JP2008081876A - Fiber processing agent and fiber product using the same - Google Patents
Fiber processing agent and fiber product using the same Download PDFInfo
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Abstract
Description
本発明はスポーツ衣料、シャツ、ブラウス、サマースーツ、パンツ、帽子、肌着、ソックスなどの衣料、消防服や溶鉱炉などの特殊ウエア、および 布団、シーツなどの寝装繊維製品、さらには、カーペット、マット、カーテンなどのインテリア繊維製品、カーシート、カーマットなどの自動車・車両内装繊維製品、テント、シェルター、フォローなど太陽熱を嫌う産業資材用途などを対象に、熱遮蔽効果、吸放湿効果、清涼効果、抗菌防臭効果などの優れた機能性を有する繊維加工剤ならびに該加工剤で加工した繊維製品を提供しょうとするものである。 The present invention includes sports clothing, shirts, blouses, summer suits, pants, hats, underwear, socks, and special clothing such as fire clothes and blast furnaces, and bedding textile products such as futons and sheets, as well as carpets and mats. For interior textile products such as curtains, automobile and vehicle interior textile products such as car seats and car mats, industrial materials that dislike solar heat such as tents, shelters and followers, etc., heat shielding effect, moisture absorption / release effect, cooling effect, An object of the present invention is to provide a fiber processing agent having excellent functionality such as an antibacterial and deodorizing effect and a fiber product processed with the processing agent.
従来から、繊維製品の清涼加工は重要な課題であり、業界でも該課題をクリアすべく、いろいろ技術検討がなされている。この清涼というキーワードに対し、機能性的には各種の方向から検討がなされている。具体的には、ソルビトール、エリスリトール、キシリトールなどの糖アルコール化合物の溶解吸熱（水和熱：負）を利用した加工（特許文献１〜５）、各種紫外線吸収剤（カット剤）を活用した加工（特許文献６〜８）、熱遮蔽性化合物を利用した加工（特許文献９〜１２）、吸放湿加工、吸放湿ポリマーによる加工（特許文献１３〜１６）、などが挙げられるが、いずれも満足できるレベルのものではなく、業界では、さらなる性能の向上を望んでいるのが実状である。 Conventionally, the refreshing processing of textile products has been an important issue, and various technical studies have been made in the industry to clear the issue. The keyword “cool” has been studied from various directions in terms of functionality. Specifically, processing (Patent Documents 1 to 5) using dissolution endotherm (heat of hydration: negative) of sugar alcohol compounds such as sorbitol, erythritol, xylitol, processing using various ultraviolet absorbers (cutting agents) ( Patent Documents 6 to 8), processing using a heat-shielding compound (Patent Documents 9 to 12), moisture absorption / release processing, processing with moisture absorption / release polymer (Patent Documents 13 to 16), and the like. The situation is not satisfactory, and the industry wants to improve performance even more.
衣料などの繊維製品を着用した際、夏場の高温多湿条件下では、ムレなどにより非常に不快感を覚えるが、この大きな要因は、夏場の太陽熱、高温状態での人体温の上昇、人体からの発汗（不感蒸泄）などが挙げられる。これらの不快要因が重なり、人間は非常に不快感を覚え、この状況の改善を強く要望するものである。本発明では、かかる不快状態を回避した着用時に快適な状況を作る衣料にすべく、清涼加工剤の開発ならびに、該加工剤で繊維製品を加工することにより、着用時の快適性を向上させることを課題とする。また、衣料以外のインテリアや寝具類、カーシート類、シェルターなどの産業資材類などにおいても、衣料と同様に快適な環境状況の創造が課題である。 When wearing textiles such as clothing, under the hot and humid conditions in summer, we feel very uncomfortable due to stuffiness, etc., but this major factor is due to solar heat in summer, increased body temperature at high temperature, Examples include sweating (insensitive digestion). These unpleasant factors overlap, and humans feel very uncomfortable and strongly desire to improve this situation. In the present invention, in order to make a garment that creates a comfortable situation when worn while avoiding such an uncomfortable state, the development of a cooling processing agent and the processing of textiles with the processing agent improve the comfort at the time of wearing. Is an issue. In addition to clothing, industrial materials such as bedding, car seats, shelters, and the like have a challenge to create a comfortable environmental situation, as with clothing.
本発明では、かかる課題をクリアするために、次のような手段を取るものである。すなわち、太陽などの熱遮蔽効果がある無機系化合物（Ａ）と、該無機系化合物（Ａ）を繊維表面に強固に付着・固着せしめるための樹脂バインダーなどの化合物（Ｂ）からなる加工剤を繊維に加工せしめるものである。その際、（Ｂ）の樹脂バインダー的な化合物に吸放湿性のある有機、無機化合物を用いるとさらに、本発明の目的を達成しやすくなる。また、キシリトール、エリスリトール、ソルビトールなどの糖アルコール類（Ｃ）を前記（Ａ）、（Ｂ）に包摂させると（Ｃ）単独使用に比べ、相乗効果を発揮すると共に、洗濯耐久性も向上する傾向にある。さらには、銀ナノコロイド、ナノ粒子径の酸化亜鉛、銀ゼオライト、キトサン、ジンクピリチオンなどの抗菌剤の少なくとも１種（Ｄ）を併用使用すると、特に衣料などの場合に、着用時における人体汗に基づく抗菌防臭性能が付加される結果、より着用快適性を高めることになり、この点も本発明のポイントの一つである。 In the present invention, the following measures are taken in order to clear such a problem. That is, a processing agent comprising an inorganic compound (A) having a heat shielding effect such as the sun and a compound (B) such as a resin binder for firmly attaching and fixing the inorganic compound (A) to the fiber surface. It is processed into fiber. At that time, when an organic or inorganic compound having moisture absorption / release properties is used as the resin binder compound (B), the object of the present invention can be achieved more easily. In addition, when sugar alcohols (C) such as xylitol, erythritol, sorbitol, etc. are included in (A) and (B), a synergistic effect is exhibited and washing durability is improved as compared with the use of (C) alone. It is in. Furthermore, when used in combination with at least one antibacterial agent (D) such as silver nanocolloid, nano-sized zinc oxide, silver zeolite, chitosan, and zinc pyrithione, it is based on human sweat at the time of wearing, especially in the case of clothing. As a result of the addition of antibacterial and deodorizing performance, the wear comfort is further enhanced, and this is one of the points of the present invention.
前述の解決手段を採用することにより、夏場の太陽熱の遮蔽効果、人体からの発汗に基づく不感蒸泄(ムレ感の主原因)の処理、さらには、人体温の上昇を抑えるため、溶解吸熱(負の水和熱)性を有する化合物の併用・包摂、ナノ微粒子径の抗菌防臭剤の併用使用により、衣料の場合は着用快適性の向上を、インテリアや寝具、産業資材類の場合は、快適な環境状況作りに寄与するものである。 By adopting the above-mentioned solution, in order to suppress the effects of solar heat in summer, treatment of insensitive excretion based on sweating from the human body (main cause of stuffiness), and to suppress the rise in human body temperature, dissolved endotherm ( (Negative heat of hydration) Combined use and inclusion of compounds with nano particles and antibacterial deodorant with nano-particle size improve comfort for clothing, comfort for interior, bedding and industrial materials It contributes to the creation of a safe environmental situation.
本発明の効果を最大に発揮させるための具体的な内容について説明する。本発明における太陽熱を遮蔽する効果のある無機化合物（Ａ）としては、酸化セリウム、酸化亜鉛、酸化チタン、酸化アルミニウムなどが挙げられるが、その中でも特に酸化セリウムが太陽などの熱遮蔽効果が高く、好ましい化合物と言える。また、太陽熱などの熱を遮蔽する効果のある無機化合物（Ａ）は、カルシウム、マグネシウムの炭酸塩、硝酸塩、リン酸塩、塩酸塩などの無機化合物もしくは、シリカ、タルク、マイカの少なくとも１種でドープされていると、さらに熱遮蔽効果が著しく高まり、本発明の目的、課題をより達成することが出来る。その際のドープ材の比率としては、酸化セリウムや酸化亜鉛などの熱遮蔽剤が１００に対し、０．１〜５０、好ましくは、３〜２０が良い。また、この酸化セリウムなどに酸化亜鉛や、酸化チタン、酸化アルミニウムを併用使用、あるいは、酸化亜鉛にγ−酸化アルミニウムなどを併用使用すると、各々単独使用した場合よりも効果が高まり、所謂、相乗効果が見受けられ、この点も本発明の大きな特徴の一つと言える。その際の配合割合は、酸化セリウムあるいは、酸化亜鉛が１に対し、他の無機化合物の使用量は０．１〜１．０の範囲が相乗効果が出やすい範囲である。なお、該無機化合物は通常の無機化合物スラリーと同様に、スラリー化をして、使用する方が作業性は良く、現実的である。 Specific contents for maximizing the effects of the present invention will be described. Examples of the inorganic compound (A) having an effect of shielding solar heat in the present invention include cerium oxide, zinc oxide, titanium oxide, and aluminum oxide. Among them, cerium oxide has a particularly high heat shielding effect such as the sun, It can be said that it is a preferable compound. In addition, the inorganic compound (A) having an effect of shielding heat such as solar heat is at least one of inorganic compounds such as calcium, magnesium carbonate, nitrate, phosphate, hydrochloride, silica, talc, and mica. When doped, the heat shielding effect is further enhanced, and the objects and problems of the present invention can be achieved. In this case, the ratio of the dope material is 0.1 to 50, preferably 3 to 20, with respect to 100 of the heat shielding agent such as cerium oxide or zinc oxide. In addition, when zinc oxide, titanium oxide, and aluminum oxide are used in combination with cerium oxide or the like, or γ-aluminum oxide is used in combination with zinc oxide, the effect is higher than when each is used alone, so-called synergistic effect. This point is also one of the major features of the present invention. In this case, the blending ratio is such that the amount of cerium oxide or zinc oxide is 1 and the amount of other inorganic compound used is in the range of 0.1 to 1.0, and the synergistic effect is likely to occur. In addition, it is more practical and practical to use the inorganic compound in the form of a slurry in the same manner as a normal inorganic compound slurry.
次に、前述の無機化合物類を繊維表面に強固に付着・固着せしめるための化合物（Ｂ）について説明する。化合物（Ｂ）としては、シリコン・アクリル共重合物、エポキシシリコン樹脂、エポキシシリコン・ウレタン併用化合物もしくは、共重合物、アクリル・ウレタン併用化合物もしくは、共重合物が挙げられるが、中では特にアクリル・シリコン共重合物が、本発明の目的を達成するために好ましい化合物と言える。 Next, the compound (B) for firmly attaching and fixing the aforementioned inorganic compounds to the fiber surface will be described. Examples of the compound (B) include silicon / acrylic copolymer, epoxy silicone resin, epoxy silicon / urethane combined compound or copolymer, acrylic / urethane combined compound or copolymer, among which acrylic / A silicon copolymer can be said to be a preferred compound for achieving the object of the present invention.
また、化合物（Ｂ）として、前述の樹脂バインダー的な化合物とは異なり、吸放湿性のある有機化合物、無機化合物の使用が、より効果的である。具体的には、有機化合物としては、ポリエチレンオキサイドあるいは、ポリエチレンオキサイドとポリプロピレンオキサイドの共重合物、あるいは、それ以外の親水性基、例えば水酸基、カルボキシル基などを有する化合物を、通常よりも多く反応せしめることにより吸放湿性能を付与せしめたポリウレタン樹脂、または、ウレタンプレポリマー樹脂、さらには、吸放湿性を有するアクリル酸、メタクリル酸、２−アクリルアミド−２−メチル−１−プロパンスルフォン酸（ＡＭＰＳ）などの吸放湿性能を有するモノマー単独、あるいは、それらにアクリルアミド、ヒドロキシエチルアクリレート、ポリエチレングリコールを付加した各種ビニルモノマーなどを共重合した吸放湿性ポリマーが挙げられる。一方、吸放湿性のある無機化合物としては、シリカ化合物が挙げられるが、この場合は、前述の樹脂バインダーあるいは、吸放湿性能を有する有機化合物との併用使用が好ましい。 Further, as the compound (B), unlike the resin binder-like compound described above, it is more effective to use an organic compound or an inorganic compound having moisture absorption / release properties. Specifically, as the organic compound, polyethylene oxide, a copolymer of polyethylene oxide and polypropylene oxide, or a compound having other hydrophilic group such as a hydroxyl group or a carboxyl group is reacted more than usual. Polyurethane resin or urethane prepolymer resin that has been provided with moisture absorption / release performance by this, and acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) having moisture absorption / release properties Examples of such a moisture-absorbing / releasing polymer include monomers having a moisture-absorbing / releasing performance such as single monomers, or various vinyl monomers obtained by adding acrylamide, hydroxyethyl acrylate, and polyethylene glycol thereto. On the other hand, examples of the hygroscopic inorganic compound include a silica compound. In this case, it is preferable to use in combination with the aforementioned resin binder or an organic compound having hygroscopic performance.
本発明では、前述の化合物（Ａ）、（Ｂ）を併用使用するが、その際の配合割合としては、（Ａ）：（Ｂ）が５：９５〜９５：５の範囲内が良く、中でも３０：７０〜７０：３０の範囲が本発明の目的を達成するためにより好ましい範囲と言える。この配合割合において、（Ａ）化合物の配合割合がこの範囲を下回ると太陽熱の遮蔽効果が乏しくなり、一方、この範囲よりも（Ａ）の配合割合が多くなると、特に衣料などに加工した場合、本発明に言う効果の洗濯耐久性が著しく低下してしまい、実用性の乏しいものになる。 In the present invention, the above-mentioned compounds (A) and (B) are used in combination, and the blending ratio at that time is preferably such that (A) :( B) is within the range of 5:95 to 95: 5, The range of 30:70 to 70:30 can be said to be a more preferable range in order to achieve the object of the present invention. In this blending ratio, when the blending ratio of the compound (A) is below this range, the solar heat shielding effect is poor, while when the blending ratio of (A) is larger than this range, especially when processed into clothing, The washing durability of the effect referred to in the present invention is remarkably lowered, and the practicality is poor.
次に、本発明において、より清涼性を高めるために、化合物（Ｃ）を併用使用するが、化合物（Ｃ）は、水に溶解した際に吸熱反応（負の水和熱）を示す化合物を意味し、具体的には、キシリトール、エリスリトール、ソルビット化合物などを言う。これらの化合物（Ｃ）は水溶性なので、油溶性のオイル物質でくるんだエマルジョン系にして用いた方が、性能の洗濯耐久性が向上するので好ましい。この化合物（Ｃ）の配合割合としては、化合物（Ｂ）の１０〜６０％の範囲が好ましい。 Next, in the present invention, the compound (C) is used in combination in order to further improve the coolness, but the compound (C) is a compound that exhibits an endothermic reaction (negative heat of hydration) when dissolved in water. Specifically, it means xylitol, erythritol, sorbit compound and the like. Since these compounds (C) are water-soluble, it is preferable to use them in an emulsion system wrapped with an oil-soluble oil substance since the washing durability of the performance is improved. As a compounding ratio of this compound (C), the range of 10 to 60% of a compound (B) is preferable.
次に、本発明において、化合物（Ｄ）を併用使用するが、この化合物（Ｄ）は、具体的には、銀ナノコロイド、ナノ微粒子径の酸化亜鉛、銀ゼオライト、キトサン、ジンクピリチオンなどの抗菌防臭性を有する化合物を意味するが、これらの化合物を併用使用する意味は、前述したように、衣料などにして着用した際に、人体からの発汗した分泌物が衣料に付着して、一般常在菌により、分解されアンモニア臭、酢酸臭、イソ吉相酸臭、などの不快な臭気発生の基になり、着用快適性を損なうことになるので、それを予め防ぐ目的で前述の抗菌防臭剤を併用使用するものである。なお、その際の併用使用量としては、化合物（Ｂ）使用量の３〜５０％の範囲が好ましい。 Next, in the present invention, the compound (D) is used in combination. Specifically, the compound (D) is an antibacterial deodorant such as silver nanocolloid, nano-sized zinc oxide, silver zeolite, chitosan or zinc pyrithione. The meaning of using these compounds in combination is that, as described above, when worn as clothing, the sweating secretions from the human body adhere to the clothing, It is decomposed by bacteria and becomes the basis of unpleasant odor generation such as ammonia odor, acetic acid odor, isoyoshinoic acid odor, etc., and wear comfort will be impaired, so the antibacterial deodorant mentioned above is used together to prevent it beforehand It is what you use. In addition, as the combined use amount in that case, the range of 3 to 50% of the compound (B) usage amount is preferable.
本発明において、これらの加工剤を繊維布帛類に付与する手段としては、特に限定されるものではなく、通常のパッド−キュア法、パッド−スプレー法、浸漬法−キュア法、コーティング法など、いずれの方法でも良い。 In the present invention, means for applying these processing agents to fiber fabrics is not particularly limited, and any of ordinary pad-cure method, pad-spray method, dipping method-cure method, coating method, etc. The method is also acceptable.
なお、本発明において、太陽熱などの熱遮蔽性データは次の方法で取った。
試験する繊維布帛類を切り取り温度センサーに巻き付けた後、自然太陽光を照射させて、そ
の温度上昇を測定する。測定は、常に未加工品と同時に行い、未加工品の上昇温度が４５℃以上の時点での、未加工品対比の最大の温度差と最小の温度差を測定する。
サンプルサイズ：４ｃｍ×４ｃｍ
測定条件：自然太陽光照射状態で未加工布の上昇温度が４５℃以上を示す。
測定時間：６０分間
In the present invention, heat shielding data such as solar heat was taken by the following method.
The fiber fabrics to be tested are cut out and wound around a temperature sensor, and then irradiated with natural sunlight, and the temperature rise is measured. The measurement is always performed simultaneously with the unprocessed product, and the maximum temperature difference and the minimum temperature difference of the unprocessed product are measured when the temperature rise of the unprocessed product is 45 ° C. or higher.
Sample size: 4cm x 4cm
Measurement conditions: The rising temperature of the unprocessed cloth is 45 ° C. or higher in the natural sunlight irradiation state.
Measurement time: 60 minutes
また、本発明において、抗菌性能のデータ取りは、ＪＩＳ Ｌ−１０９２の
静菌活性値測定法に基づいて行った。抗菌性能は、静菌活性値が２．２以上で効果ありと判
定される。
Moreover, in this invention, the antibacterial performance data collection was performed based on the bacteriostatic activity value measuring method of JIS L-1092. The antibacterial performance is determined to be effective when the bacteriostatic activity value is 2.2 or more.
本発明における清涼感（接触冷感）はＱｍａｘ値の測定で行った。
測定装置：精密迅速物性測定装置 ＫＥＳ−Ｆ７サーモラボ２型
測定条件：２０℃、６５％ＲＨ
The refreshing feeling (contact cooling feeling) in the present invention was measured by measuring the Qmax value.
Measuring device: Precise and rapid physical property measuring device KES-F7 Thermolab type 2 Measurement conditions: 20 ° C, 65% RH
本発明における洗濯耐久性のデータ取りは、ＪＩＳ Ｌ−０２１７ １０３法に基づいて行った。
以下 実施例でもって、さらに本発明について説明する。
The data of washing durability in the present invention was obtained based on JIS L-0217 103 method.
Hereinafter, the present invention will be further described with reference to examples.
（熱遮蔽加工剤の調整）
酸化セリウム３０％のスラリー状水性組成物９８部に、乳化分散剤としてポリカルボン酸型
高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。
（繊維処理）
上述の加工剤４部、ならびにシリコン・アクリル樹脂バインダー（パラソルブＧＨ−Ｓ１（４０％）：大原パラヂウム化学(株)社製）３部を水９３部に均一に混合して加工液とした。木綿１００％平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−４．５℃〜−４．０℃であった。
（比較例１）
実施例１の酸化セリウムの代わりに、酸化カルシウムを用いて実施例１と同じ加工剤を調整し、同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−０．５℃〜０℃であり、遮蔽効果はほとんどなかった。
（比較例２）
実施例１の酸化セリウムの代わりに、酸化マグネシウムを用いて実施例１と同じ加工剤を調整し、同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−０．４℃〜０℃であり、遮蔽効果はほとんどなかった。
(Adjustment of heat shielding agent)
To 98 parts of a slurry aqueous composition containing 30% cerium oxide, 2 parts of a polycarboxylic acid type polymer surfactant was added as an emulsifying dispersant to obtain a total amount of 100 parts of a processing agent.
(Fiber treatment)
4 parts of the above-mentioned processing agent and 3 parts of a silicon / acrylic resin binder (Parasolv GH-S1 (40%): manufactured by Ohara Paradium Chemical Co., Ltd.) were uniformly mixed with 93 parts of water to obtain a processing liquid. A 100% cotton plain woven fabric was dipped in this processing solution, subjected to padding at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this work cloth was −4.5 ° C. to −4.0 ° C. compared to the unprocessed cloth.
(Comparative Example 1)
Instead of the cerium oxide of Example 1, the same processing agent as in Example 1 was prepared using calcium oxide, and fiber treatment was performed under the same conditions. The sunscreen shielding effect of this work cloth was -0.5 ° C. to 0 ° C. compared to the unprocessed cloth, and there was almost no shielding effect.
(Comparative Example 2)
Instead of cerium oxide in Example 1, magnesium oxide was used to prepare the same processing agent as in Example 1, and fiber treatment was performed under the same conditions. The sunscreen shielding effect of this work cloth was -0.4 ° C. to 0 ° C. compared to the unprocessed cloth, and there was almost no shielding effect.
（熱遮蔽加工剤の調整）
重量割合にして、酸化セリウム１００に対し、炭酸カルシウム１０をドープした化合物３０％のスラリー状水性組成物９８部に、乳化分散剤としてポリカルボン酸型高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。
（繊維処理）
上述の加工剤４部、ならびにシリコン・アクリル樹脂バインダー（パラソルブＧＨ−Ｓ１（４０％）：大原パラヂウム化学(株)社製）３部を水９３部に均一に混合して加工液とした。木綿１００％平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−６．５℃〜−５．７℃であった。このものは、実施例１で示した酸化セリウム単独で、酸化カルシウムをドープしないもので−４．５〜−４．０℃であったのに対し、熱遮蔽効果は高く、明らかに炭酸カルシウムのドープ効果が見受けられる。
（比較例３）
実施例２のドープ剤である炭酸カルシウムの代わりに、炭酸銅を用いて実施例２と同じ加工剤を調整し、同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−４．７℃〜−４．３℃であり、遮蔽効果の向上性は小さかった。
（比較例４）
実施例２の酸化セリウムの代わりに、酸化鉄を用いて実施例２と同じ加工剤を調整し、同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−４．６℃〜−４．２℃であり、遮蔽効果の向上性はあまり無かった。
(Adjustment of heat shielding agent)
In a weight ratio, 2 parts of a polycarboxylic acid type polymer surfactant as an emulsifying dispersant is added to 98 parts of a slurry-like aqueous composition of 30% compound doped with calcium carbonate 10 with respect to cerium oxide 100, and the total amount 100 parts of processing agent were obtained.
(Fiber treatment)
4 parts of the above-mentioned processing agent and 3 parts of a silicon / acrylic resin binder (Parasolv GH-S1 (40%): manufactured by Ohara Paradium Chemical Co., Ltd.) were uniformly mixed with 93 parts of water to obtain a processing liquid. A 100% cotton plain woven fabric was dipped in this processing solution, subjected to padding at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this work cloth was −6.5 ° C. to −5.7 ° C. compared to the unprocessed cloth. This was cerium oxide alone as shown in Example 1 and was not doped with calcium oxide and was −4.5 to −4.0 ° C., whereas the heat shielding effect was high. Doping effect is observed.
(Comparative Example 3)
The same processing agent as in Example 2 was prepared using copper carbonate instead of calcium carbonate, which was the dopant of Example 2, and fiber treatment was performed under the same conditions. The solar heat shielding effect of this work cloth was -4.7 ° C to -4.3 ° C compared with the unprocessed cloth, and the improvement in the shielding effect was small.
(Comparative Example 4)
The same processing agent as in Example 2 was prepared using iron oxide instead of cerium oxide in Example 2, and fiber treatment was performed under the same conditions. The solar heat shielding effect of this work cloth was -4.6 ° C. to -4.2 ° C. compared to the unprocessed cloth, and there was not much improvement in the shielding effect.
（熱遮蔽加工剤の調整）
カルシウムをドープした（ドープ比率は酸化セリウム：カルシウム＝１００：４）酸化セリウム３０％のスラリー状水性組成物９８部に、乳化分散剤としてポリカルボン酸型高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。
（繊維処理）
上述の加工剤４部、ならびにシリコン・アクリル樹脂バインダー（パラソルブＧＨ−Ｓ１）３部を水９３部に均一に混合して加工液とした。木綿１００％平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−５．３℃〜−４．８℃であり、実施例１と比較して相乗効果が見受けられた。
(Adjustment of heat shielding agent)
2 parts of a polycarboxylic acid type polymer surfactant is added as an emulsifying dispersant to 98 parts of a slurry-like aqueous composition doped with calcium (dope ratio is cerium oxide: calcium = 100: 4) 30% cerium oxide, A total amount of 100 parts of processing agent was obtained.
(Fiber treatment)
4 parts of the above-mentioned processing agent and 3 parts of a silicon / acrylic resin binder (parasolve GH-S1) were uniformly mixed with 93 parts of water to obtain a processing liquid. A 100% cotton plain woven fabric was dipped in this processing solution, subjected to padding at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this work cloth was −5.3 ° C. to −4.8 ° C. compared with the non-work cloth, and a synergistic effect was observed compared to Example 1.
（熱遮蔽加工剤の調整）
酸化セリウム２０％に酸化チタン（アナターゼ型二酸化チタン）１０％を混合し、配合割合
を１：０．５とした。この混合物のスラリー状水性組成物９８部に、乳化分散剤としてポリ
カルボン酸型高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。
（繊維処理）
上述の加工剤４部、吸放湿性を有する親水性ウレタン樹脂バインダー（パラレジンＰＵ−Ｘ１００（４０％）：大原パラヂウム化学(株)社製）３部、水９３部に均一に混合して加工液とした。木綿１００％平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−５．５℃〜−５．０℃であり、相乗効果が見受けられた。
（比較例５）
酸化セリウム１０．０％に酸化マグネシウム２０．０％を混合し、固形配合割合を１．０：２．０とした。この混合物を用いて実施例２と同じ加工剤を調整し、同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−４．５℃〜−４．０℃であり、実施例１、４と比較して相乗効果は見受けられず、配合による効果は無かった。
（比較例６）
酸化セリウム２９．７％に酸化マグネシウム０．３％を混合し、固形配合割合を１：０．０１とした。この混合物を用いて実施例２と同じ加工剤を調整し、同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−４．５℃〜−４．０℃であり、実施例１、４と比較して向上しなかった。
(Adjustment of heat shielding agent)
Titanium oxide (anatase type titanium dioxide) 10% was mixed with cerium oxide 20%, and the mixture ratio was set to 1: 0.5. To 98 parts of the slurry aqueous composition of this mixture, 2 parts of a polycarboxylic acid type polymer surfactant was added as an emulsifying dispersant to obtain a total amount of 100 parts of processing agent.
(Fiber treatment)
Processing solution by uniformly mixing 4 parts of the above-mentioned processing agent, 3 parts of hydrophilic urethane resin binder having moisture absorption / release properties (Pararesin PU-X100 (40%): manufactured by Ohara Palladium Chemical Co., Ltd.) and 93 parts of water. It was. A 100% cotton plain woven fabric was dipped in this processing solution, subjected to padding at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this processed fabric was -5.5 ° C to -5.0 ° C compared with the unprocessed fabric, and a synergistic effect was observed.
(Comparative Example 5)
Magnesium oxide 20.0% was mixed with cerium oxide 10.0%, and the solid compounding ratio was 1.0: 2.0. Using this mixture, the same processing agent as in Example 2 was prepared, and fiber treatment was performed under the same conditions. The solar heat shielding effect of this processed fabric was -4.5 ° C to -4.0 ° C compared to the unprocessed fabric, and no synergistic effect was found compared to Examples 1 and 4, and there was no effect due to the blending. .
(Comparative Example 6)
Magnesium oxide (0.3%) was mixed with cerium oxide (29.7%), and the solid content ratio was set to 1: 0.01. Using this mixture, the same processing agent as in Example 2 was prepared, and fiber treatment was performed under the same conditions. The solar heat shielding effect of this work cloth was −4.5 ° C. to −4.0 ° C. compared with the unprocessed cloth, and was not improved as compared with Examples 1 and 4.
（熱遮蔽加工剤の調整）
酸化セリウム（Ａ）３０．７％のスラリー状水性組成物９８部に、乳化分散剤としてポリカ
ルボン酸型高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。この加工剤の酸化セリウム分は３０％となる。
（繊維処理）
上述の酸化セリウム（Ａ）加工剤（酸化セリウム分３０％）５部と吸放湿性を有するポリウレタン樹脂（Ｂ）加工剤（樹脂成分４０％）４部を水９１部に均一に混合して加工液とした。この加工液の（Ａ）：（Ｂ）の固形配合割合は、約５０：５０となる。木綿３５％、ポリエステル系合成繊維６５％からなる平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、加工初期が未加工布対比−４．５℃〜−４．０℃、洗濯１０回後が未加工布対比−４．５℃〜−４．０℃で、良好な洗濯耐久性があった。また、本加工織物の２０℃×６５％ＲＨ下から３０℃×８０％ＲＨでの２４時間後の吸湿性は５．２％で、またこの状態から２０℃×６５％ＲＨ・２４時間後の放湿性は４．８％で、吸放湿性も兼ね備えていた。
（比較例７）
実施例５の酸化セリウム（Ａ）加工剤（酸化セリウム分３０％）５部と吸放湿性を有するポリウレタン樹脂（Ｂ）加工剤（樹脂成分４０％）０．１部を水９４．９部に均一に混合して加工液とした。この加工液の（Ａ）：（Ｂ）の固形配合割合は、約９７．４：２．６となる。この加工液にて実施例５と同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、加工初期が未加工布対比−４．５℃〜−４．０℃、洗濯１０回後が未加工布対比−１．０℃〜−０．５℃で、洗濯耐久性が実施例５よりも低下した。
（比較例８）
(Adjustment of heat shielding agent)
2 parts of a polycarboxylic acid type polymer surfactant was added as an emulsifying dispersant to 98 parts of a slurry-like aqueous composition of 30.7% cerium oxide (A) to obtain a total amount of 100 parts of processing agent. The cerium oxide content of this processing agent is 30%.
(Fiber treatment)
The above-mentioned cerium oxide (A) processing agent (cerium oxide content 30%) 5 parts and hygroscopic polyurethane resin (B) processing agent (resin component 40%) 4 parts are uniformly mixed with water 91 parts and processed. Liquid. The solid blending ratio of (A) :( B) in this working fluid is about 50:50. A plain woven fabric made of 35% cotton and 65% polyester synthetic fiber was immersed in this processing solution, padded at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this processed fabric is as follows: -4.5 ° C to -4.0 ° C compared to the unprocessed fabric at the initial stage of processing; -4.5 ° C to -4.0 ° C compared to the unprocessed fabric after 10 washings There was good washing durability. Also, the moisture absorption of the processed fabric after 20 hours at 20 ° C. × 65% RH to 30 ° C. × 80% RH is 5.2%, and from this state, 20 ° C. × 65% RH · 24 hours later. The moisture release property was 4.8%, and it also had moisture absorption and release properties.
(Comparative Example 7)
94.9 parts of water of 5 parts of cerium oxide (A) processing agent (cerium oxide content 30%) of Example 5 and 0.1 part of moisture absorbing / releasing polyurethane resin (B) processing agent (resin component 40%) A processing solution was obtained by mixing uniformly. The solid blending ratio of (A) :( B) in this working fluid is about 97.4: 2.6. The fiber was treated with this working fluid under the same conditions as in Example 5. The solar heat shielding effect of this processed fabric is as follows: -4.5 ° C to -4.0 ° C compared to the unprocessed fabric in the initial processing, and -1.0 ° C to -0.5 ° C compared to the unprocessed fabric after 10 washings. The washing durability was lower than that in Example 5.
(Comparative Example 8)
実施例５の酸化セリウム（Ａ）加工剤（酸化セリウム分３０％）０．１６部と吸放湿性を有するポリウレタン樹脂（Ｂ）加工剤（樹脂成分４０％）１２部を水９６部に均一に混合して加工液とした。この加工液の（Ａ）：（Ｂ）の固形配合割合は、１：１００となる。この加工液にて実施例５と同じ条件で繊維処理をした。この加工布の太陽熱の遮蔽効果は、加工初期が未加工布対比−０．５℃〜０℃、洗濯１０回後が未加工布対比−０．５℃〜０℃で、太陽熱の遮蔽効果は無かった。 Uniformly mix 0.16 parts of cerium oxide (A) processing agent (cerium oxide content 30%) and 12 parts of polyurethane resin (B) processing agent (resin component 40%) of Example 5 in 96 parts of water. Mixed to make a working fluid. The solid blending ratio of (A) :( B) in this working fluid is 1: 100. The fiber was treated with this working fluid under the same conditions as in Example 5. The solar heat shielding effect of this processed fabric is -0.5 ° C to 0 ° C compared to the unprocessed fabric at the initial stage of processing, and -0.5 ° C to 0 ° C compared to the unprocessed fabric after 10 washings. There was no.
（繊維処理）
実施例５の酸化セリウム（Ａ）加工剤（酸化セリウム分３０％）５部と吸放湿性を有するポリウレタン樹脂（Ｂ）加工剤（樹脂成分４０％）４部、キシリトール（Ｃ）の４０％水溶液２部を水８４部に均一に混合して加工液とした。この加工液の（Ｂ）：（Ｃ）の固形配合割合は、１００：５０となる。ポリエステル系合成繊維１００％からなる平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、加工初期が未加工布対比−５．４℃〜−４．９℃、洗濯１０回後が未加工布対比−５．１℃〜−４．７℃で、実施例３と比較して、遮蔽効果の向上と良好な洗濯耐久性があった。また、この加工布の接触冷感（
Ｑｍａｘ値）は０．６５１と大きく、清涼効果の高い物になった。
（比較例９）
実施例６に用いたポリエステル１００％からなる平織物を一切加工することなく、その状態で接触冷感（Ｑｍａｘ値）を測定したところ、０．４４３と本実施例に比べ低く、清涼感は無かった。
(Fiber treatment)
5 parts of cerium oxide (A) processing agent (cerium oxide content 30%) of Example 5, 4 parts of polyurethane resin (B) processing agent (resin component 40%) having moisture absorption / release properties, 40% aqueous solution of xylitol (C) Two parts were uniformly mixed with 84 parts of water to obtain a working liquid. The solid blending ratio of (B) :( C) in this working fluid is 100: 50. A plain woven fabric made of 100% polyester synthetic fiber was immersed in this processing solution, padded at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this processed fabric is as follows: -5.4 ° C to -4.9 ° C compared to the unprocessed fabric at the initial stage of processing; -5.1 ° C to -4.7 ° C compared to the unprocessed fabric after 10 washings Compared with Example 3, there was an improvement in shielding effect and good washing durability. In addition, the feeling of contact cooling (
Qmax value) was as large as 0.651, and a high cooling effect was obtained.
(Comparative Example 9)
When the contact cold feeling (Qmax value) was measured in this state without processing any plain fabric made of 100% polyester used in Example 6, it was 0.443, which is lower than that of this example, and there was no cool feeling. It was.
（ナノ粒子径酸化亜鉛加工剤の調整）
ナノ粒子径の酸化亜鉛（Ｄ）２０．５％のスラリー状水性組成物９８部に、乳化分散剤としてポリカルボン酸型高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。この加工剤のナノ粒子径酸化亜鉛分は２０％となる。
（繊維処理）
実施例５の酸化セリウム（Ａ）加工剤（酸化セリウム分３０％）４部と吸放湿性を有するポリウレタン樹脂（Ｂ）加工剤（樹脂成分４０％）５部、ナノ粒子径の酸化亜鉛（Ｄ）加工剤（ナノ粒子径酸化亜鉛分２０％）４部を水８２部に均一に混合して加工液とした。この加工液の（Ｂ）：（Ｄ）の固形配合割合は、１００：２０となる。レーヨン３５％、ポリエステル系合成繊維６５％からなる平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、加工初期が未加工布対比−４．５℃〜−４．１℃、洗濯１０回後が未加工布対比−４．５℃〜−４．０℃で、実施例３と比較して、遮蔽効果の向上と良好な洗濯耐久性があった。またこの加工布の抗菌性は、加工初期、洗濯１０回後ともに静菌活性値が４．２以上で抗菌効果があった。
(Adjustment of nanoparticle size zinc oxide processing agent)
2 parts of a polycarboxylic acid type polymer surfactant as an emulsifying dispersant is added to 98 parts of a slurry-like aqueous composition of 20.5% zinc oxide (D) with a nanoparticle diameter to obtain a total amount of 100 parts of processing agent. It was. The nanoparticle size zinc oxide content of this processing agent is 20%.
(Fiber treatment)
4 parts of the cerium oxide (A) processing agent (cerium oxide content 30%) of Example 5 and 5 parts of a polyurethane resin (B) processing agent (resin component 40%) having moisture absorption / release properties, zinc oxide having a nanoparticle diameter (D ) 4 parts of a processing agent (nanoparticle diameter zinc oxide content 20%) was uniformly mixed with 82 parts of water to obtain a processing liquid. The solid blending ratio of (B) :( D) in this working fluid is 100: 20. A plain woven fabric made of 35% rayon and 65% polyester synthetic fiber was immersed in this processing solution, subjected to padding at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this processed fabric is as follows: -4.5 ° C to -4.1 ° C compared to the unprocessed fabric in the initial processing, and -4.5 ° C to -4.0 ° C compared to the unprocessed fabric after 10 washings. Compared with Example 3, there was an improvement in shielding effect and good washing durability. Further, the antibacterial activity of this processed fabric was antibacterial when the bacteriostatic activity value was 4.2 or more at the initial stage of processing and after 10 washings.
（コーティング加工）
酸化セリウム（Ａ）１２部と吸放湿性を有するポリウレタン樹脂（Ｂ）加工剤（樹脂成分４０％）６０部を水２４部に均一に混合した後、増粘剤４部を添加してホモミキサー攪拌で均一に混合して総量１００部のコーティング液を得た。このコーティング液の（Ａ）：（Ｂ）の固形配合割合は、約３３：６７となる。このコーティング液を、ポリエステル系合成繊維１００％からなる平織物にナイフコーティング（厚み０．１ｍｍ）を行い、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、加工初期が未加工布対比−５．５℃〜−５．０℃、洗濯１０回後が未加工布対比−５．５℃〜−５．０℃で、良好な遮蔽効果と洗濯耐久性があった。
(Coating process)
After uniformly mixing 12 parts of cerium oxide (A) and 60 parts of a moisture-absorbing / releasing polyurethane resin (B) processing agent (resin component 40%) with 24 parts of water, 4 parts of a thickener is added and a homomixer is added. The mixture was uniformly mixed by stirring to obtain a coating solution having a total amount of 100 parts. The solid blending ratio of (A) :( B) in this coating solution is about 33:67. This coating solution was knife coated (thickness 0.1 mm) on a plain woven fabric made of 100% polyester synthetic fiber, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this processed fabric is as follows: -5.5 ° C to -5.0 ° C compared to the unprocessed fabric in the initial stage of processing; -5.5 ° C to -5.0 ° C compared to the unprocessed fabric after 10 washings There was good shielding effect and washing durability.
（熱遮蔽加工剤の調整）
重量割合にして、酸化亜鉛１００に対し、γ−酸化アルミニウム１００の割合に混合した３０％のスラリー状水性組成物９８部に、乳化分散剤としてポリカルボン酸型高分子界面活性剤２部を添加し、総量１００部の加工剤を得た。
（繊維処理）
後は実施例１と同様に繊維処理をした。具体的には、上述の加工剤４部、ならびにシリコン・アクリル樹脂バインダー（パラソルブＧＨ−Ｓ１（４０％）：大原パラヂウム化学(株)社製）３部を水９３部に均一に混合して加工液とした。木綿１００％平織物を、この加工液に浸漬し、マングルで絞り１００％にてパディング処理後、１００℃で３分間乾燥、１６０℃で１分間熱処理をした。この加工布の太陽熱の遮蔽効果は、未加工布対比−５．５℃〜−５．１℃であった。
（比較例１０）
実施例９中の酸化亜鉛とγ−酸化アルミニウムの混合物の変わりに酸化亜鉛１００％の化合物を用いたもので、後は実施例９と同様に加工をした。このものの熱遮蔽効果は−４．０〜−３．６℃であった。このことから、熱遮蔽効果のある無機酸化物の配合により、相乗効果のあることが判る。
(Adjustment of heat shielding agent)
Add 2 parts of a polycarboxylic acid type polymer surfactant as an emulsifying dispersant to 98 parts of a 30% slurry aqueous composition mixed in a ratio of γ-aluminum oxide 100 to zinc oxide 100 in weight ratio Thus, a total amount of 100 parts of the processing agent was obtained.
(Fiber treatment)
Thereafter, the fiber treatment was performed in the same manner as in Example 1. Specifically, 4 parts of the above-mentioned processing agent and 3 parts of silicon / acrylic resin binder (Parasolv GH-S1 (40%): manufactured by Ohara Paradium Chemical Co., Ltd.) are mixed uniformly into 93 parts of water and processed. Liquid. A 100% cotton plain woven fabric was dipped in this processing solution, subjected to padding at 100% with a mangle, dried at 100 ° C. for 3 minutes, and heat treated at 160 ° C. for 1 minute. The solar heat shielding effect of this work cloth was -5.5 ° C to -5.1 ° C compared with the unprocessed cloth.
(Comparative Example 10)
A compound containing 100% zinc oxide was used in place of the mixture of zinc oxide and γ-aluminum oxide in Example 9, and the subsequent processing was performed in the same manner as in Example 9. The heat shielding effect of this product was −4.0 to −3.6 ° C. From this, it can be seen that there is a synergistic effect by blending an inorganic oxide having a heat shielding effect.
Claims (8)
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