Α7 Β7 經濟部中央標準局貝工消费合作社印袋 五、發明説明（1 ) 技術領域 本發明爲關於在建築材料和食品相關或皮革製品和衣 類’寢具等之要求防菌，防霉，防徴生物性用途中所使用 之緩釋放性異硫氰酸酯類及使用彼之異硫氰酸酯類。 背景技術 已知於芥末和山窬茉等中所含之異硫氰酸酯類爲具有 制菌，殺菌作用，不論是合成品，天然品，以數p pm〜 數十p pm之極微量的蒸氣濃度下，可取得此制菌，殺菌 效果•嘗試將此效果於工業上利用，乃提案於考慮異硫氰 酸酯類就其液髏原樣於操作上之不便，而例如將異硫氰酸 酯類含浸於矽膠中之殺菌，防霉材料，和如特公平5 — 2 8 5 8 9號公報所揭示般，令異硫氰酸酯類包接於環糊 精中之防霉材料等· 此些先前技術，於前者之情況爲速釋放性故不適用於 需要持績性之用途，後者之情況雖較前者更具備持續性， 但令包接在環糊精中之異硫氰酸酯類予以揮發，則必須爲 呈高濕度條件，又其持纊性於非食品領域中之使用上仍未 令人滿足。因此，特別爲了於非食品領域中發揮制菌，殺 菌效果，乃必須令包材內達到有效濃度地對包材花费工夫 ，並且對於不具有水分者則有無法發揮效力之問題。 於是，本發明爲以提供解決前述先前技術之玦點，且 操作爲簡單，並且不管濕度條件可長期持績釋放異硫氰酸 酯類及使用彼之異硫氰酸酯類爲其目的。 (請先Μ讀背面之注意事項再填寫本頁) 0^ -訂· • Λ_____ 本纸張尺度逋用中國國家橾準（CNS ) Α4规格（210X297公釐） A7 B7 五、發明説明（2 ) 發明之揭示 本發明之緩釋放性異硫氰酸酯類爲達成前述目的，如 申請專利範面第1項之記載’於與異硫氰酸酯類具有親和 性之高分子材料中，令其含有異硫氰酸酯類並作成膠狀物 或溶膠狀物爲其特撤· 又，申請專利範函第2項記載之緩釋放性異硫氰酸酯 類，爲於第1項記載之緩釋放性異硫氰酸酯類中，該髙分 子材料爲丙嫌酸系高分子材料，聚酯系高分子材料*聚醣 胺系高分子材料，聚苯乙烯系高分子材料，丙烯腈-丁二 烯-苯乙烯系高分子材料，或丙烯腈-苯乙烯共聚物爲其 特徴。 又，申請專利範圍第3項記載之緩釋放性異硫氰酸酯 類，爲於第1項或第2項記載之緩釋放性異硫氰酸_類中 ，相對於高分子材料1重置份以0.1〜15重置份之異 硫氰酸酯類爲其特徴· 經濟部中央標準局貝工消费合作社印製 (讀先《讀背面之注意事項再填寫本頁) 又，本發明之異硫氰酸酯類緩釋放體爲達成前述目的 ，如申請專利範圍第4項之記載*於至少一部分具備異硫 氰酸酯類透過部之收容髏內，收納第1項記載之緩釋放性 異硫氰酸醒類爲其特徴。 又，申請專利範圍第5項記載之異硫氰酸酯類緩釋放 體，爲於第4項記載之異硫氰酸酯類緩釋放體中，緩釋放 性異硫氰酸酯類爲僅以該透過部之透過速度爲以決定反應 速度之置收納於該收容體內。 本紙張尺度適用中國國家橾準（ CNS ) A4坑格（210X297公釐） • 5- ΒΊ_ 五、發明説明（3 ) 又，申請專利範困第6項記載之異硫氰酸酯類緩釋放 應，爲於第4項記載之異硫氰酸酯類緩釋放體中，該收容 髏爲由杯狀容器和蓋髏所構成，杯狀容器，蓋體之至少一 者爲由聚烯烴系樹脂所形成之異硫氰酸酯類透過性材料所 構成者爲其特徴· 又，申請專利範圍第7項記載之異硫氰酸酯類緩釋放 體，爲於第6項記載之異硫氰酸酯類緩釋放髏中，該聚烯 烴系樹脂所構成之杯狀容器的壁厚爲1 0 0〜1 0 0 0 # m，較佳爲300〜700#ηι爲其特徵《 又，申請專利範困第8項記載之異硫氰酸酯類緩釋放 體，爲於第6項記載之異硫氰酸酯類緩釋放镰中，該杯狀 容器或蓋體之任一者爲以異硫氰酸酯類不過性材料所構成 爲其特徴。 又，申請專利範圍第9項記載之異硫氰酸酯類緩釋放 體，爲於第6項記載之異硫氰酸酯類緩釋放體中，該杯狀 容器或蓋體之至少一者爲以透明構成爲其特徵。 經濟部中央樣準局貝工消费合作社印製 (請先閱讀背面之注意事項再填寫本頁) 圖面之簡單說明 圖1爲本發明異硫氰酸酯類緩釋放髏之一實施態樣的 說明線圖。 圖2爲本發明異硫氰酸酯類緩釋放體之其他實施態樣 的說明線圓》 圖3爲本發明異硫氰酸酯類緩釋放體之其他資施態樣 的說明線圖· 本紙張尺度適用中國國家標準（CNS ) Α4规格（210X297公釐） -6- 經濟部中央標準局負工消费合作杜印製 A7 _______B7 五、發明说明（4 ) 圖4爲本發明異硫氰酸酯類緩釋放髏之其他實施態樣 的說明線圖》 圖5爲本發明異硫氰酸酯類緩釋放體之其他實施態樣 的說明線圖· 圖6爲示出本發明緩釋放性異硫氰酸酯類之揮散特性 之線圖。 圖7爲示出本發明其他之緩釋放性異硫氰酸酯類之揮 散特性之線圖· 圖8爲示出本發明緩釋放性異硫氰酸酯類之釋放特性 之線圖· 圓9爲示出本發明異硫氰酸酯類緩釋放體之揮散特性 之線圖》 圖10爲示出本發明其他之異硫氰酸酯類緩釋放饑之 揮散特性之線圖· 實施發明之最佳形態 異硫氰酸酯類可使用異硫氰酸之烯丙酯和烷基酯等之 脂族系酯類，或芳香族系酯類等之各種酯類。於以食品作 爲對象之情形中，雖以使用芥末萃取物等中所含之天然的 異硫氰酸酯類爲較佳*但於非食品領域中之使用亦可運用 合成品亦無妨》 前述之異硫氰酸酯類以液«狀態之操作性差，且於容 器破損之情形中，因爲令異硫氰酸酯類直接附著至期待防 菌，防霉，防微生物性之被處理物（建築材料和食品類， 本紙張尺度適用中國困家標準（CNS ) A4规格（210X297公釐） (請先《讀背面之注意事項再填寫本頁) 訂 '.必. A7 ____ B7 五、發明説明（5 ) 或皮革製品和衣類，寢具等），而令此被處理物受到污染 ，並受到化學傷害，故爲了將其防止，乃藉由令異硫氰酸 酯類被含有於與其具有親和性之高分子材料中，並將性狀 作成膠狀和溶膠等之非液髏。又，藉由在具有此類親和性 之高分子材料中，含有異硫氰酸酯類，則可令揮散速度變 慢· 前述高分子材料可使用丙烯酸系高分子材料，聚酯系 高分子材料，聚醣胺系高分子材料，聚苯乙烯系高分子材 料，丙烯腈-丁二烯-苯乙烯系高分子材料，丙烯腈-苯 乙烯共聚物等，其中亦以聚丙烯酸酯系高分子材料，聚甲 基丙烯酸酯系高分子材料•聚酯系高分子材料或聚醣胺系 高分子材料之使用爲較佳，只要於此些高分子材料中混合 異硫氰酸酯類，則高分子材料爲於異硫氰酸酯類中泡脹， 且可簡單取得異硫氰酸酯類緩釋放性之溶膠或膠狀物。 經濟部中央標準局貝工消费合作社印裝 (請先《讀背面之注f項再填寫本頁) 前述高分子材料與異硫氰酸酯類之混合比例雖亦依0 異硫氰酸酯類之所欲的釋放速度，但以相對於高分子材料 1重量份之異硫氰酸酯類爲0 . 1〜1 5重置份之比例爲 較佳· 異硫氰酸酯類緩釋放體爲在成形性佳且具備易控制異 硫氰酸酯類之透過量特性之聚乙烯和聚丙烯等之聚烯烴系 樹脂製之異硫氰酸酯類透過性杯狀成形髏內，收納前述緩 釋放性異硫氰酸酯類，並使用可熱封之板狀蓋體予以熱封 而令至少一部分具備異硫氰酸_類透過部之收容體所構成 者爲較佳· 本紙張尺度適用中國國家標準（CNS > A4规格（210X297公釐） -8 - 經濟部中央標準局貝工消费合作社印裂 A7 _B7 五、發明説明（6 ) 此容器內之異硫氰酸酯類爲在聚烯烴系樹脂製之成形 體中進行擴散，並揮發至任何容器外•此時，異硫氰酸醋 類因揮散速度大，若絕對置不足則令顯示固定揮散速度之 時間變短，故以僅令前述透過部之透過速度爲決定反應速 度之置，收納於收容髏內爲較佳•如此，藉由令收容體內 收納充分置的異硫氰酸酯類，則可令前述揮散速度（若容 器存在之空間溫度，氣壓等之環境條件爲一定）爲受到聚 烯烴之組成和厚度，及容器內之異硫氰酸酯類份量所支配 。因此，可輕易地控制異硫氰酸酯類之揮散速度。即*可 取得具有所欲的異硫氰酸酯類揮散速度之長期緩釋放型之 緩釋放體。 圖1爲本發明異硫氰酸酯類緩釋放體之實施態樣之一 例，其爲於異硫氰酸酯類透過性材料所形成之杯狀容器1 (聚乙烯製）內，收納溶膠狀之緩釋放性異硫氰酸酯類2 ，並以異硫氰酸酯類非透過性材料所構成之片狀蓋體3予 以熱封者。異硫氰酸酯類非透過性之片狀物可使用聚酞酸 乙二醇酯和聚偏氯乙烯等之樹脂片，於此些片中設置金屬 澱積層之鋁箔等之金屬箔，或其複合髏片等。 又，於圖2之情形中，其爲於異硫氰酸_類非透性材 料所形成之杯狀容器1內收納膠狀之緩釋放性異硫氰酸酯 類2，並以異硫氰酸酯類透過性材料所構成之片狀蓋體3 (聚丙烯製）予以熱封者。 又，於圖3之情形中*其爲於前述圖2之蓋髖3中， 將異硫氰酸酯類非透過性材料所構成之片4，以可剝離地 本紙張尺度適用中國國家揉率（CNS ) A4規格（210X297公釐） (請先Μ讀背面之注ί項再填寫本買) 「裝- 訂.· • 9 - 經濟部中央橾率局負工消费合作社印製 A7 B7 五、發明説明（7 ) 安裝於異硫氰酸酯類非透過性之盖髏3上，令以防止使用 前之異硫氰酸酯類的揮發擴散。 經由令圖1至圖3之杯狀容器或蓋體之任一者以異硫 氰酸酯類不透過性材料予以構成，則可令利用異硫氰酸酯 類不透過性材料之緩釋放镰於何種場所均可設置。 又，經由令圖1至圖3之杯狀容器或蓋體之至少任一 者以透明所構成，則可由透明部確認膠狀或溶臛狀緩釋放 性異硫氰酸酯類之揮散後的固化，且亦可利用作爲膠狀或 溶膠狀緩釋放性異硫氰酸酯類使用期間之指示器· 又，於圖4之情形中，其爲於令異硫氰酸酯類透過性 材料所形成之片5，5彼此間予以熱封形成之袋體內，收 納溶膠狀之緩釋放性異硫氰酸酯類2 » 又，於圖5之情形中，其爲於令異硫氰酸酯類透過性 材料所形成之片5，和異硫氰酸酯類非透過性材料所構成 之片6予以熱封形成之袋體內，收納膠狀之異硫氰酸酯類 2 · 實施例 其次以具髏的實施例進行說明· <實施例1:使用聚酯系高分子材料作成緩釋放性異硫氰 酸酯類之其一 > 於異硫氰酸烯丙酯6 6 . 7克中加入聚酯系粉末樹脂 (東京油墨（株）製 POWDER RESIN G-120SP ) 3 3 . 3 克，並充分攪拌，取得含有約6 6 . 7%異硫氰酸烯丙酯 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁)Α7 Β7 Printed bags of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Technical Field The present invention relates to the requirements for antibacterial, mildew, and antibacterial in building materials and food-related or leather products and clothing 'bedding, etc.缓 Slow-release isothiocyanates used in biological applications and their isothiocyanates. BACKGROUND OF THE INVENTION It is known that isothiocyanates contained in wasabi, mangosteen, etc. have bacteriostatic and bactericidal effects. Whether they are synthetic products or natural products, the trace amounts are from a few p pm to several tens p pm. This bacteriostatic and bactericidal effect can be obtained under vapor concentration. • This effect is tried for industrial use. It is proposed to consider the inconvenience of isothiocyanates in terms of their liquid crossbones, such as isothiocyanate. Esters are sterilized and mold-proof materials impregnated with silicone, and, as disclosed in JP 5-2 8 5 8 9, mold-proof materials that make isothiocyanates encapsulated in cyclodextrin, etc. · These prior technologies are not quick-release in the former case and are not suitable for performance-requiring applications. Although the latter case is more sustainable than the former, they make the isothiocyanate encapsulated in cyclodextrin. To be volatilized, it must be in a high humidity condition, and its persistence in non-food applications is still unsatisfactory. Therefore, in order to exert bactericidal and bactericidal effects especially in the non-food field, it is necessary to make an effective concentration in the packaging material to spend time on the packaging material, and to have no effect on those who do not have moisture. Therefore, the present invention aims to provide a solution to the aforesaid problems of the prior art, the operation is simple, and the isothiocyanates can be released for a long period of time regardless of humidity conditions, and the use of the other isothiocyanates is the object thereof. (Please read the notes on the back before filling in this page) 0 ^ -Order · • Λ _____ This paper size is in accordance with China National Standards (CNS) Α4 size (210X297mm) A7 B7 V. Description of the invention (2) DISCLOSURE OF THE INVENTION In order to achieve the aforementioned purpose, the slow-release isothiocyanates of the present invention, for example, as described in the first aspect of the patent application 'in a polymer material having an affinity with isothiocyanates, make them Containing isothiocyanates and making them into a gel or sol is a special rule. Also, the slow-release isothiocyanates described in item 2 of the patent application letter are the ones described in item 1. Among the releaseable isothiocyanates, the tritium molecular materials are acrylic acid-based polymer materials, polyester-based polymer materials * polysaccharide amine-based polymer materials, polystyrene-based polymer materials, and acrylonitrile-butadiene Diene-styrene polymer materials, or acrylonitrile-styrene copolymers are special features. In addition, the slow-release isothiocyanates described in item 3 of the patent application range are reset to the polymer material 1 in the slow-release isothiocyanates described in item 1 or 2. Isothiocyanates of 0.1 ~ 15 replacement parts are printed as special features. · Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (read "Precautions on the reverse side before filling out this page). Also, the present invention is different. In order to achieve the aforementioned purpose, the thiocyanate-based sustained-release body is described in item 4 of the scope of the patent application. * At least a part of the storage skeleton having an isothiocyanate-permeable portion is provided with the slow-release property described in item 1. Thiocyanate is its speciality. Moreover, the isothiocyanate-type sustained-release body described in item 5 of the patent application scope is the isothiocyanate-type sustained-release body described in item 4, and the slow-release isothiocyanates are The permeation speed of the permeation portion is stored in the container in a position that determines the reaction speed. This paper size applies to China National Standard (CNS) A4 pit (210X297 mm) • 5- ΒΊ_ V. Description of the invention (3) In addition, the slow release of isothiocyanates described in item 6 of the patent application is difficult. In the isothiocyanate-type sustained-release body described in item 4, the receiving skeleton is composed of a cup-shaped container and a lid, and at least one of the cup-shaped container and the lid is made of a polyolefin resin. The formed isothiocyanate permeable material is characterized by the following characteristics: The isothiocyanate-type sustained release body described in item 7 of the scope of patent application is the isothiocyanate described in item 6 In the slow-release type skeleton, the wall thickness of the cup-shaped container made of the polyolefin resin is 100 ~ 100 ## m, preferably 300 ~ 700 # ηι. The isothiocyanate-type slow-release body according to item 8 is the isothiocyanate-type slow-release sickle according to item 6, and any of the cup-shaped container or lid is made of isothiocyanate. Ester-based materials are unique. In addition, the isothiocyanate-type sustained-release body described in item 9 of the patent application scope is the isothiocyanate-type slow-release body described in item 6, and at least one of the cup-shaped container or the lid is Features transparent structure. Printed by the Shell Sample Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Brief description of the figure. Figure 1 shows an implementation of one of the isothiocyanate slow release skeletons of the present invention Illustrate a line drawing. Fig. 2 is an explanatory line drawing of other embodiments of the isothiocyanate-type sustained-release body of the present invention "Fig. 3 is an explanatory line diagram of other embodiments of the isothiocyanate-type slow-release body of the present invention Paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -6- Work-consumption cooperation with Central Standards Bureau of the Ministry of Economic Affairs Du printed A7 _______B7 V. Description of the invention (4) Figure 4 is the isothiocyanate of the present invention Illustrative line diagram of other embodiments of the slow-releasing skeleton "Fig. 5 is an explanatory line diagram of other embodiments of the isothiocyanate-type sustained-release body of the present invention. Fig. 6 is a view showing the slow-release isosulfur of the present invention. Line diagram of the volatility characteristics of cyanate esters. Fig. 7 is a line chart showing the volatility characteristics of other slow-release isothiocyanates of the present invention. Fig. 8 is a line chart showing the release characteristics of the slow-release isothiocyanates of the present invention. Circle 9 A line chart showing the volatility characteristics of the isothiocyanate-type sustained-release body of the present invention "FIG. 10 is a line chart showing the volatility characteristics of the other isothiocyanate-type sustained-release body of the present invention As a good form of isothiocyanate, aliphatic esters such as allyl esters and alkyl esters of isothiocyanate, and various esters such as aromatic esters can be used. In the case of food, although it is better to use natural isothiocyanates contained in mustard extracts, etc., it is also possible to use synthetic products in non-food fields. Isothiocyanates have poor operability in liquid «state, and in the case of container damage, because isothiocyanates are directly attached to the treated object (building materials that expect anti-bacterial, anti-mildew and anti-microbial properties) And food, this paper size is applicable to Chinese Standards for Households (CNS) A4 (210X297 mm) (please read the precautions on the back before filling out this page) Order '. Must. A7 ____ B7 V. Description of the invention (5 ) Or leather products and clothing, bedding, etc.), and the object to be treated is contaminated and chemically damaged. Therefore, in order to prevent it, isothiocyanates are contained in substances that have affinity with them. In polymer materials, the properties are made into non-liquid skeletons such as colloids and sols. In addition, by including isothiocyanates in polymer materials with such affinity, the volatilization rate can be slowed down. The polymer materials can be acrylic polymer materials or polyester polymer materials. Polysaccharide amine polymer materials, polystyrene polymer materials, acrylonitrile-butadiene-styrene polymer materials, acrylonitrile-styrene copolymers, etc. It is better to use polymethacrylate-based polymer materials, polyester-based polymer materials or polysaccharide amine-based polymer materials. As long as isothiocyanates are mixed in these polymer materials, the polymer The material is a sol or gel that is swollen in isothiocyanates and can easily obtain the slow release properties of isothiocyanates. Printed by Shellfish Consumer Cooperative of Central Standards Bureau of Ministry of Economic Affairs (please read “Note f on the back side before filling out this page) The mixing ratio of the aforementioned polymer materials and isothiocyanates also depends on 0 isothiocyanates The desired release rate, but a ratio of 0.1 to 15 replacement parts relative to 1 part by weight of isothiocyanates of the polymer material is preferred. The isothiocyanate slow release body is Isothiocyanate-transmitting cup-shaped moldings made of polyolefin resins such as polyethylene and polypropylene with good moldability and easy-to-control permeability properties of isothiocyanates, containing the aforementioned slow release Isothiocyanate, and heat-sealed with a heat-sealable plate-like cover, so that at least a part of the containing body with an isothiocyanate permeable part is better. This paper size is applicable to China Standard (CNS > A4 specification (210X297 mm) -8-Printed and cracked by Shelley Consumer Cooperative of Central Standards Bureau of the Ministry of Economic Affairs A7 _B7 V. Description of the invention (6) The isothiocyanates in this container are in polyolefin series Resin formed body diffuses and volatilizes outside any container • At this time Due to the high volatility speed of isothiocyanate, if the absolute setting is insufficient, the time for displaying the fixed volatility speed will be shortened. Therefore, only the transmission speed of the aforementioned transmission part is used to determine the reaction speed, and it is stored in the receiving skull as Better • In this way, by allowing the isothiocyanates in the containment body to be fully contained, the aforementioned volatilization speed (if the environmental conditions such as the temperature of the space in which the container exists and the pressure of the air are constant) is subject to the composition of the polyolefin and The thickness and the amount of isothiocyanate in the container are dominated. Therefore, the volatilization speed of the isothiocyanate can be easily controlled. That is, * the long-term with the desired volatilization speed of the isothiocyanate can be obtained A slow-release type slow-release body. Fig. 1 is an example of an embodiment of the isothiocyanate-type slow-release body of the present invention, which is a cup-shaped container 1 (poly In ethylene), a sol-like slow-release isothiocyanate 2 is housed, and a sheet-like cover 3 made of an isothiocyanate-impermeable material is heat-sealed. Isothiocyanate Polyimide-like sheet can use poly Resin sheets such as ethylene glycol esters and polyvinylidene chloride, metal foils such as aluminum foils with metal deposition layers, or composite foils etc. are provided in these sheets. Also, in the case of FIG. Isothiocyanate_ cup-shaped container 1 formed of impermeable materials is a gel-like, slow-release isothiocyanate 2 and a sheet-shaped cover made of an isothiocyanate-permeable material The body 3 (made of polypropylene) is heat-sealed. In the case of FIG. 3, * it is a sheet 4 made of an isothiocyanate-impermeable material in the cover hip 3 of FIG. 2 described above. Applicable to China's national rubbing rate (CNS) A4 size (210X297 mm) with peelable paper size (please read the note on the back before filling out this purchase) "Binding-Binding. · • 9-Central Ministry of Economic Affairs 橾A7 B7 printed by the Bureau of Work and Consumer Cooperatives V. Description of the invention (7) Installed on the impermeable cover 3 of isothiocyanate to prevent the volatile diffusion of isothiocyanate before use. By making any of the cup-shaped container or lid of FIG. 1 to FIG. 3 made of an isothiocyanate-impermeable material, a slow release sickle using an isothiocyanate-impermeable material can be made. It can be installed in any place. In addition, by making at least any one of the cup-shaped container or the lid of FIG. 1 to FIG. 3 transparent, the transparent portion can be used to confirm the release of the gel-like or solvent-like slow-release isothiocyanates. It can be cured, and it can also be used as an indicator of the period of use of the gel-like or sol-like slow-release isothiocyanates. Also, in the case of FIG. The formed sheets 5 and 5 are heat-sealed in a bag body containing sol-like slow-release isothiocyanates 2 »Also, in the case of FIG. 5, they are isothiocyanates A sheet 5 made of a permeable material and a sheet 6 made of an isothiocyanate-impermeable material are heat-sealed to house a gel-like isothiocyanate 2 in the bag. Skull's example is explained. ≪ Example 1: One of slow-release isothiocyanates made of polyester polymer material > was added to 66.7 g of allyl isothiocyanate. Polyester-based powder resin (POWDER RESIN G-120SP manufactured by Tokyo Ink Co., Ltd.) 3 3. 3 g, and thoroughly stirred to obtain About 6 6.7% allyl isothiocyanate this paper applies China National scale prospective Qiao (CNS) A4 size (210X297 mm) (Please read smell precautions to fill out the back of this page)
-10· 經濟部中央標準局員工消费合作社印製 A7 ____B7_ 五、發明说明（8 ) 之溶膠》 <資施例2:使用聚酯系高分子材料作成緩釋放性異硫氰 酸酯類之其二> 於異硫氰酸烯丙酯7 5 . 0克中加入聚酯系粉末樹脂 (東京油墨（株）製 POWDER RESIN G.120SP ) 2 5 · 0 克，並充分攪拌，取得含有約7 5 . 0%異硫氛酸烯丙酯 之溶膠。 其次，準備3袋厚度4 0 之聚乙烯製附有扣件（ chuck )之袋（60mmx85mm)，並將實施例1之含 有約66.7%異硫氰酸烯丙酯之溶膠，實施例2之含有 約75.0%異硫氰酸烯丙酯之溶膠，及液狀之異硫氰酸 烯丙酯分別裝入4 . 0克，並測定異硫氰酸烯丙酯之揮散 達度時，取得如圖6所示之結果· 如圖6所闞明，可知經由使用聚酯系粉末，將異硫氰 酸烯丙酯溶膠化，則較液狀原樣，令異硫氰酸烯丙酯之揮 散速度變遲，且賦與緩釋放性。 尙，前述之高分子材料於使用聚丙烯酸酯系粉末，聚 甲基丙烯酸酯系粉末，或聚醣胺系粉末時，均f前述之聚 酯系高分子材料之情況取得同樣的賦與緩釋放性之結果。 <實施例3:使用聚丙烯酸酯系高分子材料作成緩釋放性 異硫氰酸酯類之其一> 於丙烯酸2 —乙基己酯6 0重置份和N —乙烯基吡咯 本紙張尺度適用中國國家標準（CNS > A4规格（210X297公釐） {請先閏讀背面之注f項再填寫本頁)-10 · Printed A7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ____B7_ V. Sol of Invention Note (8) < Information Example 2: Polyester-based polymer materials are used to make slow-release isothiocyanates. Second> To 75.0 g of allyl isothiocyanate, add polyester-based powder resin (POWDER RESIN G.120SP manufactured by Tokyo Ink Co., Ltd.) 2 5 · 0 g, and stir well to obtain 7 5.0% sol of allyl isothiocyanate. Next, three bags of polyethylene (chuck) with a thickness of 40 (60 mm x 85 mm) were prepared, and the sol containing about 66.7% allyl isothiocyanate in Example 1 and the content in Example 2 containing Approximately 75.0% of the sol of allyl isothiocyanate and the liquid allyl isothiocyanate were charged into 4.0 grams, and the volatility of allyl isothiocyanate was measured, as shown in the figure. Results shown in Figure 6 · As is clear from Figure 6, it can be seen that by using a polyester-based powder to solute allyl isothiocyanate, the volatilization rate of allyl isothiocyanate is changed more than it is liquid. It is late and imparts slow release. That is, when the aforementioned polymer materials use polyacrylate-based powders, polymethacrylate-based powders, or polysaccharide amine-based powders, the same conditions as those of the aforementioned polyester-based polymer materials are achieved with the same sustained release. Sexual results. < Example 3: One of slow-release isothiocyanates using polyacrylic polymer materials > 60 parts of acrylic acid 2-ethylhexyl ester and N-vinyl pyrrolide paper Standards apply to Chinese national standards (CNS > A4 specifications (210X297 mm) {Please read the note f on the back before filling this page)
-11 - A7 ___ B7 五、發明说明（9 ) 烷酮4 0重量份之混合物中，配合三丙烯酸三羥甲基丙烷 酯0 . 1莫耳％及光聚合引發劑苄基二甲基縮酮1 . 0莫 耳％後*令溶存之氧氣以氮氣取代後，流入深度1 mm之 容器中，其次，對其照射紫外線（氮氣氛圃氣下）取得交 聯聚合物。 其次，將殘留的單髓以甲醇及氯仿萃取，精製聚合物 後，減壓乾燥。 將此精製之聚合物浸潰於異硫氰酸烯丙酯中，取得含 有約8 0 %異硫氰酸烯丙醋之膠（泡膜率5 0 0 %) · 將此膠及異硫氰酸烯丙酷分別置取4 . 0克，各別裝 入厚度4 0 /zm之聚乙烯製附有扣件之袋（6 Ommx 85mm)，並測定異硫氰酸烯丙酯之揮發速度時，取得 如圖7所示之結果。 <實施例4:使用聚丙烯酸酯系高分子材料作成緩釋放性 異硫氣酸酯類之其二> 經濟部中夾樣舉局負工消费合作杜印策 (請先閱讀背面之注f項再填寫本頁) 於丙烯酸2 —乙基己酯6 0重量份和N —乙烯基吡咯 烷酮4 0重量份之混合物中，配合三丙烯酸三羥甲基丙烷 酯0 · 1莫耳％及光聚合引發劑苄基二甲基縮酮1 . 0莫 耳％後*令溶存之氧氣以氮氣取代後，流入深度1mm之 容器中，其次，對其照射紫外線（氮氣氛園氣下）取得交 聯聚合物。 其次，將殘留的單體以甲酵及氣仿萃取，精製聚合物 後，減壓乾燥· 本紙張尺度中國國家揉準（CNS ) A4规格（210X297公釐） -12- A7 _____B7____ 五、發明説明（10 ) 將此精製之交聯聚合物（0 . 9 6克）浸溃於異硫氰 酸烯丙酯中，取得含有約5 7%異硫氰酸烯丙酯之膠（ 2 . 2 4 克）· 將此膠（2 . 2 4克）及與內包於此膠同量之異硫氰 酸烯丙酯分別裝入各爲縱6 0mm，横8 0mm，厚度爲 50 和1 00 之聚乙烯製之袋中*且以熱封予以 封住。將內包此膠及異硫氰酸烯丙酯之密封聚乙烯袋，於 2 3 °C « 6 5 % RH之條件下放置，並由減少之重量測 定異硫氰酸烯丙酯之釋放率。 結果爲如圖8所示，可確認經由使用膠，令釋放速度 降低，爲賦與緩釋放性· <實施例5 :異硫氰酸酯類緩釋放髏之作成其一> 經濟部中央樣準局貝工消费合作社印製 <請先聞讀背面之注再填寫本頁) 於丙烯酸2 —乙基己磨6 0重量份和N —乙烯基吡咯 烷酮4 0重量份之混合物中，配合三丙烯酸三羥甲基丙烷 酯0 · 1莫耳％及光聚合引發劑苄基二甲基縮酮1 . 0莫 耳％後，令溶存之氧氣以氮氣取代後，流入深度1mm之 容器中，其次，對其照射紫外線（氮氣氛圍氣下）取得交 塒聚合物。 其次，將殘留的單體以甲酵及氣仿萃取*精製聚合物 後，減壓乾燥· 將此精製之聚合物浸溃於異硫氰酸烯丙酯中，取得含 有約8 0%異硫氰酸烯丙酯之膠（泡脹率5 0 096)。 其次，以熱壓成形機將厚度3 0 0 之聚丙烯製片 本紙張尺度適用中B國家揉準（CNS M4规格（2丨0X297公釐） -13· 經濟部中央標準局貝Η消费合作杜印製 A7 B7 _ 五、發明説明（11 ) •成形爲如圖1所示之杯狀容器·此容器之容器爲 2 . 1 0毫升· 於上述之聚丙烯製成形品中，量取上述含有異硫氰酸 烯丙酯之膠2 · 0克，並於開口部使用經可與聚丙烯墊封 材質所複合之鋁複合包材，且經熱封予以密封，並取得如 圓1所示之異硫氰酸烯丙_之緩釋放髏。 此緩釋放髖爲如圖9，令異硫氰酸烯丙酯以一定速度 0 . 4 lmg/h r下持績揮散3個月以上· <實施例6:異硫氰酸酯類緩釋放慵之作成其二> 於異硫氰酸烯丙酯66.7克中加入聚酯系粉末樹脂 (東京油墨（株）製 POWDER RESIN G-120SP ) 3 3 . 3 克，並充分攪拌*取得含有約6 6 · 7%異硫氰酸烯丙酯 之溶膠。 其次，準備2袋厚度4 0 之聚乙烯製附有扣件（ chuck )之袋（6 0mmx8 5mm)，並將上述含有約 6 6 . 7%異硫氰酸烯丙酯之溶膠，及異硫氰酸烯丙酯分 別裝入4克，並測定異硫氰酸烯丙酯之揮散速度時，取得 如圓1 0所示之結果· 如圚1 0所闓明，可知經由使用聚酯系粉末•將異硫 氰酸烯丙酯溶膠化，可令異硫氰酸烯丙酯之揮散速度變 遲，且賦與緩釋放性· <比較例1 > 本紙張尺度適用中國國家橾準（CNS ) Α4规格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁)-11-A7 ___ B7 V. Description of the invention (9) 40 parts by weight of an alkyl ketone is compounded with 0.1 mol% of trimethylolpropane triacrylate and photopolymerization initiator benzyldimethylketal. After 1.0 mol%, the dissolved oxygen was replaced with nitrogen, and then flowed into a container with a depth of 1 mm. Next, it was irradiated with ultraviolet rays (under a nitrogen atmosphere) to obtain a crosslinked polymer. Next, the remaining monomedulum was extracted with methanol and chloroform, the polymer was purified, and then dried under reduced pressure. The refined polymer was immersed in allyl isothiocyanate to obtain a gel containing about 80% allyl isothiocyanate (foam film rate of 50%). Acrylic acid was placed separately at 4.0 grams, and each was filled into a polyethylene bag with a thickness of 40 / zm (6 Ommx 85mm), and the volatilization rate of allyl isothiocyanate was measured. To obtain the results shown in Figure 7. < Example 4: The use of polyacrylate-based polymer materials as the second type of slow-release isothiocyanates > Du Yince, the Ministry of Economic Affairs and the Consumers' Co-operation and Consumption Cooperation (please read the note on the back first) (F-item, please fill in this page again) To a mixture of 60 parts by weight of 2-ethylhexyl acrylate and 40 parts by weight of N-vinylpyrrolidone, 0.1% mole of trimethylolpropane triacrylate and light Polymerization initiator: benzyl dimethyl ketal 1.0 mole% * After dissolving the dissolved oxygen with nitrogen, it flows into a container with a depth of 1 mm. Second, it is irradiated with ultraviolet rays (under a nitrogen atmosphere) to obtain cross-linking. polymer. Secondly, the remaining monomers are extracted with formazan and aerosol, and the polymer is refined and dried under reduced pressure. This paper is a Chinese national standard (CNS) A4 (210X297 mm) -12- A7 _____B7____ 5. Description of the invention (10) The refined cross-linked polymer (0.96 g) was immersed in allyl isothiocyanate to obtain a gum containing about 5 7% allyl isothiocyanate (2.24 G) · Put this glue (2.24g) and the same amount of allyl isothiocyanate in the glue into 60mm in length, 80mm in width, 50 and 100 in thickness respectively. In polyethylene bags * and sealed with heat seal. The sealed polyethylene bag containing this glue and allyl isothiocyanate was placed under the condition of 2 3 ° C «65% RH, and the release rate of allyl isothiocyanate was determined from the reduced weight. . As a result, as shown in FIG. 8, it was confirmed that the release rate was reduced by using a glue, and to provide a slow-release property. ≪ Example 5: Preparation of an isothiocyanate-type slow-release skeleton > Printed by the Sample Bureau Shellfish Consumer Cooperative Co., Ltd. < Please read the note on the back before filling this page) In a mixture of 60 parts by weight of 2-ethylhexyl acrylic acid and 40 parts by weight of N-vinylpyrrolidone, mix After 0.1 mol% of trimethylolpropane triacrylate and 1.0 mol% of benzyl dimethyl ketal as a photopolymerization initiator, the dissolved oxygen was replaced with nitrogen and flowed into a container having a depth of 1 mm. Next, it was irradiated with ultraviolet rays (under a nitrogen atmosphere) to obtain a crosslinked polymer. Next, the residual monomers were extracted with formic acid and aerobic extraction * to refine the polymer, and then dried under reduced pressure. The refined polymer was immersed in allyl isothiocyanate to obtain about 80% isosulfur. Gum of allyl cyanate (swelling rate 5 0 096). Secondly, a polypropylene sheet with a thickness of 3 0 by a hot-press forming machine is suitable for countries in China B (CNS M4 specification (2 丨 0X297 mm) -13 · Beijing Consumer Cooperation, Central Bureau of Standards, Ministry of Economic Affairs Printed A7 B7 _ 5. Description of the invention (11) • Shaped into a cup-shaped container as shown in Figure 1. The container of this container is 2. 10 ml. 2.0 g of allyl isothiocyanate glue, and an aluminum composite packaging material that can be compounded with a polypropylene gasket material is used at the opening portion, and sealed by heat sealing, and obtained as shown in circle 1 The slow-release skull of allyl isothiocyanate. This slow-release hip is shown in Fig. 9, which allows allyl isothiocyanate to circulate at a rate of 0.4 lmg / hr for more than 3 months. ≪ Implementation Example 6: Preparation of isothiocyanate slow-release osmium part 2> To 66.7 g of allyl isothiocyanate was added a polyester powder resin (POWDER RESIN G-120SP manufactured by Tokyo Ink Co., Ltd.) 3 3 3 grams and thoroughly stirred * to obtain a sol containing about 66.7% allyl isothiocyanate. Next, prepare 2 bags of polyethylene with a thickness of 40 A bag (60 mm x 8 5 mm) with a chuck, and 4 g of the above-mentioned sol containing about 66.7% allyl isothiocyanate and allyl isothiocyanate were respectively measured. At the volatilization rate of allyl isothiocyanate, the results shown in circle 10 were obtained. As shown in 圚 10, it can be seen that by using polyester-based powder, the allyl isothiocyanate can be sol-solubilized. Delays the volatilization rate of allyl isothiocyanate and imparts slow-release properties. ≪ Comparative Example 1 > This paper size applies to China National Standard (CNS) A4 (210X297 mm). (Read the notes on the back and fill out this page)
-14- A7 _B7 五、發明说明（12 ) 使用低密度聚乙烯及乙烯-醋酸乙烯酯共聚物各 3 3 . 3克，代替前述實施例1之聚酯系高分子材料，令 異硫氰酸烯丙酯予以溶膠化時，則均無法溶膠化，若靜置 則產生分離· 產業上之可利用性 於迄今所提案之異硫氰酸酯類之緩釋放製劑，其異硫 氰酸酯類之釋放時間爲數十分鐘至數小時左右，特別於非 食品領域中並無法揮發防菌，防霉•防微生物性之效力。 相反地，本發明之緩釋放性異硫氰酸酯類及使用彼之異硫 氰酸酯類緩釋放體，因異硫氰酸酯類之釋放期間達到數個 月，故特別於非食品領域之流通過程中可期待其防菌*防 霉，防微生物性之效果》 {請先閱讀背面之注意事項再填tr本頁) ο裝. ，1T·-14- A7 _B7 V. Description of the invention (12) Using 3,3 g each of low-density polyethylene and ethylene-vinyl acetate copolymer, instead of the polyester-based polymer material of the foregoing Example 1, let isothiocyanate When allyl esters are sol-solubilized, they will not be sol-solubilized. If they are left to stand, they will be separated and industrially available. Slow-release preparations of isothiocyanates that have been proposed so far and their isothiocyanates The release time is about tens of minutes to several hours, especially in non-food fields, it is not volatile, anti-bacterial, anti-mold and anti-microbial. In contrast, the slow-release isothiocyanates of the present invention and the isothiocyanate-based slow-release bodies using the same are particularly suitable for the non-food field because the release period of the isothiocyanates reaches several months. The anti-bacterial * anti-mildew, anti-microbial effect can be expected during the circulation process {Please read the precautions on the back before filling the tr page) ο. 1T ·
Q 經濟部中央橾準局負工消费合作社印製 本紙張尺度適用中國國家揉準（CNS > A4规格（210X297公釐） -15-Q Printed by the Ministry of Economic Affairs, Central Bureau of Standards and Labor, Consumer Cooperatives This paper size is applicable to China National Standards (CNS > A4 (210X297 mm) -15-