CN1016491B - Fibrous absorbent articles having enhanced deodoriging properties - Google Patents

Fibrous absorbent articles having enhanced deodoriging properties

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Publication number
CN1016491B
CN1016491B CN 88109236 CN88109236A CN1016491B CN 1016491 B CN1016491 B CN 1016491B CN 88109236 CN88109236 CN 88109236 CN 88109236 A CN88109236 A CN 88109236A CN 1016491 B CN1016491 B CN 1016491B
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absorbent article
molecular sieve
siliceous
fibrous
fiber
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CN 88109236
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Chinese (zh)
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CN1037646A (en
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邦妮达·克里斯托弗森·马卡斯
安东尼·约瑟夫·吉奥弗里
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环球油品公司
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Priority to US07/128,649 priority Critical patent/US4826497A/en
Application filed by 环球油品公司 filed Critical 环球油品公司
Publication of CN1037646A publication Critical patent/CN1037646A/en
Publication of CN1016491B publication Critical patent/CN1016491B/en

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Abstract

纤维吸附制品如可换尿布、月经用品、伤口敷料,绷带、失禁垫、揩擦物、内衣、鞋垫等,含有有效量的硅质结晶分子筛,具有增强的脱除待吸附体液气味的性能,上述分子筛具有至少约5.5的孔径,及相当低的水吸附容量。 The fibers can be absorbent article diaper, catamenial devices, wound dressings, bandages, incontinence pads, wipe was underwear, insole, comprising an effective amount of a crystalline siliceous molecular sieve, having enhanced body fluid to be adsorbed odor removal performance of the at least a molecular sieve having a pore size of about 5.5, and relatively low water adsorption capacity.

Description

本发明涉及用于吸附体液的、具有除臭性能的纤维吸附制品,如可换尿布、月经用品(如棉塞、卫生巾)、伤口敷料、绷带、失禁垫、揩擦物、可换内衣、鞋垫等等。 The present invention relates to the adsorption of body fluids, the absorbent article having a deodorizing fiber properties, as can changing diapers, catamenials (e.g., tampons, sanitary napkins), wound dressings, bandages, incontinence pads, wipe thereof, may for underwear, insole and so on. 具体而言,这些纤维制品中含有可提高除臭效果的含硅结晶分子筛成份。 In particular, products containing these fibers may improve the deodorizing effect siliceous crystalline molecular sieve component.

纤维吸附制品早已为人所知。 Absorbent article has been known for fiber. 其中大量纤维按一定结构排列,以吸附和保留被吸附体液。 Wherein the plurality of fibers are arranged according to a certain structure, it is adsorbed to adsorb and retain body fluids. 保留在这些吸附制品内的体液可散发难闻的气味。 In the absorbent article to retain these body fluids may be circulated unpleasant odor.

体液的气味可能来自各自化合物。 Odor of body fluid from the respective compounds may. 这些化合物或者是在体内产生并排出人体的,如排泄物、月经、汗液、或伤口渗出液,或者是微生物作用于上述体液而产生的。 These compounds or are generated and the body, such as excrement, menses, perspiration, or wound exudate, or microbial action on the bodily fluid discharge is generated in vivo. 这些气味可来自氨、铵化合物、胺类、低级羧酸或酯如异戊酸等、醛类、硫化物等等。 These odors may be derived from ammonia, ammonium compounds, amines, esters of lower carboxylic acids such as isovaleric acid or the like, aldehydes, sulfides and the like. 许多有味化合物可使人对其产生嗅感的嗅感临界浓度都相当低,如在空气中的体积浓度常常不到几个PPM。 Many odorous compounds make them produce human olfactory sense of smell critical concentrations are quite low, such as volume concentration in the air is often less than a few PPM. 一般体积浓度不到40PPb的氨就可被嗅出。 Usually volume concentration can be less than 40PPb ammonia smell. 硫化氢的嗅感临界浓度约为1PPb,异戊酸则不到100PPb。 Olfactory sense of the critical concentration of hydrogen sulfide is about 1PPb, isovaleric acid is less than 100PPb.

迄今为止,已提出许多减除这些气味的方法。 So far, many methods have been proposed deduction of these odors. 如用香粉掩盖从吸附制品中散发的气味。 A covering radiated from the odor absorbent article with the powder. 其它方法包括利用某些物质去除有味化合物。 Other methods include use of certain compounds removing odorous substances.

去除有味化合物有几种可能的机制。 Removing odiferous compounds are several possible mechanisms. 如可通过化学反应使有味物质转变成无味的和/或不挥发的化合物,或使其被不挥发物质,如一种液体或固体吸收。 As it can be passed through a chemical reaction or odiferous substance compound and converted to odorless / non-volatile, or is not so volatile substance, such as a liquid or a solid absorbent. 一种有效的除臭吸附制品、特别是用来脱除嗅感临界浓度很低的体液气味的吸附制品,必须能在使用条件下基本上脱除所有的有味化合物,而不管其浓度高低。 An effective deodorizing absorbent article, particularly for the removal of smell the odor threshold concentration low body fluid absorbent articles, must be able to remove substantially all of the odorous compound in the conditions of use, regardless of their level of concentration. 即,该吸附制品必须能吸附既使是痕量的有味化合物,并且能在接近饱和时,也能保留住被吸附的化合物。 That is, the absorbent article must be capable of adsorbing odorous compounds even trace amounts, and can be at close to saturation, the compound can also be adsorbed to retain.

在用于吸附体液的纤维除臭制品中使用固体吸附剂已是公知的了。 Using a solid adsorbent for adsorbing fibrous article deodorizing body fluids are well known in the. 其中可将硅胶、活性氧化铝、硅藻土、漂白土、及其它粘土矿物、沸石等单独或混合在一起作为气味“吸附剂”使用,但最常用的抑制气味的固体吸附剂是活性木炭或活性炭。 Which may be silica gel, activated alumina, diatomaceous earth, fuller's earth and other clay minerals, zeolites, alone or mixed together as odor "adsorbents" use, but the most commonly used solid adsorbents is activated charcoal odor inhibition or activated carbon.

1977、6、10公开的日本专利申请说明书70200中公开的是像纸和疏松纤维这样的纤维制品。 Japanese Patent Application Publication 1977,6,10 specification 70200 is disclosed in fiber products such as paper and loose fibers. 该吸附制品先在100-450℃温度下加热处理1-100分钟,然后用沸石(已经过防水剂处理)、合成沸石、活性炭或钙类皂土处理。 The absorbent article to a heat treatment at a temperature of 100-450 ℃ 1-100 minutes, and then zeolite (which had been treated water), synthetic zeolite, activated carbon or calcium soap-soil.

1983、8、17公开的日本专利申请说明书138452公开了一种含有吸附纤维的卫生巾,其中吸附纤维的外表面有一层沸石和抗坏血酸化合物,如抗坏血酸或异抗坏血酸的钠或钾盐,或是抗坏血酸或异抗坏血酸的酰基衍生物。 Japanese Patent Application 138452 discloses a sanitary napkin disclosed 1983,8,17 containing adsorbent fiber, wherein the fiber outer surface of the adsorption layer of zeolite and ascorbic acid compounds, such as ascorbic acid or sodium erythorbate or potassium salts, or ascorbic acid isoascorbic acid or acyl derivatives. 其中的沸石最好是大孔的X、或Y型沸石。 Preferably wherein the zeolite X, zeolite Y or macropores.

1981、3、30公开的日本专利申请说明书31425公开了另一种卫生巾,其中的除臭剂上涂复了一层可吸附水的高分子材料。 Japanese Patent Application Publication 1981,3,30 specification 31425 discloses another sanitary napkin, a coating layer of a polymer material wherein the adsorbed water on deodorant. 该除臭剂可是硅酸镁、硅酸钙、硅酸铝、硅胶、球藻素粉(Chlorella)叶绿素粉、离子交换树脂粉、活性炭或沸石。 But the deodorant magnesium silicate, calcium silicate, aluminum silicate, silica, Haematococcus pigment powder (Chlorella) chlorophyll powder, an ion-exchange resin powder, activated carbon or zeolite.

1981、12、16公开的欧洲专利申请41569号公开了一种含分子筛的尿布。 1981,12,16 disclosed in European Patent Application No. 41569 discloses a molecular sieve-containing diaper. 该尿布接触用者皮肤的一面上有一层纤维层,另一面是涂了分子筛的纤维层。 Contacting one surface of the skin of the diaper with a fibrous layer, the other surface of the fibrous layer is coated with molecular sieve. 其中的分子筛是能选择吸附铵离子的一种分子筛,如F、W、或A型沸石、合成的水钙型沸石、合成的或天然丝光沸石、菱沸石、钙十字沸石、斜发沸石等等。 Wherein the molecular sieve is able to select a molecular sieve adsorption of ammonium ions, such as F, W, or A-type zeolite, synthetic zeolite, calcium water, synthetic or natural mordenite, chabazite, phillipsite, clinoptilolite and the like .

1986、11、27公开的日本专利申请说明书268253公开了一种卫生用品。 Japanese Patent 1986,11,27 open specification 268 253 discloses a sanitary supplies. 该用品由天然或合成纤维制成,纤维上分散或浸上一种去辉黄煌岩系的矿物。 The articles made from natural or synthetic fibers, or immersion on one kind of dispersing mineral Huang Huang to luminance based on rock fibers. 该文公开的云辉黄煌岩(如海泡石)的吸水率约为天然沸石吸水率的4倍。 Which discloses a rock Winfair Huang Huang (e.g., sepiolite) is about four times water absorption water absorption of natural zeolite. 用云辉黄煌岩制出的用品可吸附去除人体排出的排泄物、汗液、和人体气味。 Huang Huang rock produced by the Winfair supplies can adsorb and remove exudates, sweat, and body odor discharged from the body. 这种卫生用品可用来作尿布、卫生巾、棉塞、手巾和内衣。 This hygiene products can be used to make diapers, sanitary napkins, tampons, towels and underwear.

1984、5、31公开的日本专利申请说明书95042公开了一种双轴向延伸的高聚物薄片。 Japanese Patent Application Publication 1984,5,31 specification 95042 discloses a biaxially oriented polymer sheet extends. 其中含有20-70wt%的除臭粉,如活性碳、沸石、硅藻土、粘土。 Wherein the powder comprising 20-70wt% of deodorant, such as activated carbon, zeolites, diatomaceous earth, clays. 薄片上有0.1-5微米的微孔,填上吸附剂后用作卫生擦巾或卫生巾,可充分吸收液体,防止其渗漏,同时除臭性和透气性都很好。 From 0.1 to 5 microns on the microporous sheet, after fill or adsorbent being used sanitary napkin wipes, can fully absorb the liquid, which prevents leakage, while deodorizing and air permeability are good.

1979、11、5公开的日本专利申请说明书141857公开了一种在两层之间加入除臭剂的叠层物。 Japanese Patent Application Publication 1979,11,5 specification 141,857 discloses a deodorant is added between two laminate. 其中除臭剂为活性炭、沸石、离子交换树脂、羧甲基纤维素或聚乙二醇。 Wherein the deodorant agent is activated carbon, zeolite, ion exchange resins, carboxymethylcellulose or polyethylene glycol.

由于除臭以外的其他原因,一直将沸石和分子筛用于纤维制品中。 For reasons other than deodorant, zeolite and molecular sieves have been used in fiber products. 如1986、6、26公开的日本专利申请说明书138658公开了用不渗水的聚氨酯膜作卫生包或尿布。 As disclosed in Japanese Patent Application 1986,6,26 specification 138 658 discloses a polyurethane film with a water-impermeable package for the sanitary or diapers. 其中膜上带有经离子交换引入沸石的抗细菌的金属离子。 Wherein the metal film with ion-exchanged ion is introduced antibacterial zeolite. 这些抗细菌性的金属离子可是铜、银或锌。 These metal ions bacterial resistance, but copper, silver or zinc. 其中沸石的比表面大于150m2/g,硅铝比小于14。 Wherein the zeolite surface area greater than 150m2 / g, silica to alumina ratio less than 14. 类似的,1985、6、25公布的US4525410公开了一种纤维制品,其中至少有一部分纤维交织在一起形成网络,沸石颗粒掺入并保留在该网络结构中。 Similarly, 1985,6,25 published US4525410 discloses a fiber article, wherein at least a portion of the fibers intertwined to form a network, the zeolite particles are incorporated and retained in the network structure. 该沸石的比表面至少要达到150m2/g,且硅铝比要小于14,最好小于11,并经过银、铜、或锌的离子交换处理。 At least to achieve a specific surface area of ​​the zeolite 150m2 / g, and a silica to alumina ratio less than 14, preferably less than 11, and after silver, copper, zinc, or ion exchange treatment.

用分子筛控制其它气味已是公知的。 With molecular sieves to other odor control it is well known. 如在US4437429中公开的与粘土混合的水合沸石对消除动物排泄物气味特别有效。 As particularly effective in eliminating the odor of animal waste mixed with clay hydrated zeolite disclosed in US4437429. 实验表明,单独用沸石消除动物排泄物气味,效果并不好,因为沸石本身的吸水性不如粘土好。 Experiments show that zeolite alone eliminate animal waste odor, the effect is not good, because the water-absorbing zeolite itself is not as good clay. US4437429提到,用粘土和沸石混合物吸收动物排泄物的某些臭气时,混合物中的沸石成份不仅是水合态的,而且其中的水合水是原始存在的水合水。 When referred to US4437429, with a mixture of clays and zeolites absorb certain odors of animal excrement, in the zeolite component of the mixture is not hydrated state, and wherein the water of hydration be the original water of hydration present. 该文声称,经过热处理脱去水的沸石,再加水的效果不好。 The article claimed that, after the effect of zeolite water heat off, add water is not good.

通常用于除臭的沸石,最好是骨架Si/Al比较小、对水或其他极性较强的分子如氨或硫化氢的吸附容量较大的一类沸石。 Zeolites are normally used for deodorizing, preferably skeletal Si / Al is relatively small, water or other polar molecules such as ammonia or hydrogen sulfide adsorption capacity of a zeolite is large. 但上述US4437429公开的内容与此不同。 US4437429 disclosed above but the content is different. 该文公开了许多所谓的高硅沸石类。 The paper discloses a number of so-called high silica zeolites. 这些沸石是用像四烷基铵离子这样的有机模板剂合成得到的。 These zeolites are synthesized using organic templating agents such as the tetraalkylammonium ions obtained. 其中包括ZSM-5、ZSM-11、ZSM-12,和ZSM-23。 These include ZSM-5, ZSM-11, ZSM-12, and ZSM-23. 但其中择优选用的沸石品种是标准骨架Si/Al比约10的天然斜发沸石。 Preferred species but in which the zeolite is selected standard skeletal Si / Al ratio of about 10 natural clinoptilolite zeolite. US4648977公开了用高硅分子筛,包括二氧化硅多形物硅沸石(Silicalite),吸附待净化废水中的毒性有机物,如硫醇类。 US4648977 discloses the use of high silica molecular sieves, including the silica polymorph silicalite (of Silicalite), adsorbed toxic organic wastewater to be purified, such as thiols.

本发明提供了用于吸附体液的纤维吸附制品,其中含有有效量的分子筛,以减少从该制品中散发的气味。 The present invention provides a fiber for adsorbing body fluids absorbent article, wherein the molecular sieve containing an effective amount to reduce the emitted odor from the article. 上述分子筛包括硅质的结晶分子筛,该分子筛中至少90%的骨架四面体氧化物单元为SiO2四面体,其孔径至少5.5 The above-described molecular sieves include crystalline siliceous molecular sieve, at least 90% of the molecular sieve framework tetrahedral oxide units are SiO2 tetrahedra, a pore size of at least 5.5 ,在下述标准条件下吸附水的容量不高于10wt%。 , Adsorbed water under the following standard conditions capacity of not more than 10wt%.

本发明的纤维吸附制品可基本上消除各种体液的特征气味。 Fibrous absorbent article of the present invention may substantially eliminate the characteristic odor of various body fluids. 因此,该制品特别适用于各种可换尿布、月经用品,伤口敷料、绷带、失禁垫、卫生巾、可换内衣、鞋垫、揩擦物等。 Thus, the article may be particularly applicable to a variety of diapers, catamenials, wound dressings, bandages, incontinence pads, sanitary napkins, underwear replaceable insoles, wipe, and the like.

本发明的纤维吸附制品含有硅质的结晶分子筛,该分子筛中至少约90%、最好至少约95%的骨架四面体氧化物单元是SiO2四面体,且在标准条件下对水的吸附容量低于10wt%。 Fibrous absorbent article of the present invention contains a crystalline siliceous molecular sieve, at least about 90%, preferably at least about 95 percent of the framework tetrahedral oxide units are SiO2 tetrahedra, and low adsorption capacity for water under standard conditions to 10wt%. 测定分子筛对水的吸附容量一般是在一特定的温度、压力和时间下进行的。 Determination of molecular sieve adsorption capacity for water is generally carried out at a specific temperature, pressure and time. 因此,提到水的吸附容量时,应注明“标准条件”。 Thus, referring to water adsorption capacity, marked "standard conditions." 该“标准条件”为:温度25℃,水蒸汽压4.6托,时间2小时。 The "standard conditions" are: temperature 25 ℃, the water vapor pressure of 4.6 Torr for 2 hours.

对于硅铝酸盐分子筛,最常用于本发明的是骨架SiO2/Al2O3摩尔比至少约18,如约35至无限大,最好为200-500的硅铝酸盐分子筛。 For aluminosilicate molecular sieves, it is most commonly used in the present invention, the skeleton SiO2 / Al2O3 molar ratio of at least about 18, such as from about 35 to infinity, preferably 200-500 aluminosilicate molecular sieves. 所有适用的硅质分子筛的孔径至少5.5 All applicable pore siliceous molecular sieve of at least 5.5 ,最好至少6.2 , Preferably at least 6.2 ,标准条件下吸附水的容量最好小于6wt%。 , The capacity of adsorbed water under standard conditions, preferably less than 6wt%.

用于本发明的分子筛的效果与由于水热反应而存留在微孔结构中内孔穴内的水合水无关。 Molecular sieves of the present invention to the effect of the heat of reaction due to water retained within the cavity irrespective of the water of hydration within the microporous structure. 事实上,至少大部份、通常基本上是全部的原始水合水在去除堵塞孔的模板剂(可能以分子筛合成时的形态存在)时,就已被除掉了。 In fact, at least the majority, typically substantially all of the original water of hydration is removed in the caulking hole templating agent (which may exist in the form in the molecular sieve synthesis), it had been rid of. 焙烧可有效地去除有机物部分,同时,水洗或用腐蚀性的或稀释的无机酸溶液洗涤也可有利地去除孔隙中多余的无机合成试剂,降低碱金属的含量,特别是非沸石的,如被包藏的碱金属化合物,也是十分有利的。 Firing can effectively remove the organic portion, while washing with water or washing mineral acid solution or dilute caustic may be advantageously removed with the excess pore inorganic synthesis reagents, reducing alkali metal content, particularly the non-zeolitic, such as occluded alkali metal compound, is also very advantageous. 这些过程也可用来去除原始的水合水。 These processes can also be used to remove the original water of hydration.

适用于本发明的硅质分子筛包括微孔性结晶硅铝酸盐,即沸石分子筛和所谓的二氧化硅多形体。 Useful in the present invention, siliceous molecular sieves include the microporous crystalline aluminosilicates, i.e. the zeolitic molecular sieves and so-called silica polymorphs. 对于后者的组成,最理想的是由SiO2四面体单元组成。 For the latter composition, and most preferably of SiO2 tetrahedral units. 但其合成形式中常含有至少痕量的铝,这些铝是由合成试剂中的杂质带入的。 But the synthetic forms often contain at least trace amounts of aluminum, which is aluminum impurities in the synthesis reagents entrained. 硅铝酸盐分子筛包括大量公知的结晶沸石。 Aluminosilicate molecular sieves comprise a large number of well-known crystalline zeolite. 这些高硅分子筛既可从市场购得,也可通过本领域公知的方法制备,包括直接进行水热合成或涉及某些形式的晶格脱铝过程。 These high-silica molecular sieves from either commercially available, may be prepared by methods known in the art, including direct hydrothermal synthesis or involving some form of lattice dealumination. EMFlanigen关于“高”Si/Al比沸石和二氧化硅分子筛的全面综述发表在下文中:“Proc.5th.Int.Conf.Zeolites,NaPles,1980”,LVCRees,ed.,Heyden,London,pp.760-780。 EMFlanigen on the "high" Si / Al zeolites and silica molecular sieves comprehensive review published in the following ratio: "Proc.5th.Int.Conf.Zeolites, NaPles, 1980", LVCRees, ed, Heyden, London, pp.760. -780. 这里作为参考文献列出。 Listed here as a reference.

本发明的一个重要方面是硅质分子筛对水的吸附容量在标准条件下小于10wt%,另一个重要内容是,如果晶格中有AlO-2四面体的话,该四面体单元的数目要比SiO2四面体的数目少得多。 An important aspect of the present invention is a siliceous molecular sieve adsorption capacity for water of less than 10wt% under standard conditions, another important content, if there AlO-2 tetrahedron lattice, then the number of tetrahedral units than SiO2 the number of tetrahedral much less. 实验表明,硅质分子筛骨架的SiO2/Al2O3之比与该分子筛吸附水的容量,即所谓的分子筛的疏水性之间有某种关联。 Experiments show that the ratio of molecular sieve adsorb water capacity of the siliceous molecular sieve framework SiO2 / Al2O3, namely there is a correlation between the hydrophobicity of the so-called molecular sieves. 但在某些情况下,对于如β沸石而言,骨架中硅质晶体量较高的分子筛,可能缺少足够的疏水性,或不具有所要求的吸水性。 However, in some cases, for purposes such as β zeolite, siliceous crystal framework higher amounts of molecular sieve, it may lack sufficient hydrophobicity, or having no water absorbent desired. 所以,虽然许多其骨架的SiO2/Al2O3比大于约18,特别是大于约35的分子筛,具有符合本发明要求的疏水性,但还有一些分子筛是不符合要求的。 Therefore, although many of its framework SiO2 / Al2O3 ratio greater than about 18, particularly greater than about 35 molecular sieve, having a hydrophobic meet the requirements of the present invention, but some of the molecular sieves is undesirable. 在某些情况下,降低分子筛中碱金属的含量,如使其不高于0.2wt%(以非水合物为基准),也是十分有利的。 In some cases, reduced alkali metal content molecular sieves, so as not more than 0.2wt% (with reference to non-hydrate), also very advantageous.

我们发现,无论是什么原因造成的,对上面提到的大孔的硅质分子筛,尤其是当这些分子筛已基本上脱除了原始合成时引入的水合水时,介质种类以与脱除体液气味有关的特殊方式起作用。 We found that, no matter what the cause of the above-mentioned large pore siliceous molecular sieves, especially molecular sieves when these have been substantially hydrated removal except when raw syngas introduced when, with the removal of a body fluid media type relating to odor acting special way. 采用有机模板剂,可将许多合成分子筛制成高硅分子筛-有些甚至是用不加铝的反应混合物制成的。 Organic templating agent, many synthetic zeolite molecular sieves can be made high silicon - some even without using a reaction mixture made of aluminum. 这些沸石具有明显的亲有机物性。 These zeolites have apparent organophilic properties. 其中包括ZSM-5(US3702886),ZSM-11(US3709979),ZSM-35(US4016245),ZSM-23(US4076842),及ZSM-38(US4046859),不一一列举。 These include ZSM-5 (US3702886), ZSM-11 (US3709979), ZSM-35 (US4016245), ZSM-23 (US4076842), and ZSM-38 (US4046859), to name a few. 已经发现被称为Silicalite和F-Silicalite的二氧化硅分子筛特别适用于本发明,因此是优选分子筛。 It has been found, and silica molecular sieves are referred to as F-Silicalite Silicalite is particularly suitable for use in the present invention, it is preferable because the molecular sieve. 这些材料分别公开在US4061724和US4073865中。 These materials are disclosed in US4061724 and in US4073865. 上述合成出的硅质分子筛,只要SiO2/Al2O3比大于35,一般不需进行额外处理去提高其疏水性,就可适用于本发明。 Siliceous molecular sieves synthesized above, as long as the SiO2 / Al2O3 ratio greater than 35, usually without additional treatment to increase their hydrophobicity, can be useful in the present invention. 不能通过直接合成得到Si/Al比足够高、疏水性好的分子筛,可通过脱铝处理,氟处理等,转变成亲有机物性的沸石产品。 Can not be obtained by direct synthesis Si / Al ratio is sufficiently high, hydrophobic molecular sieves, can be obtained by dealumination treatment, fluorine treatment and the like, organic transition zeolite product of marriage. PKMaher等在“Molecular Sieve Zeolites”,Advan.Chem.Ser.101,American Chemical Society,Washington,DC,1971,P.266中介绍了用高温蒸汽处理Y型沸石的方法,用该法可得到亲有机物性的产品。 PKMaher et al "Molecular Sieve Zeolites", Advan.Chem.Ser.101, American Chemical Society, Washington, DC, 1971, P.266 method described in the high-temperature steam treatment of Y-type zeolite, obtained by the method organophilic products and services. 最近报导的一种适用于沸石类的处理方法,涉及到脱铝和用硅替代脱铝后的点阵点。 Recently reported a method suitable for treating the zeolites, it involves dealumination and the alternative dealuminated silicon lattice points. 该法公开在Skeels等人申请的、1985、3、5公布的US4503023中。 The method disclosed in Skeels et al application, US4503023 1985,3,5 published. 用卤素或卤化物处理沸石,以提高其疏水性的方法公开在US4569833和US4297335中。 Halogen or halide compound treatments for zeolites to increase their hydrophobicity are disclosed in US4569833 and in US4297335.

对上述吸附剂而言,重要的是,敞开的孔体系要能使气味分子容易进入其内晶穴。 The above adsorbent, it is important that the pore system open to allow easy access to the odor molecules within the crystal cavity. 对于像四烷基铵离子这样的大有机模板剂离子制出的硅铝酸盐或二氧化硅多形体,必须去除平衡电荷的有机离子和任何包藏的模板剂,以便能够吸附气味分子。 For the tetraalkylammonium ions such as a large organic templating ions produced out of the aluminosilicates or silica polymorphs, charge balancing organic ions must be removed and any occluded templating agent, to be able to adsorb odor molecules. 在这种去除过程,以及在去除无机物杂质的过程中,同时除掉了原始的水合水。 In such a removal process, and during the removal of inorganic impurities, while the original water of hydration is removed. 虽然由于暴露在空气中而重新获得一部分水合水,但这并不影响分子筛的常规使用,因为既可用水合态分子筛,也可用脱水后的分子筛。 Although due to exposure to air and to regain a part of water of hydration, but this does not affect the use of conventional molecular sieves, either as hydrated molecular sieves, molecular sieves can also be dehydrated. 但一般择优选用脱水的分子筛。 But generally preferred molecular sieve dehydration of choice. 在上面提到的脱铝过程中,原始的水合水也被同时脱除,必要时,也同样地可以被恢复。 As in the dealumination process mentioned above, the original water of hydration is also removed at the same time, if necessary, also to be restored.

应指出的是,骨架的SiO2/Al2O3比是重要的,但无需与常规的湿法化学分析得到的Si/Al比完全一样,特别是对于采用高温蒸汽进行脱铝处理的情况。 It should be noted that, SiO2 / Al2O3 ratio of the backbone is important, but without conventional wet chemical analysis of the obtained Si / Al ratio is completely the same, especially for high temperature steam dealumination treatment situations. 因为这时沸石中含铝的四面体单元虽然受到破坏,但至少仍有一部分铝保留在沸石晶体中。 Because then the aluminum-containing tetrahedral units in the zeolite, although damaged, but still at least a portion of the retention of the aluminum in the zeolite crystals. 对于这样的沸石产品,必须借助于其他分析手段,如X-射线衍射及NMR。 For such zeolite products, we must resort to other analytical tools, such as X- ray diffraction and NMR. 已经发现一种经这样的蒸汽处理的、名为LZ-10的Y型沸石特别适用于本发明,特别是将其与二氧化硅多形体Silicalite混合使用时更好。 The thus been found that a steam treated, Y-type zeolite called LZ-10 is particularly suitable for the present invention, in particular when it is better to use Silicalite mixed with a silica polymorph. LZ-10的制备过程已在US4331694和1978、2、23申请的美国专利申请序号880561中详细公开,这里作为参考列出。 The preparation of LZ-10 is disclosed in detail in US4331694 and U.S. Patent Application Serial No. 880,561 filed in 1978,2,23, listed here by reference. 两种分子筛按各种比例混合,效果都很好。 Two kinds of molecular sieve mixed in various proportions, the effect is very good. 但每种吸附剂的择优用量至少10wt%,以两种吸附剂的总重量为基准,(以水含的重量为基准)。 However, preferred amounts of each adsorbent is at least 10wt%, based on the total weight of the two adsorbents as a reference (the water content by weight as a reference).

可采用任何形状的硅质结晶分子筛。 Any shape may be employed siliceous crystalline molecular sieve. 典型的例子是粉末状或团成大的颗粒,如最大直径约0.5-500μ或更大的团粒。 Typical examples are powders or particles into larger groups, such as the maximum diameter of about 0.5-500μ pellet or larger. 团粒可制成任何形状,如球形、圆柱形、自由形状等。 The pellet may be made of any shape, such as spherical, cylindrical, free-form and the like. 造粒时可用像氧化铝或二氧化硅这样的粘合剂。 Available such as alumina or silica binder granulation. 团粒中可含有下面将提及的纤维吸附制品所需的其他成份。 Pellets may contain other ingredients required for the absorbent article below the fibrous mentioned.

本纤维吸附制品含有能吸附体液如月经、小便、汗液、伤口渗出液等的纤维材料。 This fiber absorbent article comprising a fibrous material can absorb body fluids such as menses, urine, sweat, wound exudate or the like. 已提出可用作吸附剂的各种纤维材料包括如木纤维、纤维素衍生物(人造丝)、棉花、合成的高聚物或合成的高聚物混合物(如聚酯、聚丙烯、尼龙,聚乙烯等)。 May be used as an adsorbent have been proposed various fiber materials include wood fibers, cellulose derivatives (rayon), cotton, synthetic polymer or mixture of polymers synthetic (e.g. polyester, polypropylene, nylon, polyethylene, etc.).

纤维材料可编织成网状结构,也可是非网状结构,可加工成絮胎、或网状物、或薄片、或织物、或多孔泡沫等。 Fibrous material may be woven into a mesh structure, but also the non-mesh structure can be processed into the batting or web, or sheet, or fabric, or a porous foam. 这些结构或用任何方便的技术,包括干法和湿法制成。 These structures, or by any convenient technique, including wet and dry formed.

纤维吸附制品可以基本上是一种单组份制品,也可是多组份制品。 Absorbent article may be substantially fiber is a single component product, but also multi-component article. 具体组合方式常视制品的用途及其它成份而定。 DETAILED often depends on the use and combination products, depending on other ingredients. 具体的单组分制品有纸巾、无纺织物内衣、鞋垫等基本上由纤维材料制成的制品。 Specific products are one-component articles made of a fiber material substantially towels, underwear, nonwoven fabric, insole. 其中纤维结构内掺入硅质分子筛。 Wherein the siliceous molecular sieve incorporated within the fibrous structure. 多组份的制品则可由由不同的或相同材料构成的几层或几部份组成。 Multi-component article may be composed of several layers or several parts made of different or the same material. 例如卫生巾可由多层纤维吸附织物制成,揩擦布则可由多层纤维吸附薄层制成。 Adsorption layers of fiber such as sanitary napkins may be made of fabric, a cloth wipe can be made from thin layers of fibers adsorption. 不同成份在纤维吸附制品中起不同的作用。 Different components have different functions in the fibrous absorbent articles. 如可将纤维絮胎放在基本上不透水的外层与透水但无吸附性的与人体接触的内层之间,制成尿布、绷带或卫生巾。 The fiber wadding may be placed in a substantially water-impermeable outer layer and the inner layer between the non-permeable but adsorbent in contact with the human body, made of a diaper, sanitary napkin, or bandage. 同样,可用一种强度较大、但也许基本上无吸附性的结构网,使纤维材料附着其上。 Similarly, a larger one of intensity can be used, but perhaps substantially no net adsorptive structure, the fiber material attached thereto. 这种结构网可为制成的纤维吸附制品提供很好的强度。 This structure can provide a good web strength fibers made from absorbent article.

当将纤维吸附制品用于月经用品、失禁垫、卫生巾和尿布时,该制品内可含有其他成份,包括超级吸附材料。 When the fibers for catamenial absorbent articles, incontinence pads, sanitary napkins and diapers, within the article may contain other ingredients, including super-absorbent material. 超级吸附材料能吸附大量的水,如常常能吸附直到其干重10倍或10倍以上的水。 Super adsorbent material capable of adsorbing a large amount of water, as often until their dry weight can absorb more than 10 times, or 10 times as much water. 典型的超级吸附材料是那些水溶胀性高聚物,如多糖类、改性和再生的多糖类、接枝的多糖类、聚丙烯酸酯类、聚丙烯腈类(尤其是与聚乙烯醇接枝的聚丙烯腈类),聚乙烯醇、亲水的聚氨基甲酸乙酯、部分水解的聚丙烯酰胺类、磺化聚苯乙烯、磺化的聚醚类、聚(烯化氧)等。 Typical super-absorbent material are those water-swellable polymers, such as polysaccharides, modified polysaccharides and regenerated, grafted polysaccharides, polyacrylates, polyacrylonitrile (especially polyethylene grafted polyacrylonitrile-based alcohol), polyvinyl alcohol, hydrophilic polyurethane, partially hydrolyzed polyacrylamides, sulfonated polystyrene, sulfonated polyether, a poly (alkylene oxide) Wait. 可将超级吸附剂制成任何便于使用的形状、如纤维状、球形、膜片、或涂在纤维吸附制品的其他成份上。 Super adsorbent may be formed in any shape convenient to use, such as a fibrous, spherical, membrane, or coated on the other ingredients of the fibrous absorbent article.

可供使用的其他成份包括药物、其他吸收剂和吸附剂(包括碳酸氢钠、活性炭、粘土、硅胶和其他水吸附和/或铵离子吸附容量高的分子筛如X、Y、W、A型沸石,斜发沸石、丝光沸石、等)等等。 Other ingredients include drugs for use, other absorbents and adsorbents (including sodium bicarbonate, activated charcoal, clays, silica gel and other adsorbing water and / or an ammonium ion adsorption capacity high molecular sieves such as X, Y, W, A-type zeolite , clinoptilolite, mordenite, and the like) and the like. 可使用香料,但必须考虑分子筛的吸附性,一般择优选用大分子香料。 Perfumes may be used, but must be considered a molecular sieve adsorbent, flavor is generally preferred selection molecules.

硅质结晶分子筛在纤维吸附制品中的加入量应能使被吸附的体液气味显著减少(既使不能完全消除的话)。 Siliceous crystalline molecular sieve adsorption of the fiber product was added an amount such that the body fluid odors adsorbed significantly reduced (even if not completely eliminate it). 因此,应根据纤维吸附制品的用途,改变制品中掺入的硅质结晶分子筛的量。 Thus, the fibers should be based on the use of absorbent articles, the amount of change in the incorporated article siliceous crystalline molecular sieve. 如:将制品用于尿布时,由于大量有味液体可能要存留在尿布里,因此分子筛的加入量要比将制品用于绷带时的加入量多。 Such as: when the article is used in diapers, because a large number of odorous liquid can be retained in the diaper, the amount of molecular sieve was added so the amount added than the article for more bandage. 本发明纤维吸附制品中掺入的硅质结晶分子筛,其特征是加入量很少,效果很好。 The absorbent article of the present invention, the fibers incorporated siliceous crystalline molecular sieve, characterized in that the addition of small amounts with good results. 其原因一部份是由于这些分子筛的吸附活性,一部分是由于硅质分子筛对体液中散发的有味化合物的选择吸附。 The reason for this is because a part of the adsorption activity of these molecular sieves, silicalite molecular sieve in part due to the selective adsorption of the odorous compound in the fluid circulated in. 例如,只要0.1g硅质分子筛就能有效地除去月经用品散发的气味。 For example, as long as the siliceous zeolite 0.1g can be effectively removed catamenials odor.

可用各种方式表示纤维吸附制品中硅质分子筛的用量,如:以每件制品为基准,以有效面积为基准,以体积为基准,等等。 Represents the fiber in various ways siliceous molecular sieve adsorbent dosage article, such as: to each article as a reference, with reference to the effective area, on a volume basis, and the like. 由于纤维吸附制品的材料、构成及形状各异,纤维结构各异,因此,要建立一种正确有效的比较基准来确定硅质分子筛的含量,是有困难的。 Since the absorbent article of the fiber material, configuration and shapes, different fibrous structures, therefore, to establish a correct and valid comparison reference to determine the content of the siliceous molecular sieve, it is difficult. 但一般可用单位体积纤维结构(未挤压过、干态的)上的克数,或单位有效面积(即纤维结构主平面的面积)上的克数表示硅质分子筛的含量。 However, per unit volume generally available fibrous structure (not extruded, dry state) in grams on the number of grams, or unit effective area (i.e. area of ​​the main plane of the fibrous structure) represents the content of siliceous molecular sieves. 一般每100cm3体积纤维材料上硅质分子筛的含量至少约0.001g,有时直到50g,最好为0.01-25g,通常在0.05-10g之间。 Usually the content of the siliceous molecular sieves per 100cm3 volume of the fiber material is at least about 0.001g, sometimes up to 50g, preferably 0.01-25g, typically between 0.05-10g. 典型的,每100cm2有效面积上硅质结晶分子筛含量约0.01-25g,如约0.05-10g。 Typically, the content of the siliceous crystalline zeolite active area of ​​100cm2 per 0.01-25g, such as about 0.05-10g. 用途不同时,如用作月经用品时,每只垫或每个塞上分子筛用量约为0.01-10g;用作尿布时,其用量为每块尿布约0.05-50g,对于鞋垫,则每垫用量约为0.05-10g。 Not the same purpose, such as when used as a catamenial, each pad or each plug an amount of about 0.01 to 10 g of molecular sieve; when used as a diaper, a diaper in an amount of from about 0.05 to 50 g each, for the insole, the amount of each pad about 0.05-10g.

硅质结晶分子筛可以任何适宜方式加到纤维吸附制品中。 Siliceous crystalline molecular sieve can be applied in any suitable manner fibrous absorbent articles. 例如,可使其松散地分散在含纤维材料的絮胎或薄片内。 For example, it may be loosely dispersed within the fibrous batting or sheet material. 但一般最好将其充分固定在纤维吸附制品内,使其不易漏出,沾至人体上。 However, it is generally preferred to sufficiently fixed within the fibers absorbent articles, it is not easy to leak stick to a human body. 例如,可将分子筛放到可渗透液体的纤维吸附袋内,分子筛不能从袋内移出。 For example, molecular sieve can be adsorbed onto the fibers of the liquid-permeable pouch, the molecular sieve can be removed from the bag. 即,将分子筛置于两层经加热密封的可渗透的热塑薄片之间,薄片上可穿些小孔以达到所需的渗透性。 That is, the molecular sieve is placed between two layers of heated thermoplastic sheet permeable sealed, wear some small holes on the sheet to achieve the desired permeability. 一种将硅质结晶分子筛固定在纤维吸附制品中的颇具吸引力的方法是,在作为吸附剂的两层薄片或织物之间,放入分子筛,然后通过用针打孔的机械方式或用乳胶粘接、或用热封的方式,将两层粘接在一起。 Attractive method of fixing siliceous crystalline molecular sieve in absorbent articles is a fiber, sheet or between two layers of fabric as an adsorbent, into the molecular sieve, and then mechanically perforated with a needle or latex an adhesive, or by heat sealing manner, the two layers bonded together. 含分子筛的复合物很容易处理,包括切割、成型及装入纤维吸附制品。 Composite containing molecular sieve are easily handled, including cutting, molding and fiber loaded absorbent article.

使用分子筛的另一种方法是将其作为填料如将至少1wt%,如约1-70wt%,如5-70wt%的分子筛填入高聚物膜,或纸类材料内。 Another method uses a molecular sieve is used as an inner filler such as at least 1wt%, such as about 1-70wt%, such as 5-70wt% of molecular sieve filled polymer film, or a paper-like material. 这些膜或材料内可能含有纤维材料,或将被放入纤维吸附制品内。 These may contain a fibrous material or a film material, or is adsorbed into the fibrous article. 或者也可以类似方式将分子筛加到高分子熔融物制成的纤维材料和/或任何超级吸附材料中。 Or it may be added to fibers in a similar manner to the molecular sieve material of the polymer melt and / or any super-adsorbent material. 也可利用至少一部分吸附制品上的粘合剂材料加入分子筛(如,衬里、纤维材料、结构元件等),或甚至通过使分子筛与热塑材料(如衬里、纤维材料、结构元件等)接触,(如果热塑材料是在足够高的温度下变粘的话,)来加入分子筛。 May also be an adhesive material on at least part of the absorbent article added molecular sieves (e.g., liners, fibrous materials, structural elements, etc.), or even by a molecular sieve with a thermoplastic material (e.g., liner, fiber materials, structural elements, etc.) into contact, (If the thermoplastic material is at a sufficiently high temperature it becomes tacky,) was added to the molecular sieve.

图1是卫生巾的透视图; FIG. 1 is a perspective view of a sanitary napkin;

图2是图1所示卫生巾沿2-2剖面线的剖面图。 FIG 2 is a sectional view of the sanitary napkin shown in FIG. 1 taken along section line 2-2.

图1示出带织物贴面12的卫生巾10。 Figure 1 shows a sanitary napkin 10 with the fabric of the veneer 12. 图2是表示卫生巾10构造的剖面图。 FIG 2 is a cross-sectional view showing a configuration of the sanitary napkin 10 of FIG. 参照图2,织物贴面12为透水性的无纺织物,紧靠其内层-有一环绕卫生巾四周和底面的不透水层14。 Referring to FIG 2, the fabric 12 is permeable veneer of the nonwoven fabric, the inner layer close - with a surrounding impermeable layer of the sides and the bottom surface of the sanitary napkin 14. 在由织物贴面12和不透水层14所围成的体积内,装有用于吸附液体的纤维絮胎16,絮胎16里画出了超级吸附剂颗粒18。 Impermeable layer 12 and in 14 the volume enclosed by the fabric veneer, to adsorb the liquid containing fiber batting 16, batting 16 was drawn 18 super sorbent particles. 如图所示,无纺织物20和22构成了三明治结构,位于絮胎16中间,可渗透液体。 As shown, the nonwoven fabric 20 and 22 form a sandwich structure, located in the middle of the batting 16, a liquid-permeable. 在织物20和22之间分散有硅质分子筛,织物20和22用乳胶固定在一起。 22 between the fabric 20 and the siliceous molecular sieve is dispersed, fabric 20 and 22 are secured together by latex. 另一种方式是,把织物20和22直接附在卫生巾10的顶部或底部。 Another way is to direct the fabric 20 and 22 attached to the top or bottom 10 of the sanitary napkin.

本发明通过下面的例子予以具体说明。 The present invention shall be described in detail by the following examples. 体液,如月经中可含有低级羧酸和胺类,实例1-19说明硅质分子筛去除典型地存在于月经中的有味成份异戊酸和三乙胺的效果。 Body fluids, such as menses may contain lower carboxylic acids and amines, examples 1-19 illustrate the siliceous molecular sieve is typically present in removing odorous components menses isovaleric acid and triethylamine effect. 实例1-20中,将一定量的高硅硅铝酸盐和二氧化硅多形体以可重现及恒定不变的方式暴露于各种有味物质中,以测定被吸附气味的相对量或绝对量。 The relative amounts of Examples 1 to 20, the amount of high silica aluminosilicates and silica polymorphs in a reproducible and constant way exposed to various odorous substances, to determine the adsorbed odor or absolute amount. 实验中使用了配有聚四氟乙烯衬的硅橡胶隔片的40ml螺帽管形瓶,测得该瓶容量为43.5±0.1ml。 Used in the experiments with PTFE lined silicone rubber septa 40ml screw cap vial, the vial was measured capacity was 43.5 ± 0.1ml.

用由Analabs,Inc.,Hamden,Connecticut得到的、70/80目色谱纯的、标有ANASORB级的活性炭吸附剂。 Obtained by using Analabs, Inc., Hamden, Connecticut, 70/80 mesh is chromatographically pure, labeled activated carbon adsorbent ANASORB level. 将上述吸附剂称量,加入管形瓶,拧上盖。 The above adsorbent was weighed, added to the vial, screwing cover. 用Hamilton注射器将待吸附物加到密封的管形瓶中,用手摇动样品,使液-固-气三相混合,称量混合后5-10分钟内,用气相色谱分析管形瓶上部的气体。 Hamilton syringe with adsorbate to be added to a sealed vial, the sample was shaken by hand, so that the liquid - solid - gas-phase mixing, weighed and mixed for 5-10 minutes, analysis by gas chromatography of the upper portion of the vial gas.

为确定实验用挥发性化合物在空气中的最大蒸汽浓度,将纯化合物放入容量为43.5ml的管形瓶中,至少放置1小时后再进行分析。 To determine the maximum vapor concentrations of the volatile test compounds used in air, the pure compound was placed in vial 43.5ml capacity of at least 1 hour before analysis. 一般从43.5ml管形瓶上部取2微升样品进行分析,并注入2微升室内空气,以保持瓶内气压不变。 From 43.5ml generally tubular upper portion of the bottle taken 2 l samples were analyzed, and poured into 2 l of indoor air, in order to maintain constant pressure bottle.

每次注射样品前后,都将注射器针头置于真空下(压力估计小于5×10-3托)、200℃的注射器清洁器内。 Before and after each sample injection, the syringe needle will be placed under vacuum (estimated pressure of less than 5 × 10-3 Torr), the syringe or 200 ℃ the cleaner. 用100瓦灯泡作热源,置于注射器上方1至2英吋处,去除吸附在注射器聚四氟乙烯部件上蒸汽分子造成的任何交叉污染。 With a 100 watt light bulb as a heat source, was placed 1 to 2 inches above the syringe, remove any cross-contamination adsorbed on the Teflon parts of the syringe caused by the vapor molecules. 注射器在使用前,在真空条件下加热约5分钟,经过清洁处理后,用其分析室内空气,证明注射器内无污染。 Syringe, before use heated under vacuum for about 5 minutes, after the cleaning process, by which indoor air analysis, proved clean syringe.

用气相色谱分析测定管形瓶内上部气味组分的浓度,色谱柱为0.32mm(内径)×30m的熔氧化硅吸附剂毛细管柱,柱内有一层1微米厚聚乙二醇内涂层作为吸附剂。 Analysis of the upper portion of vial concentration determination of aroma components by gas chromatography column was 0.32 mm (i.d.) fused silica capillary column × 30m of adsorbent, 1 micron thick layer of polyethylene glycol coating the inner column as adsorbent. 用火焰离子检测器确定保留时间,炉温条件为50℃下保持4分钟,然后以每分钟10℃的速度升温至150℃。 Flame ionization detector to determine the retention time, oven temperature conditions for holding 50 ℃ 4 minutes, then warmed to 150 deg.] C at a rate of 10 deg.] C per minute.

例1(a)将10微升异戊酸放入一有盖的43.5ml管形空瓶中,按上述过程测出瓶上部蒸汽浓度为668PPM,保留时间为4.83分钟,同时在4.22分钟有一小的附加峰。 Example 1 (a) Ten microliters of isovaleric acid were placed in a tubular bottles have 43.5ml lid, according to the above process the measured vapor concentration of the upper portion of the bottle 668PPM, retention time of 4.83 minutes, while a smaller 4.22 minutes the additional peaks.

(b)向上面(a)中含有异戊酸的管形瓶内加入0.5g碳酸氢钠,发现管形瓶上部的异戊酸浓度降为2.2PPM,在步骤(a)中观察到的4.22分钟的峰仍然存在。 (B) a in the above (a) isovalerate vial was added 0.5g of sodium hydrogencarbonate, found isovaleric acid concentration is reduced to an upper portion of the vial 2.2 ppm, were observed in step (a) is 4.22 peak minutes remain. 另外,在4.87、6.36、6.61、和6.94处出现新的色谱峰。 In addition, 4.87,6.36,6.61, and at 6.94 new peaks appear.

(c)向上面(a)中含有异戊酸的管形瓶内加入0.5g等量Silicalite和LZ-10分子筛,发现管形瓶上部异戊酸浓度降至低于气相色谱检测极限,(该极限值为约0.82PPM),以外,4.22处峰消失,且无任何新的峰。 (C) a vial containing equal amounts of isovaleric acid was added 0.5g Silicalite and zeolite LZ-10 to (a) above, the upper portion of the vial was found isovaleric acid concentration falls below the GC detection limit (the limit is about 0.82PPM), other than the disappearance of the peak at 4.22, and without any new peaks.

例2-9测定了8种不同吸附材料脱除空气中三乙胺的能力。 Example 2-9 Determination of the capacity of eight kinds of different air removal adsorbent triethylamine. 三乙胺是各种动物和人类排泄物中的一种常见成份。 Triethylamine is a common ingredient in a variety of animal and human waste. 实验时,将500mg吸附剂固体放入43.5ml管形瓶内,加入足量三乙胺,使其含量达到4.37wt%。 When the experiment, the solid adsorbent is placed in 43.5ml 500mg vial, adding a sufficient amount of triethylamine, so that content of 4.37wt%. 作为对照,在另一个没有吸附剂的管形瓶内也加入三乙胺。 As a control, another vial without adsorbent is also added triethylamine. 按上述同样方法分析管形瓶上部蒸汽。 Analysis same manner as above the upper steam vial. 例2及下面例子中用的LZ-20,是一种经过蒸汽稳定处理的Y型沸石,其制备方法与制备LZ-10的方法基本相同,只是用蒸汽处理的条件较温和,得到的沸石在标准条件下的水吸附容量约10wt%,钠含量(以Na2O表示)0.2wt%,(以非水合态为基准)。 Example 2 LZ-20 and used in the following examples, through a steam stabilized Y-type zeolite, its preparation method and the preparation of LZ-10 is basically the same, except the conditions milder treated with steam, the zeolite obtained water absorption capacity under standard conditions of about 10wt%, sodium content (expressed as Na2O) 0.2wt%, (with reference to the non-hydrated state). 例9及下面例子中所用的LZ-105-5吸附剂,是一种ZSM-5型的分子筛,制备时未用有机模板剂,其SiO2/Al2O3摩尔比约为36.7,Na2/Al2比为1.19。 9 and LZ-105-5 adsorbent used in the following example embodiment, is a ZSM-5 type zeolite, not used when the organic templating agent prepared in which SiO2 Al2O3 molar ratio of / is about 36.7, Na2 / Al2 ratio of 1.19 . 例5的吸附剂组合物是等量的LZ-10和Silicalite的混合物。 The sorbent composition of Example 5 and LZ-10 is a mixture of equal amounts of Silicalite. 分析结果见下表。 The results in the table below.

表Ⅰ吸附剂 顶部的三乙胺PPM无 470. Table top Ⅰ adsorbent 470 PPM is triethylamine.

例2 LZ-20 .003例3 LZ-10 .010例4 活性炭 .017例5 LZ-10;Silicalite .033例6 硅胶 19.74例7 Silicalite <108. Example 2 LZ-20 .003 Example 3 LZ-10 .010 .017 Example 4 Example charcoal 5 LZ-10; Silicalite .033 Example 6 silica 19.74 cases 7 Silicalite <108.

例8 NaHCO3<108. Example 8 NaHCO3 <108.

例9 LZ-105-5 <108. EXAMPLE 9 LZ-105-5 <108.

例10用异戊酸和丁硫醇混合物,不断增加其加入量,以测定该混合物在由等量LZ-10和Silicalite组成的组合物上的负载量与管形瓶上部残留浓度之间的关系。 Example 10 is a mixture of isovaleric acid and butyl mercaptan, increasing the amount added to determine the relationship between the amount of the mixture was loaded on a composition of equal amounts of LZ-10 and Silicalite composition of the residual concentration of the upper vial . 结果如下。 The results are as follows.

表Ⅱ吸附剂上负载量wt% 处理后空气中的残留量(PPM)异戊酸 丁硫醇 异戊酸 丁硫醇无吸附剂 1.58 2060.93 0.83 .0012 .00111.86 1.67 .0011 .00112.79 2.65 .0019 .00973.71 3.33 .0014 .01367.43 6.67 .0021 .07629.29 8.34 .0174 4.73例11-18用另一些吸附剂重复例2-9。 Adsorbent loading table Ⅱ wt residual amount (PPM)% after treatment in air butanethiol isovaleric isovaleric acid adsorbent-butyl mercaptan 0.83 1.58 2060.93 1.67 .00111.86 .0012 2.65 .0019 .0011 .00112.79. 00973.71 3.33 6.67 .0021 .0014 .01367.43 .07629.29 8.34 .0174 4.73 cases 11-18 Example 2-9 was repeated with other adsorbents. 结果如下表Ⅲ上部的混合物PPM吸附剂 异戊酸 丁硫醇无 1.58 206例11 LZ-20 .0104 .2266例12 LZ-10 .0038 .5768例13 LZ-105-5 .5846 .0659例14 Silicalite .3160 4.326例15 硅胶 .8216 6.386例16 Silicalite;LZ-10*.0237 .2060例17 LZ-105-5;LZ-20*.0111 .0659例18 Silicalite;LZ-20*.0174 .0082 The results in the table below the upper portion of the adsorbent Ⅲ mixture PPM isovaleric butanethiol 1.58 206 cases of non-11 LZ-20 .0104 .2266 Example 12 LZ-10 .0038 .5768 Example 13 LZ-105-5 .5846 .0659 Example 14 Example 15 Silicalite .3160 ​​4.326 .8216 6.386 cases of silica gel 16 Silicalite; LZ-10 * .0237 .2060 Example 17 LZ-105-5; LZ-20 * .0111 .0659 Example 18 Silicalite; LZ-20 * .0174 .0082

例19将例11-18中样品在室温下,置于密封瓶内,24小时后再测定,结果如下。 Example 19 Examples 11-18 samples at room temperature, placed in a sealed bottle, 24 hours before the measurement results are as follows.

表Ⅳ顶部混合物PPM吸附剂 异戊酸 丁硫醇无 1.58 206Silicalite .0458 .1133LZ-20 .0190 .7416LZ-10 .0790 2.06LZ-105-5 .4266 2.47Silicalite;LZ-10 .5214 28.84例20为确定缺少所需疏水性的某些高硅分子筛不适宜作为本发明吸附剂,用一种骨架SiO2/Al2O3摩尔比25.4,标准条件下水吸附容量14.28wt%的β型沸石吸附异戊酸,由主观嗅觉实验发现,与吸附剂接触后,仍可嗅到很大的异戊酸气味。 Table top Ⅳ isovaleric acid adsorbent mixtures PPM butanethiol No 1.58 206Silicalite .0458 .1133LZ-20 .0190 .7416LZ-10 .0790 2.06LZ-105-5 .4266 2.47Silicalite; LZ-10 .5214 28.84 Examples 20 to determining a desired missing some high-silica molecular sieves are not suitable as a hydrophobic adsorbent of the present invention, in a skeleton of SiO2 / Al2O3 molar ratio of 25.4, standard conditions 14.28wt% water adsorption capacity of adsorption of zeolite β isovaleric acid, subjective smell was found that after contact with the adsorbent, still a lot of isovaleric acid smell the odor.

例21一种市售卫生巾(牌号STAYFREE,出自Johnson &amp; Johnson ComPany),已被一妇女在行经时用过。 Example 21 a commercially available sanitary napkin (designation STAYFREE, by Johnson & amp; Johnson ComPany), has been used at the time of passing a woman. 取出的卫生巾既使用香水处理后,仍能嗅到明显气味。 After removing the sanitary napkin treatment using both perfume, still smelled the odor evident. 将等量的活化Silicalite和LZ-10沸石的混合物,撒在污物部份,使其足以复盖污物,这时不再能嗅到气味。 Mixture and the same amount of activated Silicalite zeolite LZ-10 and scatter part of the dirt, soil sufficient to cover, when no longer smell the odor.

例22 Example 22

将两片由纤维素制成的无纺薄片制成含均匀分布的硅质分子筛的三明治片、每一薄片约1mm厚,12cm宽,25cm长。 The nonwoven sheet sandwich two sheets made of cellulose made uniform siliceous molecular sieves, each sheet of about 1mm thick, 12cm wide, 25cm length. 用聚酯将两薄片封合成厚度约2mm的一片,内装约1g等量的活化Silicalite和LZ-10沸石的混合物。 The two polyester sheets with a thickness of about 2mm seal Synthesis of a mixture of approximately equal amounts of the contents 1g activation Silicalite and zeolite LZ-10.

将该薄片对折后装在购来的卫生巾(牌号STAYFREE,出自Johnson &amp; Johnson Company)上面,经一妇女在行经时使用,使用后卫生巾上无可嗅出气味。 The folded sheet to be mounted on commercially available sanitary napkin (trademark Stayfree, by Johnson & amp; Johnson Company) above, in a woman when passing by, after use smell no smell of the sanitary napkin.

Claims (20)

1.一种用于吸附体液的纤维吸附制品,含有制成一定结构,适于吸附液体液的纤维材料和可减除体液气味的、有效量的硅质结晶分子筛,其特征在于该分子筛中至少90%的四面体氧化物单元是SiO2四面体,该分子筛的孔径约5.5 A fibrous material adsorbed fibrous absorbent article for body fluid, into a certain structure comprising, adapted to absorb the liquid and liquid fluids subtraction odor, an effective amount of a siliceous crystalline molecular sieve, the molecular sieve characterized in that at least 90% of the tetrahedral oxide units are SiO2 tetrahedra, of the molecular sieve pore diameter of about 5.5 ,在温度25℃、水蒸汽压4.6托和时间2小时的条件下的水吸附容量不高于10wt%。 , The water absorption capacity at a temperature of 25 ℃, the water vapor pressure of 4.6 torr and a time of 2 hours is not more than 10wt%.
2.权利要求1的纤维吸附制品,其中的硅质结晶分子筛至少有一部分是被活化的。 2. The fiber absorbent article of claim 1, wherein the crystalline siliceous molecular sieve is at least partly activated.
3.权利要求1的纤维吸附制品,其中的硅质结晶分子筛在标准条件下的水吸附容量不高于6wt%。 Fibrous absorbent article of claim 1, wherein the siliceous crystalline molecular sieve under standard conditions water adsorption capacity of not more than 6wt%.
4.权利要求1的纤维吸附制品,其中的硅质分子筛是一种骨架SiO2/Al2O3摩尔比大于35的硅铝酸盐。 Fibrous absorbent article of claim 1, wherein the siliceous molecular sieve is a skeleton SiO2 / Al2O3 molar ratio greater than 35 aluminosilicate.
5.权利要求4的纤维吸附制品,其中硅铝酸盐的SiO2/Al2O3摩尔比为200-500。 Fibrous absorbent article according to claim 4, wherein the SiO2 / Al2O3 molar ratio of aluminosilicate 200-500.
6.权利要求1的纤维吸附制品,其中的硅质分子筛包括二氧化硅多形体。 Fibrous absorbent article of claim 1, wherein the siliceous molecular sieves include silica polymorphs.
7.权利要求1的纤维吸附制品,其中的硅质分子筛包括二氧化硅多形体和骨架SiO2/Al2O3比200-500的硅铝酸盐的混合物。 Fibrous absorbent article according to claim 1, wherein the siliceous molecular sieve comprises a mixture of silica polymorph and the framework silicon SiO2 / Al2O3 ratio of aluminate 200-500.
8.权利要求1的纤维吸附制品,其中的硅质分子筛包括二氧化硅多形体和一种骨架SiO2/Al2O3比至少35的Y型沸石的混合物,其中二氧化硅多形体和Y型沸石在温度25℃、水蒸汽压4.6托和时间2小时下,各自的水吸附容量不高于10wt%。 Fibrous absorbent article of claim 1, wherein the siliceous molecular sieves include silica polymorphs and one skeleton SiO2 / Al2O3 ratio of Y zeolite mixture of at least 35, wherein the silica polymorph and a type Y zeolite at a temperature 25 ℃, the water vapor pressure of 4.6 torr and a time of 2 hours, the water absorption capacity of each of not more than 10wt%.
9.权利要求1的纤维吸附制品,其中的二氧化硅多形体是硅沸石,Y型沸石是LZ-10。 9. The fiber absorbent article of claim 1, wherein the silica polymorph is silicalite, Y zeolite is LZ-10.
10.权利要求1的纤维吸附制品,其中的硅质结晶分子筛含有不到0.2wt%的碱金属(以非水合态为基准)。 10. A fibrous absorbent article of claim 1, wherein the siliceous crystalline molecular sieve contains less than 0.2wt% of an alkali metal (in non-hydrated state as a reference).
11.权利要求1的纤维吸附制品,其中每100cm3体积的制品上,含有约0.01-50g上述硅质分子筛。 Absorbent article 11. The fiber of claim 1, wherein the volume of product per 100cm3, siliceous molecular sieve contains from about 0.01-50g above.
12.权利要求1的纤维吸附制品,其中每100cm2有效面积上含有约0.01-25g上述硅质分子筛。 Absorbent article 12. The fiber of claim 1, wherein the siliceous molecular sieve contains from about 0.01-25g above the effective area per 100cm2.
13.权利要求1的纤维吸附制品,其中纤维材料的结构是无纺絮胎。 13. A fibrous absorbent article of claim 1, wherein the structural fibers of the nonwoven batting material.
14.权利要求1的纤维吸附制品,其中的硅质分子筛分散在纤维材料中。 14. A fibrous absorbent article of claim 1, wherein the siliceous molecular sieve dispersed in the fibrous material.
15.权利要求1的纤维吸附制品,其中的硅质分子筛包在可渗透液体但又不漏出该分子筛的结构中。 15. A fibrous absorbent article of claim 1, wherein the siliceous molecular sieve pack but not liquid-permeable leakage of the molecular sieve structure.
16.权利要求5的纤维吸附制品,该制品是一种月经用品。 16. A fiber as claimed in claim 5 absorbent article, the article is a catamenial.
17.权利要求16的纤维吸附制品,该制品是卫生巾。 Absorbent article 17. The fiber of claim 16, which article is a sanitary napkin.
18.权利要求17的纤维吸附制品,其中含有约0.01-10g的硅质分子筛。 18. A fibrous absorbent article of claim 17, wherein the molecular sieve comprises silicalite of about 0.01-10g.
19.权利要求17的纤维吸附制品,其中两种硅质分子筛包在两层可透液体的薄片之间,成三明治结构,上述两层薄片放在卫生巾内。 19. A fibrous absorbent article of claim 17, wherein the two kinds of siliceous molecular sieves package sheet between two layers of liquid permeable, a sandwich structure into the two sheet placed in the sanitary napkin.
20.权利要求19的纤维吸附制品,其中含有超级吸附剂。 20. The absorbent article of fiber as claimed in claim 19, wherein the adsorbent comprises super.
CN 88109236 1987-06-30 1988-12-03 Fibrous absorbent articles having enhanced deodoriging properties CN1016491B (en)

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US7874266B2 (en) 2007-09-28 2011-01-25 T.F.H. Publications, Inc. Biodegradable waste pad or litter including nutrients for promoting microbial populations
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