TW202417060A - 病毒感染抑制劑、樹脂組成物及病毒感染抑制製品 - Google Patents
病毒感染抑制劑、樹脂組成物及病毒感染抑制製品 Download PDFInfo
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
本發明提供一種病毒感染抑制劑,其能夠形成即便置於高溫環境下亦可大致防止透明性降低之塗膜或膜等病毒感染抑制製品。本發明之病毒感染抑制劑包含具有磺基鹽之病毒感染抑制化合物、及經碳標準化之桑德森(Sanderson)電負度之總和為28以下且經碳標準化之第一離子化傾向之總和為30以下之有機酸,因此,根據病毒感染抑制劑,含有該病毒感染抑制劑之病毒感染抑制製品即便置於高溫環境下透明性亦幾乎不會降低,並且經過長時間亦呈現優異之外觀。
Description
本發明係關於一種病毒感染抑制劑、樹脂組成物及病毒感染抑制製品。
近年來,除了季節性流感病毒之流行外,新型冠狀病毒(COVID-19)亦正在全球大流行。
又,高病原性之禽流感病毒發生變異,已確認在人類之間發生感染,進而,致死率極高之SARS病毒亦令人擔憂,人們對病毒之不安感與日俱增。
針對該等問題,專利文獻1中提出了一種抗病毒性表面處理劑,其由含有抗病毒劑之塗料構成,該抗病毒劑載持有磺酸系界面活性劑之碳酸鈣,且上述塗料為紫外線硬化型塗料或電子束硬化型塗料。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2016-128395號公報
[發明所欲解決之課題]
然而,含有上述抗病毒性表面處理劑之塗膜或膜存在當置於高溫環境下時透明性降低之問題。
本發明提供一種病毒感染抑制劑,其能夠形成即便置於高溫環境下亦可大致防止透明性降低之塗膜或膜等病毒感染抑制製品,或能夠與合成樹脂混合而構成可製造病毒感染抑制製品等之樹脂組成物。
[解決課題之技術手段]
本發明之病毒感染抑制劑之特徵在於:
包含具有磺基鹽之病毒感染抑制化合物、及
經碳標準化之桑德森(Sanderson)電負度之總和為28以下且經碳標準化之第一離子化傾向之總和為30以下之有機酸。
本發明之樹脂組成物之特徵在於:包含合成樹脂、及上述病毒感染抑制劑。
本發明之病毒感染抑制製品包含基材、及含有於該基材中之上述病毒感染抑制劑。
[發明之效果]
根據本發明之病毒感染抑制劑,含有該病毒感染抑制劑之病毒感染抑制製品即便置於高溫環境下透明性亦幾乎不會降低,並且經過長時間亦呈現優異之外觀(耐熱老化性)。
本發明之病毒感染抑制劑具有優異之耐熱老化性,因此不會損害基材之色彩等外觀,能夠維持基材之外觀並且賦予基材病毒感染抑制效果。
本發明之病毒感染抑制劑包含:
具有磺基鹽之病毒感染抑制化合物、及
桑德森電負度之總和為28以下且第一離子化傾向之總和為30以下之有機酸。
[病毒感染抑制化合物]
本發明之病毒感染抑制劑含有病毒感染抑制化合物作為有效成分。病毒感染抑制化合物於分子中具有磺基(-SO
3H)鹽。
病毒感染抑制化合物發揮來自磺基(-SO
3H)的鹽之病毒感染抑制效果。病毒感染抑制化合物尤其是對於有套膜(envelope)之病毒及無套膜之病毒之任一者均具有優異之病毒感染抑制效果。
再者,病毒感染抑制效果係指消除或降低病毒對細胞之感染力,或使得即便感染亦無法在細胞中增殖之效果。作為確認此種病毒之感染性之有無的方法,例如針對纖維製品,可例舉ISO18184或JIS L1922,針對纖維製品以外之塑膠或非多孔質表面之製品,可例舉ISO21702。抗菌製品技術協議會(SIAA)對滿足抗病毒加工劑之安全性及一定之抗病毒效果之基準的製品認證抗病毒加工標誌,抗病毒效果之基準係於ISO21702之評價中,空白製品(未添加抗病毒加工劑之製品)之病毒感染效價之常用對數值與加工品(添加抗病毒加工劑之製品)之病毒感染效價之常用對數值的差(抗病毒活性值)為2.0以上。病毒感染抑制劑係添加至塗料等表面塗佈劑中而使用,並利用上述評價方法進行評價。
於本發明中,例如,按以下條件評價病毒感染抑制效果時,於空白塗膜及試驗塗膜之病毒感染效價之常用對數值之差(抗病毒活性值)為2以上之情形時,視為具有病毒感染抑制效果。此時,無論所評價之病毒之種類為何,將針對至少1種病毒之空白塗膜與試驗塗膜之病毒感染效價之常用對數值之差(抗病毒活性值)為2.0以上者視為具有病毒感染抑制效果。
例如,可按照下述要領測定抗病毒活性值。將5質量份病毒感染抑制劑及95質量份紫外線硬化型丙烯酸塗料(COATTEC公式製造,商品名「AI-N2」)混合而製作塗料組成物。使用線棒塗佈器(wire bar coater)#8將塗料組成物塗佈於聚乙烯膜上,形成厚度為18 μm之塗佈層。
使用UV輸送裝置,於25℃以累計光量成為500 mJ/cm
2之方式對塗佈層照射波長365 nm之紫外線,使紫外線硬化型丙烯酸塗料硬化而形成厚度為18 μm之塗膜。對於塗膜,藉由切出一邊為5.0 cm之平面正方形狀來製作試驗片。
對於所獲得之試驗片之塗膜之表面,使1 mL之水滲入一邊為10 cm之平面正方形狀之不織布(例如,由NIPPON PAPER CRECIA公司製造,以商品名「Kimwipe S-200」於市面販售之不織布),並用不織布來回擦拭塗膜表面10次,製成試驗塗膜。
對於所獲得之試驗塗膜,依據ISO21702進行抗病毒試驗。對於反應後之病毒懸浮液,藉由溶斑(plaque)法算出試驗塗膜之病毒感染效價。
除不含有病毒感染抑制劑以外,按照與上述相同之要領製作空白塗膜,基於該空白塗膜,按照與上述相同之要領算出病毒感染效價(常用對數值)(PFU/cm
2)。
自空白塗膜之病毒感染效價減去試驗塗膜之病毒感染效價,藉此算出抗病毒活性值。
除此之外,還可例舉如「醫藥科病毒學」(1990年4月初版發行)中記載之溶斑法及紅血球凝集效價(HAU)測定法等。
病毒感染抑制劑之抗病毒活性值更佳為2.0以上,更佳為3.0以上。
作為磺基(-SO
3H)鹽,無特別限定,例如可例舉:鈉鹽(-SO
3Na)、鈣鹽[(-SO
3 -)
2Ca
2+]、銨鹽(-SO
3 -NH
4 +)、鎂鹽[(-SO
3 -)
2Mg
2+]、鋇鹽[(-SO
3 -)
2Ba
2+]等,較佳為鈉鹽。
作為含有磺基鹽之病毒感染抑制化合物,只要於分子中具有1個以上磺基鹽即可,例如可例舉:直鏈烷基苯磺酸鹽、α-烯烴磺酸鹽、烷基苯醚磺酸鹽、烷基二苯醚磺酸鹽、聚氧伸烷基烷基醚硫酸酯鹽、月桂基硫酸鹽、於線型聚合物之側鏈具有磺基鹽之聚合物、聚苯乙烯磺酸鹽、甲脒亞磺酸(formamidinesulfinic acid)鹽、3-胺基苯磺酸鹽、羥基苯磺酸鹽、間二甲苯-4-磺酸鹽、5-磺基水楊酸鹽、磺胺酸鹽、2-胺基-3,5-二甲基苯磺酸鹽、1,3-苯二胺-4-磺酸鹽、磺化(苯乙烯-二乙烯苯共聚物)鹽、鹿角菜膠鹽、磺化聚醚碸鹽、木質素磺酸鹽等。
作為直鏈烷基苯磺酸鹽,例如可例舉:十二烷基苯磺酸鈉、十二烷基苯磺酸鈣、十二烷基苯磺酸銨、十二烷基苯磺酸鎂、十二烷基苯磺酸鋇、十三烷基苯磺酸鈉、十三烷基苯磺酸銨、十四烷基苯磺酸鈉、十四烷基苯磺酸銨等,較佳為十二烷基苯磺酸鈉。
作為α-烯烴磺酸鹽,例如可例舉:C12~C18之烯烴磺酸鈉、C12~C18之烯烴磺酸鈣、C12~C18之烯烴磺酸銨、C12~C18之烯烴磺酸鎂、C12~C18之烯烴磺酸鋇等,較佳為C14之十四烯磺酸鈉。
作為烷基二苯醚磺酸鹽,例如可例舉烷基為C6~C18之烷基二苯醚磺酸之鈉鹽、鈣鹽、銨鹽、鎂鹽及鋇鹽等。
作為烷基苯醚磺酸鹽,例如可例舉烷基為C6~C18之烷基苯醚磺酸之鈉鹽、鈣鹽、銨鹽、鎂鹽及鋇鹽等。
於本發明中,烷基係自脂肪族飽和烴中除去1個氫原子後剩下之一價原子團。
關於在線型聚合物之側鏈具有磺基鹽之聚合物,線型聚合物無特別限定,例如較佳為乙烯聚合物、聚酯、聚胺酯(polyurethane),更佳為乙烯聚合物。
於線型聚合物之側鏈具有磺基鹽之聚合物無特別限定,例如可例舉包含含有磺基鹽之含磺基鹽單體作為單體單元之聚合物等。
作為包含含有磺基鹽之含磺基鹽單體作為單體單元之聚合物,例如可例舉:含有苯乙烯磺酸鹽單元之聚合物、苯乙烯磺酸鹽之均聚物、苯乙烯-苯乙烯磺酸鹽共聚物、對聚苯乙烯之苯環進行磺化而得之化合物之磺酸鹽、對包含苯乙烯成分之聚合物之苯環進行磺化而得的化合物之磺酸鹽等。
含磺基鹽單體無特別限定,例如可例舉:對苯乙烯磺酸鈉、間苯乙烯磺酸鈉、鄰苯乙烯磺酸鈉、對苯乙烯磺酸鈣、間苯乙烯磺酸鈣、鄰苯乙烯磺酸鈣、對苯乙烯磺酸銨、間苯乙烯磺酸銨、鄰苯乙烯磺酸銨等,較佳為苯乙烯磺酸鈉,就對於與病毒之反應性立體阻礙較少而言,更佳為對苯乙烯磺酸鈉。
於病毒感染抑制化合物為聚合物之情形時,可為含磺基鹽單體之均聚物,亦可為含磺基鹽單體和可與該含磺基鹽單體共聚之單體的共聚物。
可與含磺基鹽單體共聚之單體無特別限定,例如可例舉:丙烯酸烷基酯、甲基丙烯酸烷基酯、乙烯基烷基醚、乙酸乙烯酯、乙烯、丙烯、丁烯、丁二烯、二異丁烯、氯乙烯、偏二氯乙烯、2-乙烯基萘、苯乙烯、丙烯腈、丙烯醯胺、甲基丙烯醯胺、二丙酮丙烯醯胺、乙烯基甲苯等。再者,可與含感染抑制官能基之單體共聚之單體可單獨使用,亦可併用二種以上。
成為病毒感染抑制化合物之上述聚合物使用通用之聚合方法進行聚合即可。例如,可藉由使含有含磺基鹽單體之單體組成物在通用之自由基聚合起始劑之存在下聚合而獲得病毒感染抑制化合物。再者,作為自由基聚合起始劑,可例舉:1-羥基環己烷-1-基苯基酮、過氧化特戊酸第三己酯、過氧化苯甲醯、偶氮雙異丁腈等熱裂解型自由基聚合起始劑等。
於病毒感染抑制化合物包含聚合物之情形時,聚合物之重量平均分子量較佳為1000以上,更佳為5000以上,更佳為10000以上,更佳為100000以上。當病毒感染抑制化合物之重量平均分子量為1000以上時,能夠提升病毒感染抑制劑之耐熱老化性。於使基材含有病毒感染抑制劑之情形時,可在不損害基材外觀之情況下更有效地表現病毒感染抑制效果,並且病毒感染抑制化合物每一分子與病毒之吸附點增大,病毒感染抑制化合物與病毒之相互作用增強,從而能夠提升病毒感染抑制劑之病毒感染抑制效果。
病毒感染抑制化合物中所含之聚合物之重量平均分子量較佳為1000000以下,更佳為900000以下,更佳為800000以下,更佳為500000以下。當病毒感染抑制化合物之重量平均分子量為1000000以下時,能夠提升病毒感染抑制劑之耐熱老化性。於使基材含有病毒感染抑制劑之情形時,可在不損害基材之外觀之情況下更有效地表現病毒感染抑制效果。
再者,於本發明中,聚合物之重量平均分子量係藉由GPC(凝膠滲透層析法)法測得且經聚苯乙烯換算而得之值。
例如,可利用下述測定裝置及測定條件進行測定。
凝膠滲透層析儀:Waters公司製造,商品名「2690 Separations Model」
管柱:昭和電工公司製造,商品名「GPC KF-806L」
檢測器:示差折射計
樣品流量:1 mL/min
管柱溫度:40℃
溶離液:THF(tetrahydrofuran,四氫呋喃)
病毒感染抑制化合物較佳為形成為粒子狀。病毒感染抑制化合物之D90粒徑較佳為2 μm以上,更佳為2.5 μm以上,更佳為3 μm以上,更佳為3.5 μm以上。病毒感染抑制化合物之D90粒徑較佳為25 μm以下,更佳為22 μm以下,更佳為20 μm以下,更佳為18 μm以下,更佳為16 μm以下,更佳為14 μm以下,更佳為12 μm以下。當D90粒徑為2 μm以上時,病毒感染抑制化合物整體之表面積變小,病毒感染抑制劑之凝集性降低,成為病毒感染抑制化合物與病毒容易相互作用之形態,病毒感染抑制劑之病毒感染抑制效果提升。當D90粒徑為25 μm以下時,能夠減少病毒感染抑制劑之凝集且增加表面積而容易與病毒接觸,從而提升病毒感染抑制化合物之病毒感染抑制效果,並且能夠減少病毒感染抑制劑之凝集,減少病毒感染抑制製品在高溫環境下之透明性降低。
藉由將病毒感染抑制化合物之D90粒徑調整至上述範圍,將病毒感染抑制化合物中粒徑較大之粒子之粒徑調整至特定範圍,減少了病毒感染抑制化合物中含有粗大粒子之情況。病毒感染抑制化合物雖於其表面具有磺基鹽,但藉由將病毒感染抑制化合物之粒徑調整至上述範圍,能夠調整存在於病毒感染抑制化合物表面之磺基鹽之量,對病毒感染抑制劑賦予優異之病毒感染抑制效果,並且提升病毒感染抑制劑之耐熱老化性。
病毒感染抑制化合物之D50粒徑較佳為0.5 μm以上,更佳為1 μm以上,更佳為1.5 μm以上,更佳為2.0 μm以上。病毒感染抑制化合物之D50粒徑較佳為25 μm以下,更佳為20 μm以下,更佳為14 μm以下,更佳為12 μm以下,更佳為11 μm以下。
於病毒感染抑制化合物中,藉由將D50粒徑及D90粒徑設為上述範圍,能夠減少病毒感染抑制化合物中含有具有與D50粒徑相差較大之粒徑之粗大粒子之情況,能夠將病毒感染抑制化合物之粒徑設為更適當之大小。
而且,藉由將病毒感染抑制化合物之粒徑調整至更適當之範圍,來更適當地調整存在於病毒感染抑制化合物表面之磺基鹽之量,更有效地對病毒感染抑制劑賦予優異之病毒感染抑制效果,並且對病毒感染抑制劑賦予優異之分散性,減少了病毒感染抑制製品在高溫環境下之透明性降低。
病毒感染抑制化合物之D90粒徑及D50粒徑分別係指利用雷射散射法所得之體積基準之粒度分佈中之頻率之累積(自粒徑較小之粒子起進行累積)達到90%及50%之粒徑(90%累積粒徑及50%累積粒徑)。於病毒感染抑制化合物包含複數種病毒感染抑制化合物之情形時,病毒感染抑制化合物之D90粒徑及D50粒徑設為以病毒感染抑制化合物整體為基準而測得之值。
[有機酸]
病毒感染抑制劑含有有機酸作為有效成分。有機酸係與上述含有磺基鹽之病毒感染抑制化合物不同之化合物。有機酸於分子中不含有磺基鹽。有機酸不包括具有磺基鹽之有機酸。病毒感染抑制劑藉由組合上述特定之病毒感染抑制化合物及有機酸,而提升了含有病毒感染抑制劑之病毒感染抑制製品之耐熱老化性,且即便於置於高溫環境下之情形時,病毒感染抑制製品之色彩亦不會受損。於病毒感染抑制製品為透明之情形時,即便置於高溫環境下經過長時間亦能夠穩定地維持透明性。
有機酸係指於分子中包含至少1個(較佳為2個以上)碳且包含碳-氫鍵(C-H鍵)之酸性化合物。有機酸較佳為具有選自由羧基(-COOH)、磺基(-SO
3H)及膦酸基[-P(=O)(OH)
2]所組成之群中之至少一種酸性官能基,更佳為具有羧基。作為有機酸,無特別限定,例如可例舉:苯六甲酸、烏頭酸、檸檬酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、反丁烯二酸、順丁烯二酸、伊康酸、檸康酸、中康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、亞甲基二水楊酸、順-Δ4-四氫鄰苯二甲酸、葡萄糖酸、黏液酸、3,3'-硫代二丙酸、2,2'-硫代二乙醇酸、3,3'-二硫代二丙酸、2,2'-二硫代二乙醇酸、2,2'-二硫代水楊酸、4,4'-二硫代二丁酸、3-(十二烷基硫基)丙酸、吡啶甲酸、甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、丁烯酸、乙醇酸、乳酸、蘋果酸、酒石酸、奎尼酸、水楊酸、苯甲酸、香草酸、沒食子酸、苦杏仁酸、根皮酸、香豆酸、咖啡酸、阿魏酸、芥子酸、4-胺基苯甲酸、氮川三乙酸(triglycolamic acid)、二乙三胺五乙酸(diethylenetriamine pentaacetic acid)、羧甲基纖維素、羧甲基化殼聚糖、羧甲基化甲殼素、羧甲基葡聚糖、羧甲基-β-環糊精、羧基蔗糖、果膠、三仙膠、海藻酸、玻尿酸、富里酸、腐植酸、糖醛酸、阿拉伯糖酸、果糖酮酸、塔格糖酮酸、葡萄糖醛酸、艾杜糖醛酸、半乳糖醛酸、甘露糖醛酸、古羅糖醛酸(guluronic acid)等。再者,有機酸可單獨使用,亦可併用二種以上。
有機酸中,經碳標準化之桑德森電負度之總和為28以下。藉由使經碳標準化之桑德森電負度之總和為28以下,有機酸之各原子間之相互作用變高,有機酸分子之結構穩定化,因此分子結構之劣化得到抑制,病毒感染抑制劑之耐熱老化性得到提升。
有機酸中,經碳標準化之桑德森電負度之總和係指按照下述要領測得之值。關於桑德森電負度,例如已知:碳為2.746、氫為2.592、氧為3.654等。藉由將該等原子之值分別除以碳之2.746而進行標準化後之值分別為:碳為1.00、氫為0.944、氧為1.33等,將該等之值作為經碳標準化之桑德森電負度。算出有機酸中具有之各原子之經碳標準化之桑德森電負度之值的總和,並將該值作為有機酸之經碳標準化之桑德森電負度之總和。
有機酸中,經碳標準化之桑德森電負度之總和為28以下,較佳為27以下,更佳為25以下,更佳為22以下。有機酸中,經碳標準化之桑德森電負度之總和較佳為5以上,更佳為7以上,更佳為10以上。當經碳標準化之桑德森電負度之總和為28以下時,病毒感染抑制劑之耐熱老化性得到提升。當經碳標準化之桑德森電負度之總和為5以上時,病毒感染抑制劑之病毒感染抑制效果得到提升。
有機酸中,經碳標準化之桑德森電負度之總和可藉由減少分子中之碳數、碳-碳雙鍵數、羧酸及苯環等官能基數而減小。有機酸中,經碳標準化之桑德森電負度之總和可藉由增加分子中之碳數、碳-碳雙鍵數、羧酸及苯環等官能基數而增大。
有機酸中,經碳標準化之第一離子化傾向之總和為30以下。藉由使第一離子化傾向之總和為30以下,使得有機酸與氧分子之反應性變低,不易發生有機酸分子之氧化劣化,因此耐熱老化性得到提升。
有機酸之經碳標準化之第一離子化傾向之總和係指按照下述要領測得之值。關於第一離子化傾向,例如已知:碳為1086.5、氫為1312、氧為1313.9等。藉由將該等原子之值除以碳之1086.5而進行標準化後之值分別為:碳為1.00、氫為1.208、氧為1.209等,將該等之值作為經碳標準化之第一離子化傾向。算出有機酸中具有之各原子之經碳標準化之第一離子化傾向之值的總和,並將該值作為有機酸之經碳標準化之第一離子化傾向之總和。
有機酸中,經碳標準化之第一離子化傾向之總和為30以下,較佳為27以下,更佳為25以下,更佳為22以下。有機酸中,經碳標準化之第一離子化傾向之總和較佳為5以上,更佳為7以上,更佳為10以上。當經碳標準化之第一離子化傾向之總和為30以下時,不易產生能量不穩定之離子狀態,有機酸分子穩定化,因此分子結構之劣化得到抑制,病毒感染抑制劑之耐熱老化性得到提升。當經碳標準化之第一離子化傾向之總和為5以上時,病毒感染抑制劑之病毒感染抑制效果得到提升。
對於有機酸,藉由將經碳標準化之桑德森電負度之總和及經碳標準化之第一離子化傾向之總和限定於特定範圍內,可使得有機酸之各原子間之相互作用變高,另一方面,有機酸與氧分子之反應性變低,能夠提升病毒感染抑制劑之耐熱老化性。
於有機酸中,第一離子化傾向之總和可藉由減少分子中之碳數、碳-碳雙鍵數、或羧酸及苯環等官能基數而減小。有機酸中,第一離子化傾向之總和可藉由增加分子中之碳數、碳-碳雙鍵數、或羧酸及苯環等官能基數而增大。
有機酸之sp3碳之數量較佳為10以下,更佳為8以下,更佳為6以下。有機酸亦可不具有sp3碳,但有機酸之sp3碳之數量較佳為1以上,更佳為2以上。當有機酸之sp3碳之數量為10以下時,有機酸分子之結晶性得到提升,不易發生有機酸劣化,病毒感染抑制劑之耐熱老化性得到提升。當有機酸不具有sp3碳、或有機酸之sp3碳之數量為1以上時,有機酸之不飽和鍵減少,有機酸之氧化劣化減少,病毒感染抑制劑之耐熱老化性得到提升。
sp3碳係指與4個其他原子形成單鍵之碳,不包括藉由雙鍵及三鍵與其他原子鍵結之碳。
於病毒感染抑制劑中,經碳標準化之桑德森電負度之總和超過28之有機酸與經碳標準化之第一離子化傾向之總和超過30之有機酸的總含量,可在不阻礙病毒感染抑制劑之作用之範圍內含有,相對於病毒感染抑制化合物100質量份,較佳為5質量份以下,更佳為3質量份以下,更佳為1質量份以下,更佳為0質量份。
有機酸於25℃之pKa1較佳為5.5以下,更佳為4.6以下,更佳為3.6以下。酸性化合物於25℃之pKa1較佳為1.0以上,更佳為2.0以上,更佳為2.8以上。當有機酸於25℃之pKa1為5.5以下時,促進病毒向病毒感染抑制劑之吸附,病毒感染抑制製品之病毒感染抑制效果得到提升。當有機酸於25℃之pKa1為1.0以上時,可抑制有機酸所致之病毒感染抑制製品之劣化,並對病毒感染抑制製品賦予優異之耐熱老化性,即便於置於高溫環境下之情形時,病毒感染抑制製品之透明性等色彩亦不會受損。
其中,於本發明中,當電解質HA游離成A
-及H
+並構成游離平衡式(1)時,酸解離常數Ka由式(2)定義,pKa由酸解離常數Ka之反數之常用對數(3)定義。
於有機酸為多元酸之情形時,多元酸多階段地進行游離,但pKa1係指基於第一階段之游離常數而算出之pKa。
有機酸於25℃之pKa1係指藉由滴定測得之值。具體而言,使用有機酸及氫氧化鈉於25℃進行滴定,測定半當量點(滴加中和完成之量之一半之點)時於25℃之pH,藉此可求出pKa1。
有機酸之0.5質量%水溶液於25℃之pH較佳為4.5以下,更佳為4.0以下,更佳為3.5以下。當有機酸之0.5質量%水溶液於25℃之pH為4.5以下時,病毒感染抑制劑彼此之相互作用變強,因此能夠對病毒感染抑制製品賦予優異之耐熱老化性,即便於置於高溫環境下之情形時,亦能夠進一步減少病毒感染抑制製品之透明性等色彩受損。再者,有機酸之0.5質量%水溶液於25℃之pH係指將有機酸0.5 g加入純化水99.5 g中均勻混合而成之溶液(混合液)於25℃之pH值。於混合液中析出有機酸之情形時,只要混合液對於所析出之全部有機酸為飽和溶液即可。再者,於有機酸為混合物之情形時,有機酸之pH設為有機酸整體之pH。
相對於病毒感染抑制化合物100質量份,病毒感染抑制劑中之有機酸之含量較佳為40質量份以上,更佳為100質量份以上,更佳為500質量份以上。相對於病毒感染抑制化合物100質量份,病毒感染抑制劑中之有機酸之含量較佳為6000質量份以下,更佳為5000質量份以下,更佳為4000質量份以下。當有機酸之含量為40質量份以上時,藉由有機酸促進病毒感染抑制劑對病毒之吸附,能夠賦予更優異之病毒感染抑制效果,因此較佳。當有機酸之含量為6000質量份以下時,能夠減少由有機酸所引起之病毒感染抑制製品之劣化,並對病毒感染抑制製品賦予更優異之耐熱老化性,即便於置於高溫環境下之情形時,病毒感染抑制製品之透明性等色彩亦不會受損。
有機酸較佳為載持於基底粒子之表面。藉由使有機酸載持於基底粒子之表面,能夠提升病毒感染抑制劑之耐熱老化性,並且能夠減少病毒感染抑制劑之凝集,使病毒感染抑制劑均勻地含有於基材中,能夠賦予基材均勻且優異之病毒感染抑制效果。作為有機酸附著於表面之基底粒子,只要不妨礙病毒感染抑制劑之耐熱老化性,便無特別限定。粒子包括樹脂粒子及無機粒子。粒子可單獨使用,亦可併用兩種以上。
作為構成無機粒子之無機材料無特別限定,例如可例舉二氧化矽、沸石、矽藻土、高嶺土、水滑石、碳酸鈣、檸檬酸鈣、碳酸鎂、氫氧化鋁、氫氧化鎂、氧化鈦、滑石等。
作為構成樹脂粒子之合成樹脂,例如可例舉:苯乙烯系樹脂、丙烯酸系樹脂、胺酯系樹脂、氯乙烯系樹脂、ABS樹脂;苯乙烯-丁二烯橡膠(SBR)、丁腈橡膠(NBR)等合成橡膠等;較佳為苯乙烯系樹脂,更佳為聚苯乙烯。
苯乙烯系樹脂無特別限定,例如可例舉:包含苯乙烯、甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、二甲基苯乙烯、氯苯乙烯、溴苯乙烯等苯乙烯系單體作為單體單元之均聚物或共聚物;包含苯乙烯系單體、及可與該苯乙烯系單體共聚之一種或二種以上之乙烯單體作為單體單元之共聚物等。
作為可與苯乙烯系單體共聚之乙烯單體,例如可例舉:丙烯腈、甲基丙烯腈、丙烯酸、甲基丙烯酸、丙烯酸酯(丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯等)、甲基丙烯酸酯(甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等)等丙烯酸系單體、順丁烯二酸酐、丙烯醯胺等。
丙烯酸系樹脂無特別限定,例如可例舉:包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯等丙烯酸系單體作為單體單元之均聚物或共聚物;包含丙烯酸系單體、及可與該丙烯酸系單體共聚之一種或二種以上之乙烯單體作為單體單元之共聚物等。再者,(甲基)丙烯酸酯係指丙烯酸酯或甲基丙烯酸酯。
作為可與丙烯酸系單體共聚之乙烯單體,可例舉:丙烯腈、甲基丙烯腈、順丁烯二酸酐、丙烯醯胺等。
有機酸於以碳-氫鍵部分為代表之有機鏈部分(疏水性部分)具有疏水性。有機酸之有機鏈部分對樹脂粒子具有優異之親和性,另一方面,對樹脂粒子之親和性較有機鏈部分低之酸性官能基部分(例如羧基等)容易朝向外側,因此與病毒感染抑制化合物之相互作用得到提升,病毒感染抑制劑之耐熱老化性得到提升。
構成樹脂粒子之合成樹脂較佳為含有芳香族環。芳香族環能夠起到吸引附著於樹脂粒子之表面之有機酸之疏水性部分並使有機酸之酸性官能基(例如-COOH等)朝外側配向之作用,更有效地發揮病毒感染抑制劑之耐熱老化性。
芳香族環可為單環狀之芳香族環,亦可為單環狀之芳香族環複合並縮合而成者(縮合芳香族環)。芳香族環無特別限定,例如可例舉苯環、萘環、蒽環、聯苯、苯氧基苯基等。關於芳香族環,芳香族環及縮合芳香族環中之任一個或複數個氫原子被奪去,藉由共價鍵而與其他原子鍵結。
基底粒子之D50粒徑較佳為0.1 μm以上,更佳為0.2 μm以上,更佳為1 μm以上,更佳為2 μm以上。基底粒子之D50粒徑較佳為200 μm以下,更佳為100 μm以下,更佳為80 μm以下,更佳為60 μm以下,更佳為40 μm以下,更佳為20 μm以下,更佳為10 μm以下。
當基底粒子之D50粒徑為0.1 μm以上時,能夠使有機酸分散並載持於基底粒子之表面,能夠提升病毒感染抑制化合物與有機酸之相互作用,提升病毒感染抑制劑之耐熱老化性。
當基底粒子之D50粒徑為200 μm以下時,能夠減少含有病毒感染抑制劑之病毒感染抑制製品之表面產生之結塊等外觀異常,能夠獲得具有優異之外觀之病毒感染抑制製品。
基底粒子之D50粒徑係指利用雷射散射法所得之體積基準之粒度分佈中之頻率之累積(自粒徑較小之粒子起進行累積)為50%之粒徑(50%累積粒徑)。於基底粒子包括複數種基底粒子之情形時,基底粒子之D50粒徑設為以基底粒子整體為基準測得之值。
相對於基底粒子100質量份,有機酸於基底粒子上之附著量較佳為1質量份以上,更佳為5質量份以上,更佳為7質量份以上,更佳為10質量份以上。相對於基底粒子100質量份,有機酸於基底粒子上之附著量較佳為600質量份以下,更佳為500質量份以下,更佳為400質量份以下,更佳為300質量份以下。當有機酸之附著量為1質量份以上時,能夠使有機酸均勻地附著於基底粒子之表面,能夠更有效地發揮病毒感染抑制劑之耐熱老化性。當有機酸之附著量為600質量份以下時,有機酸彼此不進行結合,有機酸有效地配置於基底粒子表面,病毒感染抑制劑之耐熱老化性得到提升。
將有機酸載持於基底粒子表面之要領無特別限定,例如可藉由有機酸之接著力,亦可使用黏合劑樹脂將有機酸接著於基底粒子之表面,但基於病毒感染抑制劑之耐熱老化性得到提升之方面而言,較佳為藉由有機酸自身之接著力而使有機酸附著於基底粒子之表面。
[病毒感染抑制劑]
病毒感染抑制劑可藉由以通用要領將病毒感染抑制化合物與有機酸均勻地混合來製造。
於病毒感染抑制劑中,病毒感染抑制化合物及有機酸之總量較佳為50質量%以上,更佳為60質量%以上,更佳為70質量%以上,更佳為80質量%以上,更佳為90質量%以上,更佳為95質量%以上,更佳為99質量%以上,更佳為100質量%。
病毒感染抑制劑藉由病毒感染抑制化合物之作用而對於各種病毒具有病毒感染抑制效果,對於套膜病毒及無套膜病毒兩者均發揮優異之病毒感染抑制效果。
作為套膜病毒,例如可例舉:流感病毒(例如A型、B型等)、風疹病毒、伊波拉病毒、冠狀病毒[例如SARS病毒、新型冠狀病毒(SARS-CoV-2)]、麻疹病毒、水痘-帶狀疱疹病毒、單純疱疹病毒、腮腺炎病毒、節肢足動物攜帶性病毒、RS病毒、肝炎病毒(例如B型肝炎病毒、C型肝炎病毒等)、黃熱病毒、愛滋病病毒、狂犬病病毒、漢他病毒、登革熱病毒、立百病毒(Nipah virus)、麗沙病毒等。
作為無套膜病毒,例如可例舉:貓杯狀病毒、腺病毒、諾羅病毒、輪狀病毒、人類乳突病毒、脊髓灰白質炎病毒、腸病毒、柯薩奇病毒、人類小病毒、腦心肌炎病毒、鼻病毒等。
病毒感染抑制劑係含有於「期望賦予病毒感染抑制效果之基材」中而使用,含有病毒感染抑制劑之基材係製成病毒感染抑制製品並表現病毒感染抑制效果。
而且,病毒感染抑制劑具有優異之耐熱老化性,因此含有病毒感染抑制劑之基材不會因病毒感染抑制劑而發生變色,即便置於高溫環境下,經過長時間亦能夠維持基材本來之外觀。尤其是,於基材為透明之情形時,使病毒感染抑制劑包含於基材中而獲得之病毒感染抑制製品即便置於高溫環境下經過長時間亦能夠維持優異之透明性。
作為含有病毒感染抑制劑之基材,只要能夠含有病毒感染抑制劑,便無特別限定,例如可例舉:膜等合成樹脂成形體、塗料、壁紙、裝飾片材、地板材、纖維製品(織物、非織物、針織物)、交通工具(例如汽車、飛機、船等)用之內部用品及內裝材(座椅、兒童座椅及構成該等之發泡體等)、廚房用品、嬰兒用品、建築內裝材等。
作為構成合成樹脂成形體之合成樹脂無特別限定,例如可例舉:熱塑性樹脂(例如聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚乙酸乙烯酯、聚胺酯、鐵氟龍(註冊商標)、丙烯腈丁二烯苯乙烯樹脂、丙烯腈苯乙烯樹脂、丙烯酸樹脂、聚乙烯醇、聚醯胺、聚縮醛、聚碳酸酯、改質聚苯醚、聚酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、環狀聚烯烴、聚苯硫醚、聚四氟烯、聚碸、聚醚碸、聚芳酯、聚醚醚酮、熱塑性聚醯亞胺、聚醯胺醯亞胺等)、熱硬化性樹脂(例如酚樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、不飽和聚酯樹脂、醇酸樹脂、聚矽氧樹脂、聚胺酯、熱硬化性聚醯亞胺等)等。再者,合成樹脂可單獨使用,亦可併用二種以上。
病毒感染抑制劑可混練至合成樹脂中而使用。作為將病毒感染抑制劑混練至合成樹脂中之方法,可在作為原料之合成樹脂中混合病毒感染抑制劑以製作樹脂組成物,使用該樹脂組成物,藉由通用之合成樹脂之成形方法,製成成形品而獲得所需形狀之病毒感染抑制製品。作為通用之合成樹脂之成形方法,例如可例舉:擠出成形法、射出成形法、吹塑成形法等。可製成包含合成樹脂及病毒感染抑制劑之合成樹脂成形用母料,與作為原料之合成樹脂混合,使用通用之合成樹脂之成形方法,製成成形品而製造病毒感染抑制製品。
作為塗料,使用以往公知之塗料,例如可例舉油性塗料(例如調和塗料、油性清漆等)、纖維素塗料、合成樹脂塗料等。塗料亦包括藉由紫外線等放射線之照射而聚合並生成黏合劑成分之光硬化性塗料。
病毒感染抑制劑具有優異之耐熱老化性,由含有病毒感染抑制劑之塗料生成之塗膜經過長時間亦不會變色。因此,表面形成有塗膜之物品經過長時間亦能夠維持該物品所具有之外觀。尤其是,於塗膜為透明之情形時,形成有塗膜之物品經過長時間亦能夠維持該物品本身所具有之外觀。
於不損害塗料之物性之範圍內,塗料可含有顏料、塑化劑、硬化劑、增量劑、填充劑、抗老化劑、增黏劑、界面活性劑等添加劑。再者,作為使塗料中含有病毒感染抑制劑之方法,例如可例舉將病毒感染抑制劑及塗料供給至分散裝置並均勻地混合之方法等。再者,作為分散裝置,例如可例舉高速研磨機、球磨機、砂磨機等。
建築內裝材無特別限定,例如可例舉地板材、壁紙、天花板材、塗料、門把手、開關、開關蓋、蠟等。
交通工具內部用品及交通工具內裝材無特別限定,例如可例舉:座椅、兒童座椅、安全帶、車墊、座椅套、門、天花板材、腳墊、門飾板、儀錶面板、控制台、副駕駛座置物箱、吊環、扶手等。
[實施例]
以下,使用實施例對本發明具體地進行說明,但本發明不限於此。
準備下述化合物作為病毒感染抑制化合物及有機酸。於病毒感染抑制化合物為聚合物之情形時,將重量平均分子量示於表1之「Mw」欄。
[病毒感染抑制化合物]
・聚苯乙烯磺酸鈉(聚苯乙烯磺酸Na)
・α-烯烴磺酸鈉(α-烯烴磺酸Na)
・烷基二苯醚二磺酸鈉(烷基二苯醚二磺酸Na)
・十二烷基苯磺酸鈉(十二烷基苯磺酸Na)
[有機酸]
使用於表1之有機酸之「種類」欄中記載之化合物。有機酸中,將「經碳標準化之桑德森電負度之總和」、「經碳標準化之第一離子化傾向之總和」、「sp3碳之數量」、「25℃之pKa1」及「0.5質量%之水溶液於25℃之pH」分別記載於表1之「電負度」、「第一離子化傾向」、「sp3碳數量」、「pKa1」及「pH」欄中。
[基底粒子(粒子)]
・苯乙烯樹脂粒子(D50粒徑:4 μm)
・丙烯酸系樹脂粒子(D50粒徑:5 μm)
・二氧化矽粒子(D50粒徑:4.5 μm)
[病毒感染抑制化合物之粒子之製作]
使用輥壓裝置(Seishin企業公司,商品名「150型」)在轉速25 rpm、按壓力25 t之運轉條件下,將冷凍乾燥而獲得之病毒感染抑制化合物之粉末粗粉碎後,使用噴射磨機裝置(Nisshin Engineering公司製造,商品名「SJ-500」),在原料供給速度1 kg/h、壓縮空氣壓力0.75 MPa之運轉條件下進行粉碎,以獲得病毒感染抑制化合物之粒子。將所獲得之病毒感染抑制化合物之粒子之D50粒徑及D90粒徑示於表1中。再者,烷基二苯醚二磺酸鈉於室溫呈液狀,因此無法粒子化。
[載持於苯乙烯樹脂粒子之蘋果酸(苯乙烯樹脂粒子載持蘋果酸)之製作]
相對於蘋果酸之粒子及基底粒子(苯乙烯樹脂粒子)之合計質量,準備7倍質量之水。將10質量份蘋果酸之粒子、及30質量份苯乙烯樹脂粒子供給至水中並均勻地混合以製作分散液。
繼而,使用噴霧乾燥器以霧化器轉速20000 rpm將分散液粉體化,使蘋果酸之粒子全部附著(載持)於苯乙烯樹脂粒子之表面後,使用噴射磨機裝置(Nisshin Engineering公司製造,商品名「SJ-500」),於原料供給速度1 kg/h、壓縮空氣壓力0.75 MPa之運轉條件下進行粉碎,從而獲得蘋果酸之粒子載持(附著)於表面之苯乙烯樹脂粒子。
[載持於丙烯酸系樹脂粒子之蘋果酸(丙烯酸系樹脂粒子載持蘋果酸)之製作]
相對於蘋果酸之粒子及基底粒子(丙烯酸系樹脂粒子)之合計質量,準備7倍質量之水。將10質量份蘋果酸之粒子、及30質量份丙烯酸系樹脂粒子供給至水中並均勻地混合以製作分散液。
繼而,使用噴霧乾燥器以霧化器轉速20000 rpm將分散液粉體化,使蘋果酸之粒子全部附著(載持)於丙烯酸系樹脂粒子之表面後,使用噴射磨機裝置(Nisshin Engineering公司製造,商品名「SJ-500」),於原料供給速度1 kg/h、壓縮空氣壓力0.75 MPa之運轉條件下進行粉碎,從而獲得蘋果酸之粒子載持(附著)於表面之丙烯酸系樹脂粒子。
[載持於二氧化矽粒子之蘋果酸(二氧化矽粒子載持蘋果酸)之製作]
相對於蘋果酸之粒子及基底粒子(二氧化矽粒子)之合計質量,準備7倍質量之水。將10質量份蘋果酸之粒子、及30質量份二氧化矽粒子供給至水中並均勻地混合以製作分散液。
繼而,使用噴霧乾燥器以霧化器轉速20000 rpm將分散液粉體化,使蘋果酸之粒子全部附著(載持)於二氧化矽粒子之表面後,使用噴射磨機裝置(Nisshin Engineering公司製造,商品名「SJ-500」),於原料供給速度1 kg/h、壓縮空氣壓力0.75 MPa之運轉條件下進行粉碎,從而獲得蘋果酸之粒子載持(附著)於表面之二氧化矽粒子。
(實施例1~22、比較例1~6)
將表1所示之「種類」欄中分別記載之病毒感染抑制化合物及有機酸以表1之「含量」所示之量混合,以製作病毒感染抑制劑。
將5質量份病毒感染抑制劑及95質量份紫外線硬化型丙烯酸塗料(COATTEC公司製造,商品名「AI-N2」)混合,以製作塗料組成物。使用線棒塗佈器#8將塗料組成物塗佈於聚乙烯膜上,形成厚度為18 μm之塗佈層。
使用UV輸送裝置(EYE GRAPHICS公司製造之「ECS301G1」)於25℃以累計光量成為500 mJ/cm
2之方式向塗佈層照射波長365 nm之紫外線,使紫外線硬化型丙烯酸塗料硬化而形成厚度為18 μm之塗膜。
對於所獲得之塗膜,按照下述要領測定抗病毒試驗及耐熱老化性,將其結果示於表1中。
(抗病毒試驗)
對於塗膜,藉由切出一邊為5.0 cm之平面正方形狀來製作試驗片。
對於所獲得之試驗片之塗膜之表面,使1 mL之水滲入一邊為10 cm之平面正方形狀之不織布(NIPPON PAPER CRECIA公司製造之商品名「Kimwipe S-200」),用不織布來回擦拭塗膜表面10次,製成試驗塗膜。
對於所獲得之試驗塗膜,依據ISO21702進行流感病毒及貓杯狀病毒之抗病毒試驗。對於反應後之病毒懸浮液,藉由溶斑法算出試驗塗膜之病毒感染效價。
除不含有病毒感染抑制劑以外,按照與上述相同之要領製作空白塗膜,基於該空白塗膜,按照與上述相同之要領算出病毒感染效價(常用對數值)(PFU/cm
2)。空白塗膜之病毒感染效價(常用對數值)為6.5 PFU/cm
2。
自空白塗膜之病毒感染效價減去試驗塗膜之病毒感染效價,藉此算出抗病毒活性值。
(耐熱老化性)
將試驗塗膜於120℃處理1000小時。依據JIS K7361分別評價試驗塗膜處理前後之霧度。霧度(%)係於室溫25℃、相對濕度40%之環境下,使用霧度計(村上色彩技術研究所公司製造,「HM-150」)測得。自處理後之霧度值減去處理前之霧度值,藉此算出Δ霧度。Δ霧度越小,則可判斷耐熱老化性越優異。
[表1]
[產業上之可利用性]
病毒感染抑制化合物 | 有機酸 | 含量 (質量份) | 抗病毒活性值 | 耐熱老化性 | |||||||||||
種類 | Mw | D50粒徑 (μm) | D90粒徑(μm) | 種類 | 電負度 | 第一離子化傾向 | sp3碳數量 | pKa1 | pH | 病毒感染抑制化合物 | 有機酸 | 流感病毒 | 貓杯狀病毒 | Δ霧度 | |
實施例1 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 水楊酸 | 16.6 | 17.9 | 0 | 3.0 | 2.5 | 100 | 600 | 4.8 | 4.7 | 5 |
實施例2 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 蘋果酸 | 16.3 | 17.3 | 2 | 3.4 | 2.5 | 100 | 600 | 4.6 | 4.4 | 4 |
實施例3 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 反丁烯二酸 | 13.1 | 13.7 | 0 | 3.0 | 2.3 | 100 | 600 | 4.7 | 4.4 | 5 |
實施例4 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 順丁烯二酸 | 13.1 | 13.7 | 0 | 1.9 | 1.8 | 100 | 600 | 4.4 | 4.3 | 4 |
實施例5 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 檸康酸 | 16.0 | 17.1 | 1 | 2.3 | 2.0 | 100 | 600 | 4.2 | 4.3 | 4 |
實施例6 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 酒石酸 | 17.6 | 18.5 | 2 | 3.2 | 2.3 | 100 | 600 | 4.4 | 4.2 | 5 |
實施例7 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 鄰苯二甲酸 | 19.0 | 20.1 | 0 | 2.9 | 2.3 | 100 | 600 | 3.9 | 4.1 | 6 |
實施例8 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 2,2'-二硫代二乙醇酸 | 17.1 | 17.9 | 2 | 3.3 | 2.3 | 100 | 600 | 4.1 | 3.9 | 5 |
實施例9 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 2,2'-硫代二乙醇酸 | 16.0 | 17.0 | 2 | 3.3 | 2.3 | 100 | 600 | 4 | 3.8 | 6 |
實施例10 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 3,3'-二硫代二丙酸 | 22.9 | 24.8 | 4 | 4.1 | 3.1 | 100 | 600 | 3.5 | 3.3 | 7 |
實施例11 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 氮川三乙酸 | 23.6 | 25.4 | 3 | 3.0 | 2.2 | 100 | 600 | 3.5 | 3.2 | 8 |
實施例12 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 葡萄糖酸 | 26.6 | 29.0 | 5 | 3.9 | 2.8 | 100 | 600 | 3.1 | 2.7 | 7 |
實施例13 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 3,3'-硫代二丙酸 | 21.8 | 23.8 | 4 | 4.1 | 3.2 | 100 | 600 | 3 | 2.7 | 9 |
實施例14 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 順-Δ4-四氫鄰苯二甲酸 | 22.7 | 24.9 | 4 | 3.9 | 2.8 | 100 | 600 | 3.1 | 2.8 | 13 |
實施例15 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 苯乙烯樹脂粒子載持蘋果酸 | 16.3 | 17.3 | 2 | 3.4 | 2.5 | 100 | 600 | 4.6 | 4.4 | 3 |
實施例16 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 丙烯酸系樹脂粒子載持蘋果酸 | 16.3 | 17.3 | 2 | 3.4 | 2.5 | 100 | 600 | 4.2 | 4.2 | 3 |
實施例17 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 二氧化矽粒子載持蘋果酸 | 16.3 | 17.3 | 2 | 3.4 | 2.5 | 100 | 600 | 3.9 | 3.8 | 3 |
實施例18 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 鄰苯二甲酸 | 19.0 | 20.1 | 0 | 2.9 | 2.3 | 100 | 50 | 2.3 | 2.2 | 6 |
實施例19 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 鄰苯二甲酸 | 19.0 | 20.1 | 0 | 2.9 | 2.3 | 100 | 3500 | 3.2 | 3.1 | 9 |
實施例20 | α-烯烴磺酸鈉 | - | 18 | 24 | 鄰苯二甲酸 | 19.0 | 20.1 | 0 | 2.9 | 2.3 | 100 | 600 | 3.8 | 4 | 7 |
實施例21 | 烷基二苯醚二磺酸鈉 | - | - | - | 鄰苯二甲酸 | 19.0 | 20.1 | 0 | 2.9 | 2.3 | 100 | 600 | 3.8 | 4.1 | 8 |
實施例22 | 十二烷基苯磺酸鈉 | - | 17 | 24 | 鄰苯二甲酸 | 19.0 | 20.1 | 0 | 2.9 | 2.3 | 100 | 600 | 3.9 | 4.1 | 9 |
比較例1 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 乙二胺四乙酸 | 32.2 | 34.7 | 4 | 2.0 | 2.9 | 100 | 600 | 3.8 | 1.2 | 21 |
比較例2 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 月桂酸 | 37.3 | 43.4 | 11 | 4.9 | 6.8 | 100 | 600 | 1.2 | 0.9 | 24 |
比較例3 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | 二苯乙醇酸 | 29.3 | 32.1 | 1 | 3.0 | 2.7 | 100 | 600 | 3.4 | 3.2 | 25 |
比較例4 | 聚苯乙烯磺酸鈉 | 1000000 | 3.4 | 6.2 | - | - | - | - | - | - | 100 | 0 | 1.2 | 0.6 | 10 |
比較例5 | - | - | - | - | 順丁烯二酸 | 13.1 | 13.7 | 0 | 1.9 | 1.8 | 0 | 100 | 3.5 | 3.2 | 19 |
比較例6 | - | - | - | - | 檸康酸 | 16.0 | 17.1 | 1 | 2.3 | 2.0 | 0 | 100 | 3.2 | 3.3 | 20 |
根據本發明之病毒感染抑制劑,能夠製造即便置於高溫環境下透明性亦幾乎不會降低且經過長時間亦呈現優異外觀之病毒感染抑制製品。
(相關申請之相互參照)
本申請主張基於2022年8月10日申請之日本專利申請第2022-128508號之優先權,該申請之揭示內容藉由參照其整體而併入本說明書中。
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Claims (9)
- 一種病毒感染抑制劑,其特徵在於:包含具有磺基鹽之病毒感染抑制化合物、及 經碳標準化之桑德森(Sanderson)電負度之總和為28以下且經碳標準化之第一離子化傾向之總和為30以下之有機酸。
- 如請求項1之病毒感染抑制劑,其中,上述有機酸之sp3碳之數量為10以下。
- 如請求項1或2之病毒感染抑制劑,其中,上述有機酸於25℃之pKa1為5.5以下。
- 如請求項1至3中任一項之病毒感染抑制劑,其中,上述有機酸之0.5質量%水溶液於25℃之pH值為4.5以下。
- 如請求項1至4中任一項之病毒感染抑制劑,其中,上述有機酸載持於基底粒子之表面。
- 如請求項1至5中任一項之病毒感染抑制劑,其中,上述基底粒子為丙烯酸系樹脂粒子、苯乙烯系樹脂粒子或無機粒子。
- 一種樹脂組成物,其特徵在於:包含合成樹脂、及請求項1至6中任一項之病毒感染抑制劑。
- 如請求項7之樹脂組成物,其用作合成樹脂成形用母料。
- 一種病毒感染抑制製品,其包含基材、及含有於上述基材中之請求項1至6中任一項之病毒感染抑制劑。
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