthetic pulp has the advantage of superior chemical resistance. When synthetic pulp is used, since it is sometimes difficult to carry the adsorbent particles by entanglement of the powder between the fibers, it is also possible to melt a part of the fibers in the drying step after papermaking to increase the adhesion between the powder and the fibers, or A part of the fibers is mixed with another thermosetting resin fiber. Thus, the natural pulp and the synthetic pulp are mixed and used in an appropriate ratio, and paper having various characteristics can be obtained. Generally, the proportion of the synthetic pulp is increased to obtain paper having superior strength, water resistance, chemical resistance, oil resistance, and the like. On the other hand, when the proportion of the natural pulp is increased, paper having excellent water absorbability, gas permeability, hydrophilicity, moldability, texture, and the like can be obtained.
使本發明酸性氣體用吸附劑受載於片材的方法並沒有特別地限制。本發明酸性氣體用吸附劑之載持可為製造片材時或製造片材後任一者，例如受載於紙時，有下述方法：在抄紙步驟之任一步驟中導入吸附劑，或將已使黏結劑與吸附劑一起分散之液體塗佈、浸漬或吹附於預先製造之紙上。 以下以一範例說明關於抄紙步驟時導入本發明酸性氣體用吸附劑的方法。抄紙步驟本身根據已知的方法進行即可，例如：首先，於以預定比例含有吸附劑與紙漿之漿料中，添加各佔全部漿料質量之5質量%以下的陽離子性及陰離子性凝集劑以生成凝集體。接著，將該凝集體以已知的方法進行抄紙並以100℃~190℃的溫度使其乾燥，可獲得載持有酸性氣體用吸附劑之紙。The method of carrying the acid gas adsorbent of the present invention on the sheet is not particularly limited. The carrier for the acid gas adsorbent of the present invention may be either a sheet material or a sheet after the sheet is produced. For example, when it is loaded on paper, there is a method of introducing an adsorbent in any step of the papermaking step, or The liquid in which the binder is dispersed together with the adsorbent is coated, impregnated or blown onto the pre-manufactured paper. Hereinafter, a method of introducing the adsorbent for acid gas of the present invention at the papermaking step will be described by way of an example. The papermaking step itself may be carried out according to a known method. For example, first, a cationic and anionic aggregating agent each containing 5% by mass or less of the total mass of the slurry is added to the slurry containing the adsorbent and the pulp in a predetermined ratio. To generate agglomerates. Next, the aggregate is subjected to papermaking by a known method and dried at a temperature of from 100 ° C to 190 ° C to obtain a paper carrying an adsorbent for acid gas.
本發明酸性氣體用吸附劑於片材上之載持量，一般來說若是載持量增加則可使除臭性能強力地發揮且可長時間持續，但是由於載持某種程度以上在除臭效果上不會產生巨大差異，故以吸附劑的較佳載持量而言，在抄紙步驟時使吸附劑或除臭組成物受載於片材表面與內部全體的情形下，每100質量份片材宜為0.1~10質量份；在藉由塗敷等利用後加工使吸附劑僅受載於片材表面的情形下則為0.05~15g/m2 。 使用本發明吸附劑之除臭片材可以利用於各種需要除臭性能之範疇，例如：醫療用包裝紙、食品用包裝紙、電性設備用捆包紙、護理用紙製品、保鮮紙、紙製衣料、空氣清淨濾材、壁紙、面紙及廁紙等。In the carrier amount of the adsorbent for acid gas of the present invention, generally, when the amount of the carrier is increased, the deodorizing performance can be strongly exhibited and can be continued for a long period of time, but the deodorization is carried out to some extent or more. There is no significant difference in the effect. Therefore, in the case of the preferred loading amount of the adsorbent, the adsorbent or the deodorant composition is loaded on the surface of the sheet and the entire interior in the papermaking step, per 100 parts by mass. The sheet is preferably 0.1 to 10 parts by mass; it is 0.05 to 15 g/m 2 in the case where the adsorbent is only supported on the surface of the sheet by post-processing by coating or the like. The deodorizing sheet using the adsorbent of the present invention can be utilized in various fields requiring deodorizing performance, for example, medical packaging paper, food packaging paper, packaging paper for electrical equipment, nursing paper products, wrap paper, paper Clothing, air cleaning media, wallpaper, facial tissue and toilet paper.
2-5.除臭樹脂成形品 作為本發明酸性氣體用吸附劑之用途可舉例如應用於樹脂成形品。 添加本發明酸性氣體用吸附劑於樹脂時，可將樹脂及吸附劑直接混合並置入成形機予以成型，也可以預先調製含有高濃度酸性氣體用吸附劑的丸粒狀樹脂，再將該丸粒狀樹脂與主樹脂混合後予以成型。再者，為了改善樹脂的物性，也可視所需而摻合顏料、染料、抗氧化劑、耐光安定劑、抗靜電劑、發泡劑、耐衝擊強化劑、玻璃纖維、防潮劑及增量劑等各種其他添加劑。 用於製造使用了本發明吸附劑之除臭樹脂成形品的成型方法，可使用如射出成型、擠製成型、充氣成型、真空成型等一般樹脂成型方法。 使用本發明吸附劑之除臭樹脂成形品可以利用於各種需要除臭性能之範疇，例如：空氣清淨器、冰箱等家電製品及垃圾桶、瀝水器件等一般家庭用品、可攜式便器等各種看護用品、日用品等。 實施例2-5. Deodorizing resin molded article The use of the adsorbent for acid gas of the present invention is, for example, applied to a resin molded article. When the adsorbent for acid gas of the present invention is added to the resin, the resin and the adsorbent may be directly mixed and placed in a molding machine to be molded, or a pelletized resin containing a high-concentration acid gas adsorbent may be prepared in advance, and the pellet may be further prepared. The granular resin is mixed with the main resin and then molded. Furthermore, in order to improve the physical properties of the resin, pigments, dyes, antioxidants, light stabilizers, antistatic agents, foaming agents, impact stabilizers, glass fibers, moisture-proofing agents, extenders, etc. may be blended as needed. Various other additives. As a molding method for producing a deodorant resin molded article using the adsorbent of the present invention, a general resin molding method such as injection molding, extrusion molding, inflation molding, vacuum molding or the like can be used. The deodorant resin molded article using the adsorbent of the present invention can be utilized in various fields requiring deodorizing performance, for example, household appliances such as air cleaners and refrigerators, general household articles such as garbage cans and draining devices, and portable toilets. Supplies, daily necessities, etc. Example
以下將更進一步具體地說明本發明，但並不受限於此。此外，%為質量%。依據下述方法測定本發明酸性氣體用吸附劑及比較用吸附劑之粉末物性及除臭性能等。The present invention will be more specifically described below, but is not limited thereto. In addition, % is % by mass. The powder physical properties and deodorizing performance of the acid gas adsorbent and the comparative adsorbent of the present invention were measured by the following methods.
(1)粉末結晶性 粉末結晶性係使用Rigaku公司製之X射線繞射裝置「RINT2400V」(型號名)，以銅靶激發射線(Cu Kα ray)進行而得到X射線繞射影像。測定條件設為管電壓40kV及電流150mA。若可得到明確的繞射峰便為結晶質，若無法得到則判定為非晶質。(1) Powder crystallinity The powder crystallinity was obtained by using an X-ray diffraction apparatus "RINT 2400V" (model name) manufactured by Rigaku Co., Ltd., and an X-ray diffraction image was obtained by a copper target excitation ray (Cu Kα ray). The measurement conditions were a tube voltage of 40 kV and a current of 150 mA. If a clear diffraction peak is obtained, it is crystalline, and if it is not available, it is judged to be amorphous.
(2)元素組成 使用Rigaku公司製之ZSX100e型螢光X射線分析裝置，依據螢光X射線分析來測定，以物質量基準解析結果而算出元素組成(莫耳)比。(2) Elemental composition The ZSX100e type fluorescent X-ray analyzer manufactured by Rigaku Co., Ltd. was measured by fluorescence X-ray analysis, and the elemental composition (mole) ratio was calculated based on the mass quality reference analysis result.
(3)粒度D50及D90 吸附劑之粒度D50及D90的測定係以雷射繞射式粒度分佈儀測定並以體積基準解析結果。另外，粒度分布含有率%從該解析方法而言為全部粒子中的體積%，但因測定粉末的密度是固定的，所以意同質量%。具體為藉由Malvern公司製之雷射繞射式粒度分佈測定裝置「MS2000」測定。(3) Particle size D50 and D90 The particle size of the adsorbent D50 and D90 were measured by a laser diffraction type particle size distribution analyzer and the results were analyzed on a volume basis. Further, the particle size distribution content percentage is the volume % of all the particles from the analysis method, but since the density of the measurement powder is fixed, the mass % is equivalent. Specifically, it was measured by a laser diffraction type particle size distribution measuring apparatus "MS2000" manufactured by Malvern.
(4)粉末的化學吸附容量 將吸附劑粉末0.01g置入乙烯醇系聚合物膜製之試驗袋中，並於其中注入10L的醋酸(初始濃度為100ppm)，30分鐘後以氣體檢測管測定泰德拉袋(Tedlar bag)中殘存的氣體濃度。(4) Chemical adsorption capacity of the powder 0.01 g of the adsorbent powder was placed in a test bag made of a vinyl alcohol polymer film, and 10 L of acetic acid (initial concentration: 100 ppm) was injected therein, and after 30 minutes, it was measured by a gas detecting tube. The concentration of gas remaining in the Tedlar bag.
(5)除臭成形品的醋酸除臭性能 將除臭成形品100cm2 置入乙烯醇系聚合物膜製之試驗袋中，並於其中注入3L的醋酸(初始濃度為30ppm)，2小時後以氣體檢測管測定試驗袋中殘存的氣體濃度。(5) Acetic acid deodorizing performance of deodorant molded article 100 cm 2 of the deodorant molded article was placed in a test bag made of a vinyl alcohol polymer film, and 3 L of acetic acid (initial concentration: 30 ppm) was injected therein, 2 hours later. The gas concentration in the test bag was measured by a gas detecting tube.
(6)除臭纖維的異戊酸除臭性能 將除臭纖維1g置入乙烯醇系聚合物膜製之試驗袋中，並於其中注入500mL的異戊酸(初始濃度為38ppm)，2小時後以氣體檢測管測定試驗袋中殘存的氣體濃度。(6) Isovaleric acid deodorizing performance of deodorizing fiber 1 g of deodorizing fiber was placed in a test bag made of a vinyl alcohol polymer film, and 500 mL of isovaleric acid (initial concentration: 38 ppm) was injected therein for 2 hours. The concentration of gas remaining in the test bag was measured by a gas detecting tube.
＜實施例1＞ 將SiO2 /Na2 O莫耳比為2.1之矽酸鈉水溶液乾燥，並在650℃~660℃下將乾燥所得固體燒製3小時。將燒製所得白色粉末粉碎後得到結晶質矽酸鈉，測量其結晶性、組成、粒度D50、D90及粉末的醋酸除臭容量並記載於表1。<Example 1> An aqueous solution of sodium silicate having a SiO 2 /Na 2 O molar ratio of 2.1 was dried, and the dried solid was fired at 650 ° C to 660 ° C for 3 hours. The white powder obtained by baking was pulverized to obtain crystalline sodium citrate, and the crystallinity, composition, particle size D50, D90 and the acetic acid deodorizing capacity of the powder were measured and described in Table 1.
＜實施例2＞ 除了燒製條件設為870℃~880℃下1小時之外，進行與實施例1相同之操作、分析等，其結果示於表1。<Example 2> The same operation, analysis, and the like as in Example 1 were carried out except that the firing conditions were set to 870 ° C to 880 ° C for 1 hour, and the results are shown in Table 1.
＜實施例3＞ 除了SiO2 /Na2 O莫耳比設為1.9之外，進行與實施例1相同之操作、分析等，其結果示於表1。<Example 3> The same operation, analysis, and the like as in Example 1 were carried out except that the SiO 2 /Na 2 O molar ratio was 1.9. The results are shown in Table 1.
＜實施例4＞ 除了SiO2 /Na2 O莫耳比設為1.7、燒製條件設為720℃~730℃下1小時之外，進行與實施例1相同之操作、分析等，其結果示於表1。<Example 4> The same operation, analysis, and the like as in Example 1 were carried out except that the SiO 2 /Na 2 O molar ratio was 1.7 and the firing conditions were 720 ° C to 730 ° C for 1 hour. In Table 1.
＜實施例5＞ 除了SiO2 /Na2 O莫耳比設為2.8之外，進行與實施例1相同之操作、分析等，其結果示於表1。<Example 5> The same operation, analysis, and the like as in Example 1 were carried out except that the SiO 2 /Na 2 O molar ratio was 2.8. The results are shown in Table 1.
＜實施例6＞ 除了SiO2 /Na2 O莫耳比設為1.9之外，進行與實施例1相同之操作、分析等，其結果示於表1。<Example 6> The same operation, analysis, and the like as in Example 1 were carried out except that the SiO 2 /Na 2 O molar ratio was 1.9. The results are shown in Table 1.
＜比較例1＞ 使用市售的氫氧化氧鋯測定其結晶性、組成、粒度D50、D90及對醋酸之化學吸附容量，並將測定結果記載於表1。<Comparative Example 1> The crystallinity, composition, particle size D50, D90, and chemical adsorption capacity to acetic acid were measured using commercially available zirconium hydroxide hydroxide, and the measurement results are shown in Table 1.
＜比較例2＞ 使用市售的非晶質氧化鋅測定其結晶性、組成、粒度D50、D90及對醋酸之化學吸附容量，並將測定結果記載於表1。<Comparative Example 2> The crystallinity, composition, particle size D50, D90, and chemical adsorption capacity to acetic acid were measured using commercially available amorphous zinc oxide, and the measurement results are shown in Table 1.
＜比較例3＞ 使用市售的水滑石測定其結晶性、組成、粒度D50、D90及對醋酸之化學吸附容量，並將測定結果記載於表1。<Comparative Example 3> The crystallinity, composition, particle size D50, D90, and chemical adsorption capacity to acetic acid were measured using commercially available hydrotalcite, and the measurement results are shown in Table 1.
[表1] [Table 1]
＜實施例7＞聚酯樹脂成形品 藉由乾摻於UNITIKA聚酯樹脂MA2101中混合4%實施例1之吸附劑，並以射出成型機成形出1mm厚的板片。 使用所得之成形板片100cm2 來實施使用了醋酸氣體的除臭試驗，其結果記載於表2。<Example 7> A polyester resin molded article was mixed with 4% of the adsorbent of Example 1 by dry blending in UNITIKA polyester resin MA2101, and a sheet of 1 mm thick was formed by an injection molding machine. A deodorization test using acetic acid gas was carried out using the obtained molded sheet 100 cm 2 , and the results are shown in Table 2.
＜實施例8＞聚酯樹脂成形品 藉由乾摻於UNITIKA聚酯樹脂MA2101中混合4%實施例2之吸附劑，並以射出成型機成形出1mm厚的板片。 使用所得之成形板片100cm2 來實施使用了醋酸氣體的除臭試驗，其結果記載於表2。<Example 8> A polyester resin molded article was mixed with 4% of the adsorbent of Example 2 by dry blending in UNITIKA polyester resin MA2101, and a sheet of 1 mm thick was formed by an injection molding machine. A deodorization test using acetic acid gas was carried out using the obtained molded sheet 100 cm 2 , and the results are shown in Table 2.
＜比較例4＞聚酯樹脂成形品 藉由乾摻於UNITIKA聚酯樹脂MA2101中混合4%比較例1之吸附劑，並以射出成型機成形出1mm厚的板片。 使用所得之成形板片100cm2 來實施使用了醋酸氣體的除臭試驗，其結果記載於表2。<Comparative Example 4> A polyester resin molded article was mixed with 4% of the adsorbent of Comparative Example 1 by dry blending in UNITIKA polyester resin MA2101, and a sheet having a thickness of 1 mm was formed by an injection molding machine. A deodorization test using acetic acid gas was carried out using the obtained molded sheet 100 cm 2 , and the results are shown in Table 2.
＜比較例5＞聚酯樹脂成形品 藉由乾摻於UNITIKA聚酯樹脂MA2101中混合4%比較例2之吸附劑，並以射出成型機成形出1mm厚的板片。比較例2的加工性非常差，因裂隙及發泡等而無法得到美觀的成形板片。 將較大的破片狀成形板片作成100cm2 來使用並實施使用了醋酸氣體的除臭試驗，其結果記載於表2。<Comparative Example 5> A polyester resin molded article was prepared by mixing 4% of the adsorbent of Comparative Example 2 with UNITIKA polyester resin MA2101, and forming a sheet having a thickness of 1 mm by an injection molding machine. The workability of Comparative Example 2 was extremely poor, and it was not possible to obtain an aesthetically formed formed sheet due to cracks, foaming, or the like. A large flaky shaped sheet was used to make 100 cm 2 and a deodorization test using acetic acid gas was carried out. The results are shown in Table 2.
＜比較例6＞聚酯樹脂成形品 藉由乾摻於UNITIKA聚酯樹脂MA2101中混合4%比較例3之吸附劑，並以射出成型機成形出1mm厚的板片。 比較例3的加工性非常差，因裂隙及發泡等而無法得到美觀的成形板片，故無法實施除臭試驗。<Comparative Example 6> Polyester resin molded article An adsorbent of Comparative Example 3 was mixed with 4% of UNITIKA polyester resin MA2101, and a sheet having a thickness of 1 mm was formed by an injection molding machine. In Comparative Example 3, the workability was extremely poor, and a beautifully formed sheet was not obtained due to cracks, foaming, etc., and thus the deodorizing test could not be performed.
[表2] [Table 2]
＜實施例9＞聚酯纖維 作成一於UNITIKA聚酯樹脂MA2101中摻合了20%實施例1之吸附劑的母料(master batch)。將所得母料以UNITIKA聚酯樹脂MA1201稀釋成10分之1，並以單絲纖維紡絲機4倍延伸除臭聚酯絲進行紡絲。 紡絲可在無斷絲及濾過壓上升等情形之下加工。使用所得之除臭纖維來實施使用了異戊酸的除臭試驗，其結果記載於表3。<Example 9> Polyester fiber A master batch in which 20% of the adsorbent of Example 1 was blended in UNITIKA polyester resin MA2101 was prepared. The obtained master batch was diluted to 1/10 with UNITIKA polyester resin MA1201, and spun by a 4-fold extended deodorizing polyester yarn of a monofilament fiber spinning machine. Spinning can be processed without breaking the yarn and increasing the filtration pressure. A deodorization test using isovaleric acid was carried out using the obtained deodorant fiber, and the results are shown in Table 3.
＜比較例7＞聚酯纖維 作成一於UNITIKA聚酯樹脂MA2101中摻合了20%比較例1之吸附劑的母料。將所得母料以UNITIKA聚酯樹脂MA2101稀釋成10分之1，並以單絲纖維紡絲機將除臭聚酯絲進行紡絲。 紡絲可在無斷絲及濾過壓上升等情形之下加工。使用所得之除臭纖維來實施使用了異戊酸的除臭試驗，其結果記載於表3。<Comparative Example 7> Polyester fiber A masterbatch in which 20% of the adsorbent of Comparative Example 1 was blended in UNITIKA polyester resin MA2101 was prepared. The obtained master batch was diluted to 1/10 with UNITIKA polyester resin MA2101, and the deodorized polyester yarn was spun by a monofilament fiber spinning machine. Spinning can be processed without breaking the yarn and increasing the filtration pressure. A deodorization test using isovaleric acid was carried out using the obtained deodorant fiber, and the results are shown in Table 3.
＜比較例8＞聚酯纖維 嘗試作成一於UNITIKA聚酯樹脂MA2101中摻合了20%比較例2之吸附劑的母料，但樹脂黏度顯著地降低而無法作成母料。因此，無法實施紡絲及除臭試驗。<Comparative Example 8> Polyester fiber A masterbatch in which 20% of the adsorbent of Comparative Example 2 was blended into UNITIKA polyester resin MA2101 was attempted, but the resin viscosity was remarkably lowered to make a master batch. Therefore, the spinning and deodorization test cannot be performed.
[表3] [table 3]
實施例之吸附劑相較於比較例之吸附劑有較高的醋酸氣體吸附容量，並且可與聚酯樹脂捏合加工成形。此外，實施例的吸附劑在聚酯樹脂成形品及紡絲品的除臭評價中也有優越的除臭效果。 產業上之可利用性The adsorbent of the example has a higher adsorption capacity of acetic acid gas than the adsorbent of the comparative example, and can be formed by kneading with a polyester resin. Further, the adsorbent of the examples also has an excellent deodorizing effect in the evaluation of deodorization of the polyester resin molded article and the spun product. Industrial availability
本發明酸性氣體用吸附劑對酸性氣體有優越的除臭效果，加工性亦優越，故可作為除臭劑用於各種用途。並且，因吸附劑的色調為白色，可於紙及纖維等製品進行塗佈或捏合加工，從而可提供使用該吸附劑而發揮優越除臭性能的紙、不織布及纖維等除臭加工製品。The acid gas adsorbent of the present invention has an excellent deodorizing effect on acid gas and is excellent in processability, and thus can be used as a deodorant for various purposes. Further, since the color tone of the adsorbent is white, it can be applied or kneaded in a product such as paper or fiber, and a deodorant processed product such as paper, nonwoven fabric, or fiber which exhibits superior deodorizing performance using the adsorbent can be provided.
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