TW200536867A

TW200536867A - High molecular compound suppressing absorption of protein blots and composition containing the same

Info

Publication number: TW200536867A
Application number: TW093133444A
Authority: TW
Inventors: Yusuke Hara; Yoshio Shimizu; Masanori Komatsu; Kiyoharu Itoh; Manabu Hattori
Original assignee: Lion Corp
Priority date: 2004-05-13
Filing date: 2004-11-03
Publication date: 2005-11-16
Also published as: WO2005111102A1; WO2005111102A9

Abstract

A high molecular compound suppressing absorption of protein blots and composition containing the same are provided. The compound can prevent the absorption of protein blots on hard surface such as glass, ceramics, stainless steel, plastic, on soft surface such as hair, textile fiber, and on gelatin surface and contact lens surface. The effect is lasting even with low concentration or a short time. The compound is obtained by copolymerizing monomer A, monomer B, and monomer C. A is the monomer expressed by formula (1) and/or formula (2), and B is by formula (3). C is a nonionic water-soluble monomer. (In formula (1), R1 represents hydrogen atom or methyl group. A represents oxygen atom or NH. R2 and R3 represent independent hydrogen atom or alkyl group. R4 and R5 represent alkyl group), (In formula (2), R6 represents hydrogen atom or methyl group. A represents oxygen atom or NH. R7 and R8 represent independent hydrogen atom or alkyl group. R9, R10 and R11 represent alkyl group, n means 0, 1, or 2. X represents Halogen atom), (In formula (3), R12 represents hydrogen atom or alkyl group. R13 represents alkyl group.)

Description

200536867 15195pif.doc 九、發明說明：【發明所屬之技術領域】本發明是有關於-種防止蛋白質附著之高分子化合物及含有此化合物之組成物，且特別是有關於一種對於以蛋白質為代表的生物衍生物質所附著，而擔心材料之物適合性,惡化的醫療用具等材料表面，包括：玻璃、陶究、 ===種塑料等的硬表面、所謂毛髮、纖維的軟表面， =膠特，形眼鏡表面等，以低濃度且短時处T⑽於則述表面上’賦與持久且出色之防止分子化合物及含有此化合物之組成物。各種=等醫::表具:的膠_表面、隱形眼鏡表面等，由於會被是的生物衍生物質所附著、為代表在矣而m〗接觸特殊的有機溶劑的話，大多容易 =:=理水溶性類型的商品作為處= 表面處二一般的使用方式，用處理劑而具有耐久性，且從使’可很簡單地不使儘可能低的處理劑濃度做短時間=觀::言’期盼以效果。並且，亦期盼針對盘人，也能得到良好的全性。 T 人體接觸的用途上，考量其安作為表面處理劑，目前提出有含有3級胺基的高分子 200536867 15195pif.doc 化合物、沖洗劑組成物β上成物(例如，參考專利文獻丨：日^洗性防污劍叙開2〇〇2·256〇30號）。具體而言，讀期公開公報之特含有某成分，此成分之特徵在二以：开:眼鏡用沖洗劑 (polyoxyalkylene oxide)單體為必兩二乳烷撑氧化物構成，對來自_之蛋白f的;;二==，所但是，對於限制於蛋白質髒污的才田出色。 J覆表面上未被沖洗下來而有所殘二:::、:從情況下的耐久性有更進—步的爲“於沒種，物質的附著很出色，但是對:防 ^面’期望在以趙時間處理或域度的高分處理上，有更進一步的效果。门刀十化““液同時，作為防止髒污附著於隱含有10〜45莫耳(mol)% 4級 \之技術建礒如參考專利文獻2:日本^ ^向分子化合物(例號)。具體而言，已經提出本了鏡上之組成物及方法。狹而白質畜積於隱形眼 ^對本發，之= 到= ^分子化合物溶液處理方面，無法得表面上，且能賦與此表面有效之防止蛋白質附子 >(卜艾二提出了具離子性之隱形眼鏡用途的高分 2=^專利文獻3:日本專利早期公開公報之、幵σ 947就）。具體而言，已提出了可提高表面滋 200536867 15195pif.doc =，及方法’主要係藉由在離子性隱形眼鏡細皮 ^有與表面相反電荷之保水持久性能高的高分子化合物。=而，對本發明目的之防止蛋白質的附著而言，即使 j短日寸間處理或減度的高分子化合物紐處理，亦益法 :=於表面上，且能輪表面有效之防止㈣此，還提出有含有乙烯系聚合物之陽離子性衍 tf ^子化合物(參考專利文獻4:日本專利早期公開么^之特開平1-50014號），雖然明確地指出了藉由高分子即使以短時間處理或=而言’ =r_於-上，且;防: 蛋白質附著的機能。穷双之防止 2·^=/ :日本專利早Μ開公報之特開報之特表2__號。 54-116947號。 #利早期公開公報之特開昭號。專利讀4··日本專料#松開公報之特解ι_蕭4 【發明内容】本發明鑑於上述情況，作玻璃、陶-一鋼、各種塑科等的硬;面的=、： 200536867 15195pif.d〇c 纖維的軟表面，或是凝膠(gel)表面、隱形眼鏡於會被以蛋自料絲的生物衍生物f $由 =的生物適合性惡化。對於這樣的材料(前述作八專的材料），本發明的目的就是在提供=用 ='子化合物’以織或短時間處理即可= =防止蛋白質附著的能力。而且，本發的就疋在提供-種不會輕㈣被水沖掉，可吸附在面j現其防污性之防污·祕、㈣具有洗淨性^防 :性的防污劑組成物、眼科用組成物以及隱形眼鏡用組成為了達到上述目的，本發明者經過審慎檢討之後，提出一種高分子化合物，此高分子化合物係將含有特定玫200536867 15195pif.doc IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a high-molecular compound for preventing protein attachment and a composition containing the same, and in particular, to a protein representative Bio-derived substances are attached, and the surface of materials such as medical appliances, which are worried about the suitability of the material, deteriorates, including: glass, ceramics, hard surfaces such as === plastics, so-called soft surfaces of hair, fibers, etc. On the surface of the eyeglasses, etc., at a low concentration and for a short time, the surface is' improved with a durable and excellent preventive molecular compound and a composition containing the compound. Various = waiting doctor :: tableware: glue_surface, contact lens surface, etc., because it will be attached to the biological derivative substance, as a representative of 矣, if you contact a special organic solvent, it is often easy =: = water soluble Sexual type products are generally used in the same way as surface = surface. It is durable with a treatment agent, and it is easy to make the concentration of the treatment agent as low as possible for a short period of time. Looking forward to the effect. In addition, I also look forward to getting good comprehensiveness for Panren. T For human contact applications, considering its safety as a surface treatment agent, a polymer containing a tertiary amine group 200536867 15195pif.doc compound, a compound of a rinsing agent β (for example, refer to patent document 丨: Japanese ^ Washing anti-fouling sword No. 200 · 2563030). Specifically, the special issue of the reading publication contains a certain component. The characteristics of this component are as follows: On: the eyeglass rinse agent (polyoxyalkylene oxide) monomer is composed of two lactic acid oxides. f's ;; two ==, but it is excellent for talents that are limited to protein soiling. The surface of J cover is not washed down and remains a bit 2: :::,: The durability in the case has been further improved-the step is "Yu no kind, the adhesion of the material is excellent, but the: anti-face" expectations In the Zhao time treatment or the high score processing, there is a further effect. The door knife is ten "" liquid, at the same time, to prevent the dirt from attaching to the hidden 10 ~ 45 mole (mol)% hidden level 4 \ For technical details, refer to Patent Document 2: Japan ^ ^ molecular compounds (example number). Specifically, the composition and method on the mirror have been proposed. Narrow and white matter accumulates in the invisible eye. = To = ^ In terms of solution treatment of molecular compounds, it cannot be obtained on the surface and can prevent protein aconite which is effective on this surface> (Bu Ai Er proposed a high score for the use of ionic contact lenses 2 = ^ Patent Document 3 : Japanese Patent Laid-Open Publication No. 就 σ 947). Specifically, it has been proposed to improve the surface nourishment 200536867 15195pif.doc =, and the method 'mainly by the fine skin of the ionic contact lens ^ has the opposite of the surface Polymer compounds with high water retention and long-lasting properties. For the purpose of preventing the attachment of proteins for the purpose of the present invention, even if it is treated in a short period of time or treated with a reduced polymer compound, it is also beneficial: = on the surface, and can effectively prevent the wheel surface. Therefore, it is also proposed that Cationic derivative tf ^ sub-compounds containing ethylene-based polymers (refer to Patent Document 4: Japanese Patent Laid-Open No. Hei 1-50014), although it is clearly pointed out that the use of polymers even when processed for a short time or = In terms of '= r_ 于-, and; prevention: the function of protein attachment. Poor double prevention 2 · ^ = /: Special table 2__ of Japanese Patent Early Publication No. 54-116947 . # 利 Early Publication Bulletin JP-A. Patent reading 4 ·· 日本专料 # Loose bulletin special solution _ Xiao 4 [Summary of the invention] In view of the above situation, the present invention is made of glass, ceramics-steel, various Plastics and other hard; surface = ,: 200536867 15195 pif.d〇c The soft surface of the fiber, or the surface of the gel (gel), the contact lens is a biological derivative that will be made of silk from eggs. Biocompatibility deteriorates. For such materials (the materials described above as the eight specialties), the present invention The purpose is to provide = the ability to use 'sub-compounds' for weaving or short-term processing = = the ability to prevent protein attachment. In addition, the present invention is provided-a species that will not be easily washed away by water and can be adsorbed on The anti-fouling and anti-fouling properties of the anti-fouling agent are as follows. The anti-fouling: anti-fouling agent composition, ophthalmic composition, and contact lens composition. In order to achieve the above purpose, the inventors have carefully reviewed , Proposed a polymer compound, this polymer compound will contain a specific rose

Si單體及/或含有特定4級銨基之單體、(甲基)丙烯酸酉4體以及非離子性水溶性單體以特定量共聚合而成，且重量平均分子量為5，_〜_〇，_。以此化合物對上述硬表面、軟表面及凝膠表面，即使進行低濃度短時間之處理，發現其具有持久之防止蛋白質附著的功能。更審慎檢討的、、、。果’發現藉由將上述高分子化合物含於水溶性組成物中，即使以低濃度短時間處理，亦可吸附於目標表面並具有良好的防止蛋白質附著的功能，且在以水沖洗的洗淨程序中，上述共聚物並不會被沖洗掉而作為有效成分吸附於目標表面上，展現其防污性，因而完成了本發明。因此，本發明的目的就是在提供一種用以防止蛋白質附著的高分子化合物，以及含有此高分子化合物之防污劑 200536867 15195pif.doc 組成物、洗淨劑組成物、眼科用組成物以及隱形眼鏡用組成物。此咼分子化合物係由下述(A)、（B)以及(c)共聚而成’且重量平均分子量為5，⑻〇〜〗，⑻〇,〇⑻。一⑷為(A])及/或(A_2)，（A-1)係以下述化學式⑴所表不之含有3級胺基的單體，含量為〇1〜75質量％，（A_2) 係以下述=學式(2)所表示之含有4級銨基的單體，含量為〇·^7質量％，（B)係以下列化學式(3)表示之（甲基）丙烯酸體，含量為21〜8〇質量％，（C)為⑷、⑻單體以外的非離子性水溶性單體，含量為Q1〜78 化學式（1) 、Si monomer and / or a monomer containing a specific fourth-order ammonium group, a (meth) acrylic acid hydrazone 4 body, and a nonionic water-soluble monomer are copolymerized in a specific amount, and the weight average molecular weight is 5, _ ~ _ 〇, _. This compound was found to have a long-lasting function of preventing protein adhesion even if the above-mentioned hard surface, soft surface, and gel surface were treated with a low concentration for a short time. More prudent review. Guo 'found that by including the above-mentioned polymer compound in a water-soluble composition, even if treated at a low concentration for a short time, it can adsorb on the target surface and have a good function of preventing protein adhesion, and it can be washed with water. In the procedure, the above-mentioned copolymer is not washed away and is adsorbed on the target surface as an active ingredient to exhibit its antifouling property, thus completing the present invention. Therefore, the object of the present invention is to provide a polymer compound for preventing the adhesion of proteins, and an antifouling agent containing the polymer compound. 200536867 15195pif.doc composition, detergent composition, ophthalmic composition, and contact lens Using composition. This fluorene molecular compound is formed by copolymerization of the following (A), (B), and (c), and has a weight average molecular weight of 5, ⑻〇～〖, 〇〇, 〇⑻. (1) is (A)) and / or (A_2), (A-1) is a monomer containing a tertiary amine group represented by the following chemical formula (1), and the content is 0 to 75% by mass; (A_2) is A monomer containing a fourth-order ammonium group represented by the following formula: (2) is represented by the following formula: (7) 7% by mass; (B) is a (meth) acrylic body represented by the following chemical formula (3): 21 to 80% by mass, (C) is a non-ionic water-soluble monomer other than rhenium and rhenium monomers, and the content is Q1 to 78. Chemical formula (1),

R4 (1) 巾’Rl為氫原子或？基’ A表示氧原子或NH，八// 氣原子或碳數1〜4直鏈或支鏈絲，R4、 ^ί(ί)示碳數1〜4直鍵或支鏈烧基，爪為0、1或2);R4 (1) Is R 'a hydrogen atom or? The radical 'A represents an oxygen atom or NH, an eight gas atom or a carbon number of 1 to 4 straight or branched filaments, and R4, ^ ί (ί) shows a carbon number of 1 to 4 straight or branched chain radicals, and the claw is 0, 1 or 2);

(ch2)] 十/ R9 10 11 χ· (2) HR6表錢軒或甲基，Α表示氧原子或ΝΗ，氫原蝴數1〜4之直鏈或支鏈烧基， A0 i A分別表示，碳數為1〜4之直鏈或支鏈烷丞’η句（j、i式上士劣 Χ 為卣素、〇Η、1/2S04、HS04、1/3Ρ04、 200536867 15195pif.doc hco2 或 ch3co2) CH2-C(R12)COOR13 (3) (化學式(3)中，R12為氫原子或曱基，Ri3為碳數丨〜^ 鏈或支鏈烧基）。依，本發明，對於會被以蛋白質為代表的生物衍生物貝所附著，因而擔心材料的生物適合性惡化之醫療用具等材料，包括··玻璃、陶瓷、不鏽鋼、各種塑料等的硬表面、、所謂毛髮、纖_軟表面，或是凝縣面、_眼鏡表面等，可提供防止蛋白質附著之高分子化合物，以低濃度或短時間處理即可具有出色且具耐久性的防止蛋白質附^能力，以作為有效之防污劑，以及含有此化合物之防污劑組成物、洗淨性防污劑組成物、眼科用組成物以及隱形眼鏡用組成物。為讓本發明之前述和其他目的、特徵和優點能更明顯易懂，下文特舉較佳實施例，作詳細說明如下。【實施方式】以下，針對本發明作更詳細地說明。本發明的高分子化合物是將上述(A)〜(〇的單體，相對於單體總量（1〇〇質量百分率(％))以特定比例摻配並共聚合而得之化合物。因此’組成本發明之共聚物的各單體之含量，與進行聚合時各單體的摻配量相同。本發明中所使用之單體為(A」)及/或(A_2)，（A]) 係以上述化學式(1)所表示之含有3級胺基的單體，（A-2) 係以上述化學式(2)所表示之含有4級銨基(ammonium)的 12 200536867 15195pif.doc 單體。上述化學式(1)中，R1為氫原子或曱基，A表示氧原子或NH4, R\、R3分別表示氫原子或碳數1〜4直鏈或支鏈烷基，R4、R5分別表示碳數丨〜4直鏈或支鏈烷基，m為〇、 1或2。碳數1〜4直鏈或支鏈烷基包括：曱基、乙基、丙基、異丙基、丁基、第三丁基、異丁基。上述化學式(2)中，R6表示氫原子或曱基，a表示氧原子或NH，R7、R8分別表示氳原子或碳數丨〜4之直鏈或支鏈烧基，R9、R1G以及Rii分別表示碳數為丨〜4之直鏈或支鏈烷基，η 為〇、1 或 2，乂為_ 素、〇H、1/2S04、HS04、 1/3Ρ〇4、HC〇2或CH3C02。碳數1〜4直鏈或支鏈烷基包括·曱基、乙基、丙基、異丙基、丁基、第三丁基、異丁含有3級胺基的(A-1)包括：（曱基)丙烯酸二曱基胺基乙酯（以下，「（曱基）丙烯酸」表示「丙烯酸」和「曱基丙烯酸」）、（曱基)丙烯酸二乙基胺基乙酯、（曱基)丙烯酸二丙基胺基乙S旨等（甲基）丙稀酸二烧基胺基烧g旨化合物、二曱基胺基乙基（曱基)丙烯醯胺、二曱基胺基丙基（曱基)丙烯醯胺、二乙基胺基丙基（甲基）丙烯醯胺等二烷基胺基烷基 (曱基）丙烯醯胺化合物。其中，較佳的是（曱基)丙烯酸二曱基胺基乙酯、（甲基）丙烯酸二乙基胺基乙酯、（甲基）丙烯酸二丙基胺基乙酯等（曱基）丙烯酸二烷基胺基烷酯化合物、二曱基胺基乙基（曱基）丙烯醯胺、二曱基胺基丙基（曱基) 丙烯醯胺、二乙基胺基丙基（曱基）丙烯醯胺等二烷基胺基 13 200536867 15195pif.doc 烷基（曱基）丙烯醯胺化合物，更佳的是（曱基)丙烯酸二曱基胺基乙酯、（甲基）丙烯酸二乙基胺基乙酯、二曱基胺基丙基（曱基）丙烯醯胺、二乙基胺基丙基（曱基）丙烯醯胺等。含有4級銨基的(A-2)單體，包括：氣化（曱基)丙烯酸二曱基胺基乙基曱酯、氯化（甲基）丙烯酸二甲基胺基乙基乙酯、硫酸（曱基）丙烯酸二曱基胺基乙基乙酯、磷酸（甲基) 丙烯酸二曱基胺基乙基曱酯、磷酸（曱基）丙烯酸二曱基胺基乙基乙酯、氣化（曱基）丙烯酸二乙基胺基乙基曱酯、氣化（曱基)丙稀酸二乙基胺基乙基乙醋、硫酸（曱基)丙稀酸二乙基胺基乙基乙酯、構酸（曱基）丙稀酸二乙基胺基乙基曱酯、磷酸（曱基）丙烯酸二乙基胺基乙基乙酯、氯化二曱基胺基丙基（甲基)丙烯酸胺基甲酯、氯化二甲基胺基丙基（曱基）丙烯酸胺基乙酯、硫酸二甲基胺基丙基（甲基）丙烯酸胺基乙酯、磷酸二甲基胺基丙基（甲基）丙烯酸胺基甲酯、磷酸二曱基胺基丙基（甲基）丙烯酸胺基乙酯等等，其中，較佳的是氣化（曱基)丙烯酸二曱基胺基乙基曱酯、氣化（曱基) 丙烯酸二甲基胺基乙基乙酯、硫酸（曱基）丙烯酸二曱基胺基乙基乙酯、氣化（曱基）丙烯酸二乙基胺基乙基甲酯、氣化（曱基)丙細酸二乙基胺基乙基乙酯、硫酸（曱基）丙稀酸二乙基胺基乙基乙S旨、氣化二曱基胺基丙基（甲基）丙稀酸胺基甲酯、氣化二甲基胺基丙基（曱基）丙烯酸胺基乙酯、硫酸二曱基胺基丙基（曱基）丙烯酸胺基乙酯，更佳的是氣化 (曱基)丙烯酸二曱基胺基乙基曱酯、氯化（曱基)丙烯酸二曱基胺基乙基乙酯、硫酸（曱基）丙稀酸二曱基胺基乙基乙酯。 14 200536867 15195pif.doc (A-1)單體與(A-2)單體可個別獨立使用或合併使用之此外，這些單體可單獨以1種或適當地組合2種以上而使用。在本發明中，從組成物製作之容易性和耐久性的觀點而言，使用1種2或種以上(A-1)單體為佳。夕單體的含量為下列各範圍。若(A)單體的含量太夕έ因為對水的溶解性高，而不具耐久性，且以低濃度，理、短時間處理的性能降低。不僅如此，若(Α)單體的含 I太少’在高分子化合物中作為吸附位置(site)的單體沒 f充分作用的機能，妓耐久性，以減度處理及短時間處理的性能降低。當含有(A_l)這種具3級胺基的單體時，其含量佔總單體之0.1〜75夤夏％，較佳的是2〜55質量％、更佳的〜35質量％。當含有(A_2)這種具4級銨基的單猶，其含量佔總單體置之0.1〜7質量％、較佳的是0.5〜6質量％、更佳的是 1〜5質量❶/〇。人| w疋用於本發明中的⑻單體係以下列化學式(3)表示基)丙烯酸酯單體。 CH2 二 C(R12)COOR13 ⑶ 此處’在上述化學式(3)中，Rl2為氮原子或甲基，Ri3 為碳數1〜6 ’較佳的是w之直鏈或支鏈烧基。作為(B)單體，更具體而言包括：（甲基)丙稀酸甲醋、 (甲基)丙烯酸乙酯、(甲基)丙烯酸丙醋、(甲基娜丁醋、(甲基娜第三丁醋二基 200536867 15195pif.doc 烯酸異丁酷、(甲基)兩烯酸己醋。其 =酸甲醋、(甲基)丙稀酸乙醋、二(甲基) 基）丙烯酸異丙酯、（甲基）丙悦缺丁& " 丁萨φ ^ ΛΛ a ^ ^ )丙烯S欠丁酯、（曱基）丙烯酸第三丁酉:’更仏的疋曱基兩烯酸甲酿、甲基丙烯酸乙美丙烯酸第三丁醋。這此單體=猶:ί丙烯酸丁醋、甲基 2種以上使用之。了早獨使用1種或適當地組合 (Β)單體的含量，是佔她置曰(ch2)] 十 / R9 10 11 χ · (2) HR6 means Qianxuan or methyl, A represents oxygen atom or NΗ, straight or branched alkyl group of hydrogen atom number 1 ~ 4, A0 i A respectively , Straight-chain or branched alkane 丞 'η sentences with carbon numbers of 1 to 4 (j, i, Sergeant inferiority X are halogen, 〇Η, 1 / 2S04, HS04, 1 / 3Ρ04, 200536867 15195pif.doc hco2 or ch3co2) CH2-C (R12) COOR13 (3) (In the chemical formula (3), R12 is a hydrogen atom or a fluorenyl group, and Ri3 is a carbon number; a chain or a branched alkyl group). In accordance with the present invention, materials such as medical appliances and medical materials that are likely to be attached to biological derivatives shellfish represented by proteins, and therefore are concerned about the deterioration of the biocompatibility of the materials, include hard surfaces such as glass, ceramics, stainless steel, various plastics, etc. , The so-called hair, fiber _ soft surface, or Ningxian surface, _ glasses surface, etc., can provide high molecular compounds to prevent protein adhesion, low concentration or short-term treatment can have excellent and durable protein adhesion prevention ^ Ability to serve as an effective antifouling agent, as well as an antifouling agent composition, a cleaning antifouling agent composition, an ophthalmic composition, and a contact lens composition containing the compound. In order to make the foregoing and other objects, features, and advantages of the present invention more comprehensible, preferred embodiments are described below in detail as follows. [Embodiment] Hereinafter, the present invention will be described in more detail. The polymer compound of the present invention is a compound obtained by blending and copolymerizing the monomers (A) to (0) at a specific ratio with respect to the total amount of monomers (100 mass percent (%)). Therefore, ' The content of each monomer constituting the copolymer of the present invention is the same as the compounding amount of each monomer during the polymerization. The monomers used in the present invention are (A ") and / or (A_2), (A)) It is a monomer containing a tertiary amine group represented by the above chemical formula (1), and (A-2) is a monomer containing a tertiary ammonium group (ammonium) represented by the above chemical formula (2) 12 200536867 15195pif.doc In the above chemical formula (1), R1 is a hydrogen atom or a fluorenyl group, A represents an oxygen atom or NH4, R \ and R3 represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R4 and R5 respectively represent Carbon number 丨 ~ 4 straight or branched alkyl group, m is 0, 1 or 2. Carbon number 1 ~ 4 straight or branched alkyl group includes: fluorenyl, ethyl, propyl, isopropyl, butyl In the above formula (2), R6 represents a hydrogen atom or a fluorenyl group, a represents an oxygen atom or NH, and R7 and R8 respectively represent a fluorene atom or a straight chain or branch having a carbon number of 1 to 4 Chain burner , R9, R1G, and Rii respectively represent a linear or branched alkyl group having a carbon number of 丨 ~ 4, η is 0, 1 or 2, and 乂 is _ prime, 〇H, 1 / 2S04, HS04, 1 / 3Ρ〇4 , HC〇2 or CH3C02. Linear or branched alkyl groups having 1 to 4 carbon atoms include fluorenyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, and isobutyl containing tertiary amino groups. (A-1) includes: (fluorenyl) difluorenylaminoethyl acrylate (hereinafter, "(fluorenyl) acrylic acid" means "acrylic acid" and "fluorenylacrylic acid"), (fluorenyl) diethylamine acrylic acid Ethyl ester, (meth) acrylic acid, dipropylaminoethyl, etc. (meth) acrylic acid, dialkylamino, ethylamine, dimethylaminoethyl (fluorenyl) allylamine, Dialkylaminoalkyl (fluorenyl) acrylamide compounds such as difluorenylaminopropyl (fluorenyl) acrylamide, diethylaminopropyl (meth) acrylamide, etc. Among them, preferable Dialkylamino (meth) acrylate, diethylamino (meth) acrylate, diethylamino (meth) acrylate, dipropylamino (meth) acrylate, etc. Alkyl ester compounds, di Dialkylamino groups such as aminoaminoethyl (fluorenyl) acrylamide, difluorenylaminopropyl (fluorenyl) acrylamine, diethylaminopropyl (fluorenyl) acrylamine 13 200536867 15195pif.doc Alkyl (fluorenyl) acrylamide compounds, more preferably difluorenylaminoethyl (fluorenyl) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (Fluorenyl) acrylamide, diethylaminopropyl (fluorenyl) acrylamine, etc. (A-2) monomers containing a 4th ammonium group, including: vaporized (fluorenyl) acrylic acid difluorene Ethylaminoethylethyl Ethyl Ester, Dimethylaminoethyl Ethyl Chloride (Meth) acrylate, Diethylamino Ethyl Ethyl Sulphate (Ethyl) Acrylate, Diethyl Ethyl Phosphate (Methyl) Acrylate Aminoethylfluorenyl ester, difluorenylaminoethylethyl phosphate (fluorenyl) acrylate, diethylaminoethylfluorinated (fluorenyl) acrylate, gasified (fluorenyl) acrylic acid Ethylaminoethylethylacetate, diethylaminoethylethyl sulfate (fluorenyl) acrylate, diethylaminoethylphosphonium acrylate (fluorenyl) acrylic acid, phosphoric acid (fluorenyl) ) C Diethylaminoethylethyl acid, Dimethylaminopropylpropyl (meth) acrylate aminomethyl chloride, Dimethylaminopropyl (fluorenyl) aminoethyl chloride, sulfuric acid Dimethylaminopropyl (meth) acrylate aminoethyl, dimethylaminopropyl (meth) acrylate aminomethyl, diamido phosphate (meth) acrylate amino Ethyl esters and the like, among them, preferred are vaporized (fluorenyl) bisaminoaminoethylethyl acrylate, gasified (fluorenyl) dimethylaminoethyl ethyl acrylate, and sulfuric acid (fluorenyl) Diethylaminoethyl ethyl acrylate, diethylaminoethyl methyl acrylate (fluorenyl) diethylaminoethyl ethyl acrylate, fluorinated diethylamino ethyl ethyl propionate, sulfuric acid (fluorene Radical) diethylaminoethyl ethyl acetate, vaporized dimethylaminopropyl (methyl) acrylic acid methyl ester, vaporized dimethylaminopropyl (fluorenyl) Aminoethyl acrylate, diamidosulfonyl propyl (fluorenyl) amine ethyl acrylate, more preferably difluorinated (fluorenyl) acrylate diethylaminoethyl fluorenyl acrylate, chlorinated (fluorenyl) ) Acrylic Diethylaminoethyl ethyl acid, diethylaminoethyl ethyl sulfate (fluorenyl) acrylic acid. 14 200536867 15195pif.doc (A-1) monomer and (A-2) monomer can be used individually or in combination. In addition, these monomers can be used alone or in appropriate combination of two or more. In the present invention, it is preferable to use one kind of two or more (A-1) monomers from the viewpoint of ease of production of the composition and durability. The content of the monomer is in the following ranges. If the content of (A) monomer is too high, because of its high solubility in water, it is not durable, and at low concentrations, the performance of physical and short-term treatment will be reduced. Not only that, if the (A) monomer contains too little I 'in the polymer compound as the site of adsorption of the monomer (site) does not fully function, prostitute durability, degraded performance and short-term processing performance reduce. When (A-1) a monomer having such a tertiary amine group is contained, the content thereof is 0.1 to 75% by mass of the total monomer, preferably 2 to 55 mass%, and more preferably 35% by mass. When containing (A_2) such a monovalent ammonium group, its content accounts for 0.1 to 7 mass% of the total monomer, preferably 0.5 to 6 mass%, and more preferably 1 to 5 mass. 〇. Human | w 疋 The fluorene monomer system used in the present invention is represented by the following chemical formula (3)) acrylate monomer. CH2 Di C (R12) COOR13 (3) Here, in the above-mentioned chemical formula (3), R12 is a nitrogen atom or a methyl group, and Ri3 is a carbon number of 1 to 6 ', preferably a linear or branched alkyl group of w. The (B) monomer more specifically includes (meth) acrylic acid methyl acetate, (meth) acrylic acid ethyl ester, (meth) acrylic acid acrylic acid ester, (methylnadinate, (methylnaphthalene) Tertiary butyl acetate 200536867 15195pif.doc Isobutyrenoic acid, hexanoic acid (meth) dienoic acid. It is acid methyl acetate, ethyl (meth) acrylic acid, di (meth) acrylic acid Isopropyl ester, (meth) propane butane & " Dingsa φ ^ Λ Λ a ^ ^) Propylene S butyl ester, (fluorenyl) acrylic acid tert-butyl fluorene: 'more fluorenyl dienoic acid Carbohydrate, Ethyl Methacrylate, Tertiary Butyl Vinegar. These monomers = still: ί butyl vinegar, methyl 2 or more. In order to use the content of one (1) monomer alone or appropriate combination, it accounts for her

&伯、、、心早體夏之21〜80質量％、勒佳的是22〜55質量。/〇、牿别杜从3 μ 、辦的人旦去、圭91所旦特佳的疋23〜50質量％。出）專 *、3里貝夏％時，以低濃度處理或短時間處理時’防止蛋白質附著的能力下降’若超過8〇質量％，難以得到均一的溶解性。& Bo ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ~~~~~~~~~~~~~~~~~ / 〇, 牿 bedou from 3 μ, the people who go to the office, the best 91 旦 23 ~ 50% by mass. (Export) Specialty, 3 mil Bescia%, low-level treatment or short-term treatment ‘the ability to prevent protein adhesion decreases’ If it exceeds 80% by mass, it is difficult to obtain uniform solubility.

本發明中所使用之(〇單體為⑷、⑼單體以外的非離子，(nomomc)水溶性單體。藉由將(Α)及(Β)以外的非離子性單體進行共聚合，不會使防止蛋白質附著之能力下降，並可k咼尚分子化合物的水溶性，做成含有本發明高分子化合物之組成物的話，可防止不溶性物的沉澱等令人困擾的情形。作為(C)單體，包括··以（甲基)丙烯醯胺，二甲基（曱基) 丙稀酿胺’ N-乙稀_2-σ此略烧酮，含有類糖(sugar analogue) 基之單體’以下列化學式（4)表示含有聚環氧化物 (polyalkylene oxide)基的單體等。 CH2=C( (R14)COO(CpH2pO)qR15 (4) (式(4)中，R14為氫原子或曱基，Ri5為氫原子、碳數i〜4 16 200536867 15195pif.doc 的烷基或苯基。P為2〜4的整數，q是2〜250的整數，分子中亦可以有p不同之2種以上的環氧化物基。）上述化學式(4)所示含有聚環氧化物基的單體包括：聚卓（甲基）丙細酸乙二g旨（poly ethyleneglycol mono(meth)acrylate)、聚乙二醇-聚單（曱基）丙烯酸丙二酯 (poly ethyleneglycol-poly propyleneglycol mono(meth)acrylate)等聚單（曱基）丙烯酸烷二酯 (polyalkyleneglycol mono(meth)acrylate)、曱氧聚單（曱基) 丙稀酉夂乙一 g 旨(methoxy poly ethyleneglycol m〇n〇(meth)aCrylate)、甲氧聚乙二醇-聚單（曱基）丙烯酸丙一酉曰、乙氧聚（甲基)丙稀酸乙二酯、乙氧聚乙二醇-聚單（甲基）丙烯酸丙一酯等聚單（曱基）丙烯酸烧二酯等，以碳數 1〜3之烷基經烷氧基化之後而成之烷氧聚單（甲基）丙烯酸，二酯、苯氧聚單（甲基)丙烯酸乙二酿、苯氧聚乙二醇聚單（曱基）丙烯酸丙二酯等。The monomers (0) used in the present invention are nonionics other than fluorene and fluorene monomers, and (nomomc) water-soluble monomers. By copolymerizing nonionic monomers other than (A) and (B), It does not reduce the ability to prevent the adhesion of proteins, and can also dissolve the water solubility of molecular compounds. When the composition containing the polymer compound of the present invention is made, it can prevent troublesome situations such as precipitation of insoluble matters. (C ) Monomers, including ... (meth) acrylamide, dimethyl (fluorenyl) acrylamine 'N-ethylene_2-σ this slightly burned ketone, containing sugar analogue Monomer 'represents a monomer containing a polyalkylene oxide group by the following chemical formula (4): CH2 = C ((R14) COO (CpH2pO) qR15 (4) (In the formula (4), R14 is hydrogen Atom or fluorenyl group, Ri5 is a hydrogen atom, an alkyl or phenyl group having a carbon number of i ~ 4 16 200536867 15195pif.doc. P is an integer of 2 ~ 4, q is an integer of 2 ~ 250, and p may be different in the molecule Two or more kinds of epoxide groups.) The monomer containing a polyepoxide group represented by the above chemical formula (4) includes poly (methyl) propionic acid ethylene g g (p oly ethyleneglycol mono (meth) acrylate), polyethyleneglycol-poly propyleneglycol mono (meth) acrylate, etc. polyalkyleneglycol mono (meth) acrylate, methoxy poly ethyleneglycol m (n) (meth) aCrylate, methoxypolyethyleneglycol-meth (acryl) acrylate In short, poly (meth) acrylic acid diesters such as ethoxy poly (meth) acrylic acid ethylene glycol, ethoxy polyethylene glycol-poly ((meth) acrylic acid propylene monoacrylate), etc. Alkoxy polymono (meth) acrylic acid formed by alkyl groups of 1 to 3, diester, phenoxy polymono (meth) acrylic acid ethylene glycol, phenoxy polyethylene glycol polymono (Fluorenyl) propylene acrylate and the like.

作為(c)單體，較佳的是：（甲基)丙烯醯胺，N_乙烯_2_ 此各烧_ ’曱氧聚單（曱基）丙烯酸乙二酯，更佳的是：N_ 乙烯2此咯烷酮，（C2H4〇)的平均重複數目（mean repeat number)為2〜25之甲氧聚單（甲基)丙烯酸乙二醋。⑹單體並?^於上述化合物，亦可以1種單獨使用或組合2種以上使用之。 (曰Q單體的含量，佔總單體量之〇·1〜78.9質量％，較 ΐϊί 15〜3質量％，更佳的是3G〜65質量％。（〇單體、3里夕則水洛性降低，太多則會對目標表面的吸附性 17 200536867 15195pif.doc 變差。本發明之高分子化合物，其重量平均分子量為5〇⑻ 〜1，000,000，較佳的是10,000〜500,000，更佳的是1〇〇〇〇〜400,000。若重量平均分子量太小，例如使用在凝膠表面時，會比此表面之孔隙(pore size)還小，若太大，則高分子化合物溶液的黏度過高，而產生製劑設計上的限制。另外，在本發明中，重量平均分子量可藉由凝膠滲透層析法(gd permeation chromatography)，以 0.5 莫耳/公升（m〇1/L)醋酸、0.5mol/L醋酸鈉的水/乙二醇二50/50(v/v%)溶液為移^ 相(mobile phase)，以聚乙二醇為標準而求得。本發明之高分子化合物的製造方法，只要是可將上述 (A)〜(C)單體共聚合而成共聚物，並沒有特別的限制，^ 以藉由如溶液聚合、懸浮聚合、塊狀聚合而進行聚合反應。工業上而言，較佳的是藉由溶液聚合、懸浮聚合的自由基聚合反應，尤其以溶液聚合的方法更佳。另外，本發明之As the (c) monomer, preferred are: (meth) acrylamidonium, N_ethylene_2_ each of these are fired_'oxopolymono (fluorenyl) ethylene acrylate, and more preferably: N_ethylene 2This rolidone, (C2H4〇) has an average repeat number (mean repeat number) of 2 to 25, methoxy polymono (meth) acrylate. The monomers may not be combined with the above compounds, and may be used alone or in combination of two or more. (The content of the Q monomer accounts for 0.1 to 78.9% by mass of the total monomer amount, which is 15 to 3% by mass, and more preferably 3G to 65% by mass. (0 monomer, 3 miles of water) If the viscosity is reduced, too much will cause poor adsorption on the target surface. 17 200536867 15195 pif.doc The polymer compound of the present invention has a weight average molecular weight of 50 to 1,000,000, preferably 10,000 to 500,000. More preferably, it is 10000 to 400,000. If the weight average molecular weight is too small, for example, when used on the surface of a gel, it will be smaller than the pore size of the surface. If it is too large, the The viscosity is too high, which leads to a limitation in the formulation design. In addition, in the present invention, the weight average molecular weight can be determined by gel permeation chromatography (gd permeation chromatography) at 0.5 mol / liter (m01 / L) A 50/50 (v / v%) solution of acetic acid and 0.5 mol / L sodium acetate in water / ethylene glycol is a mobile phase and is obtained by using polyethylene glycol as a standard. The polymer of the present invention There is no method for producing a compound as long as it is a copolymer capable of copolymerizing the above (A) to (C) monomers. It is particularly limited to carry out the polymerization reaction by, for example, solution polymerization, suspension polymerization, or block polymerization. Industrially, it is preferably a radical polymerization reaction by solution polymerization, suspension polymerization, especially solution polymerization. The method is better. In addition, the invention

共水物為無規共聚物(rand〇m C〇p〇ly mer)或塊狀妓聚物亦佳。 A >如果藉由溶液聚合而進行聚合反應，可使用例如水、甲醇—乙醇、異丙醇等的低級酒精、苯、曱苯、二甲苯、 %^烧、己烧等的芳香族、脂職或雜賴化合物、醋酸乙酉曰、丙_、丁酮等各種有機溶劑作為溶劑。聚合濃度並無特2限制，但通常以1G〜5G f量％進行聚合為佳。聚合開始劑(initiator)，可使用例如··過硫酸銨、過硫酸鈉、過硫酸鉀等過硫酸鹽、過氧化苯曱醯__ 18 200536867 15195pif.doc per〇xlde)、過氧化月桂醯(lauroyl peroxide)等過氧化物、氫過氧化異丙苯（cumene hydroperoxide)、氫過氧化物、偶氮二異丁腈(azobisisobutyronitrile)等的偶氮化合物等。聚合開始劑濃度，通常是所用總單體量的〇·〗〜！〇莫耳％為佳。並且，為了限制分子量，使用如烷硫醇(alkyl mercaptan)之類的連鎖移動劑、路易斯酸化合物等的聚合促進劑、磷酸、檸檬酸、酒石酸、乳酸等pH調整劑亦佳。聚合溫度可根據所使用之溶劑、聚合開始劑作適當選擇，不過，通常以室溫〜150°C為佳。所得到之高分子化合物中所含之殘餘單體等低分子量雜質，可藉由活性碳、薄膜過濾、透析膜等處理去除之，並加以，製。—般而言’活性碳可使用如木材、煤、挪子殼等以Sao或瘵氣活化後之物質，至於活性碳的形狀，有粉狀、破碎狀’纖維狀等’並無特別之限定。而超微過滤膜的材貝，可使用聚砜（p〇lysulf〇ne)、聚醚砜 (polyethersulfbne)、聚偏氟乙稀(⑽㈣町脇狀础·㈣、醋酸纖維素、狐纖維料。至於薄狀雜包括有平膜狀、中空纖維狀等，並沒有特別之限定。 *用作醫療用具等的材料’如玻璃、卩㈣、獨鋼、塑料等的硬表面、毛髮、纖維等的軟表面、凝膠表面及隱形眼，表面’擔心、會被生物衍生物_如最典型之蛋白質所附著，而使此些材制生物適合性惡化，本發明之防止白質附著用高分子化合物，以低濃度或短時間處理即可且有出色的防止蛋白質附著能力。此高分子化合物吸附在^ 19 200536867 15195pif.doc 些表面（前述醫療用具材料)上，可賦與表面防污性，由以水清洗時不會輕易地被沖掉，可用於防污性組成物上。不僅如此，還此在洗務目標物的同時賦與防污性，即使是在以水洗滌所伴隨的沖刷程序中，由於高分子會被沖掉，並吸附於目標面上而能表現其防污性:故可用作沖洗性防污劑組成物。同時，含有本發明之防止蛋白質附著用高分子化合物的組成物，由於具有上述特性，適宜作為眼科用組成^， ^特別適合隱形眼鏡用。眼科用組成物包括：一般點眼藥、抗菌性點眼藥、人工淚液、隱形眼鏡包裝液、洗眼藥等。隱形眼鏡用組成物，具體而言，包括：隱形眼鏡用處理液、沖洗液、保存液、沖洗保存液、沖洗消毒液等。本發明之高分子化合物在上述各組成物t的含量，雖然沒^特別的限制，-般，是佔各組成物全體之〇.嶋〜 20質量％，較佳的是議〜⑺f量％、更佳高分子化合物的含量太少，則無法充分地發 =機雜止蛋白質附著)’若太多則產生製劑設計上當各種組成物含有本發明之高分子化合其用途，單獨使用丨種或並用2 ]^ 口性低分子量界面：離二： :里==括:獅黃酸鹽、硫酸垸基聚氧乙稀 ^烷基聚乳乙烯醚、脂肪酸二乙醇醯胺、队 (N-alkyienebet—、聚氧乙歸硬化萬麻油 20 20053 麵。c HCO-60、日本界面活性劑(Nihon Surfactant)工業股份有限公司等的聚氧乙烯硬脂酸三酸甘油脂、聚山梨酸酯 80(polysorbate80)(例如TO-10MV，曰本界面活性劑工業股份有限公司等的單油酸聚氧乙烯山梨醇脂肪酸，聚氧乙稀聚氧丙稀欲段聚合物(polyoxyethylene polyoxypropylene block polymer)、保麗視明（poloxamine)(例如， TETRONIC1107，巴斯夫曰本股份有限公司(BASF Japan Ltd.)等。各種組成物中，除了上述成分以外，可使用消毒劑、防腐劑、酵素、緩衝劑、安定劑、等滲透壓化劑(isotonizing agent)、助溶劑，清涼化劑、黏稠化劑等，可單獨使用1 種或併用2種以上。具體而言，消毒劑包括：鹽酸聚六甲撑雙胍、泊利氯胺(polidronium chloride)等。P方腐劑包括：氯化苄烧銨 (benzalkonium chloride)、氯化録躐基°比咬(cetylpyridinium chloride)、己二烯酸、己二烯酸鉀、對經基安息香酸甲醋 (para-hydroxymethyl benzonate)、對經基安息香酸乙 g旨、對羥基安息香酸丙酯、對羥基安息香酸丁酯等。酵素包括：胰蛋白酶、胰凝乳蛋白酶、胰酶、木瓜酶、膠原蛋白晦、鳳梨酵素(bromelian)、氨基肽酶、麴菌(aspergillo) ·肽酶、鏈黴蛋白酶E (pronaseE)、離散酶(dispase)、枯草桿菌蛋白 S# A、枯草桿菌蛋白酶b、脂酶、葡萄糖酶、mutanaze、 α "氣粉酶、聚葡萄糖酶。緩衝劑包括：碗酸二氫鈉、磷酸氫二鈉、檸檬酸、檸檬酸鈉，碳酸氳鈉、碳酸鈉、L-天 21 200536867 15195pif.doc 冬氨酸鉀、ε -氨基癸酸（ε _aminocapric acid)、麩胺酸鈉等。安定劑包括·· α-環糊精，乙二胺四乙酸鈉、亞硫酸氫納、硫代硫酸鈉等。等滲透壓化劑包括··氨基乙磺酸、氯化鉀、氯化納、氣化|弓、甘油、葡萄糖、甘露醇(D_mannit〇1) 等。溶解化劑包括··乙醇、尿素、丙二醇、macr〇g〇l4_ 等聚乙二醇、單乙醇胺等。清涼化劑包括··茴香油、dl_樟腦液、香葉醇（geraniol)、薄荷油、佛手油、d_龍腦 (d-bomeol)、1-薄荷腦、由加利樹油等。黏稠化劑包括··軟月素硫西夂納(sodium chondroitin sulfate)、玻尿酸及其鹽類、右旋糖酐(deXtran)70、羥基纖維素、聚乙二醇、聚乙烯吡咯細等。同時，可視需要而各個單獨使们種或適宜地組合使用2種以上的低級酒精、抗㈣、色素及香料等。特別是，作為醫療用具等之材料的表面，如玻璃、陶兗、不鏽鋼、塑料等的硬表面、毛髮、纖維等的軟表面、凝膠表面及隱魏絲面，這些原本私會被生物衍生物質例如取典型之蛋白質所附著，而使材料的生物適合性惡化’如將含有本發明高分子化合物之組成物用於這些材料的表面時，具有能夠摻配水溶性高分子化合物的優點。別應用於隱形輯表面時，II著搭配本發明的高分子化人物和水溶性高分子化合物，例如，可減少觀時的雜: 更有效地防止目標物的破損。 τIt is also preferable that the co-hydrate is a random copolymer (rand copolymer) or a block prostitute. A > If the polymerization reaction is performed by solution polymerization, for example, water, methanol-ethanol, isopropyl alcohol, lower alcohols, benzene, xylene, xylene,%, hexane, hexane, etc. Various organic solvents such as organic compounds, acetic acid, ethyl acetate, acetone, butanone and the like are used as solvents. The polymerization concentration is not specifically limited, but it is usually preferred to perform polymerization at 1G to 5G f%. As the polymerization initiator, for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, benzene peroxide __ 18 200536867 15195pif.doc per〇xlde), and laurel oxide ( lauroyl peroxide), azo compounds such as cumene hydroperoxide, hydroperoxide, azobisisobutyronitrile, and the like. The concentration of the polymerization starter is usually 0. to the total amount of monomers used! 〇Molar% is preferred. In order to limit the molecular weight, it is also preferable to use a chain shifting agent such as alkyl mercaptan, a polymerization accelerator such as a Lewis acid compound, and a pH adjusting agent such as phosphoric acid, citric acid, tartaric acid, and lactic acid. The polymerization temperature can be appropriately selected according to the solvent and polymerization initiator used, but it is usually preferably room temperature to 150 ° C. Low molecular weight impurities such as residual monomers contained in the obtained polymer compound can be removed by treatment with activated carbon, membrane filtration, dialysis membrane, etc., and prepared. -In general, activated carbon can be used such as wood, coal, or husk shells after being activated by Sao or radon gas. As for the shape of activated carbon, there are powdery and broken forms such as "fibrous" and there is no particular limitation. . As the material of the ultrafiltration membrane, polysulfone (polysulfone), polyethersulfone (polyethersulfbne), poly (vinylidene fluoride) (Takimachi Waki-shaped base, ㈣, cellulose acetate, and fox fiber material) can be used. As for the thin impurities, there are no particular limitations on flat membranes, hollow fibers, etc. * Materials used as medical appliances, such as hard surfaces, hair, fibers, etc. of glass, tincture, steel, plastic, etc. Soft surfaces, gel surfaces, and invisible eyes, the surface is 'worried' and may be attached by biological derivatives such as the most typical proteins, which deteriorates the biological suitability of these materials. The polymer compound for preventing white matter adhesion of the present invention, It can be treated with low concentration or short time and has excellent ability to prevent protein adhesion. This polymer compound is adsorbed on ^ 19 200536867 15195pif.doc, these surfaces (the aforementioned medical equipment materials) can impart antifouling properties to the surface. It is not easily washed away when washing with water, and can be used on antifouling compositions. Not only that, it also imparts antifouling properties while washing the target object, even in the flushing process accompanying washing with water ,by The polymer will be washed away and adsorbed on the target surface to show its antifouling property: it can be used as a flushing antifouling agent composition. At the same time, the composition containing the polymer compound for preventing protein adhesion of the present invention, Due to the above characteristics, it is suitable as an ophthalmic composition ^, especially suitable for contact lenses. Ophthalmic compositions include: general eyedrops, antibacterial eyedrops, artificial tears, contact lens packaging liquid, eyewash, etc. Contact lenses The composition includes, in particular, a treatment solution for contact lenses, a rinsing solution, a preservation solution, a rinsing solution, a rinsing disinfection solution, etc. The content of the polymer compound of the present invention in each of the above-mentioned compositions t, although not particularly The limit is-in general, 0. to 20% by mass of each composition, preferably 1 to 2% by mass. More preferably, the content of the polymer compound is too small, so it cannot be fully developed. (Protein attachment) If there are too many, the formulation will be designed. When various components contain the polymer compound of the present invention, its use may be used alone or in combination. 2) ^ Low-molecular-weight interface: ：: 里 == Includes: lignoxanthate, ammonium sulfate polyoxyethylene ^ alkyl polylactic acid ether, fatty acid diethanol amidamine, N-alkyienebet—, polyoxyethylation hardened sesame oil 20 20053 noodles C HCO-60, polyoxyethylene stearic acid triglyceride, polysorbate 80 (such as TO-10MV, Japanese surfactant) Industrial oleic acid polyoxyethylene sorbitol fatty acid, polyoxyethylene polyoxypropylene block polymer, poloxamine (for example, TETRONIC 1107, BASF Japan Corporation (BASF Japan Ltd.), etc. In various compositions, in addition to the above components, disinfectants, preservatives, enzymes, buffers, stabilizers, isotonizing agents, solubilizers, cooling agents, thickeners, etc. Use 1 type or 2 or more types together. Specifically, disinfectants include polyhexamethylene hydrochloride, poridronium chloride, and the like. The P-preservatives include: benzalconium chloride, cetylpyridinium chloride, adiponic acid, potassium adipate, para-hydroxymethyl benzonate, paraben Ethyl benzoate, propyl p-hydroxybenzoate, butyl p-benzoate and the like. Enzymes include: Trypsin, chymotrypsin, trypsin, papaya, collagen, bromelian, aminopeptidase, aspergillo, peptidase, pronaseE, discrete enzyme (dispase), subtilisin protein S # A, subtilisin b, lipase, glucosidase, mutanaze, α " aerosol, polyglucose. Buffering agents include: sodium dibasic acid, disodium hydrogen phosphate, citric acid, sodium citrate, sodium carbonate, sodium carbonate, L-day 21 200536867 15195pif.doc potassium aspartate, ε-aminocapric acid (ε_aminocapric acid), sodium glutamate, and the like. Stabilizers include α-cyclodextrin, sodium ethylenediamine tetraacetate, sodium bisulfite, sodium thiosulfate, and the like. Isotonic pressure agents include aminoethanesulfonic acid, potassium chloride, sodium chloride, gasification | bow, glycerol, glucose, mannitol (D_mannit〇1), and the like. The solubilizing agents include polyethylene glycols such as ethanol, urea, propylene glycol, and macromolecules, and monoethanolamine. Cooling agents include: fennel oil, dl_camphora solution, geraniol, peppermint oil, bergamot oil, d-bomeol, 1-menthol, yuca oil, and the like. Viscosity agents include: Sodium chondroitin sulfate, hyaluronic acid and its salts, dextran 70, hydroxycellulose, polyethylene glycol, polyvinylpyrrole, and the like. At the same time, if necessary, each of them may be used alone or in a suitable combination of two or more types of lower alcohol, anti-pimple, pigment, and flavor. In particular, the surfaces used as materials for medical appliances, such as hard surfaces such as glass, ceramics, stainless steel, and plastic, soft surfaces such as hair, fibers, gel surfaces, and cryptic silk surfaces, were originally biologically derived. For example, a substance is attached to a typical protein, thereby deteriorating the biocompatibility of the material. For example, when a composition containing the polymer compound of the present invention is used on the surface of these materials, it has the advantage of being able to incorporate a water-soluble polymer compound. When it is not applied to the surface of the invisibility series, II can be combined with the polymerized human and water-soluble polymer compound of the present invention, for example, it can reduce the obscuration of observation: more effectively prevent the damage of the target. τ

水溶性高分子化合物包括：經基纖維素、經基丙基纖維素、經基乙基纖維素、曱基纖維素等的纖維古分子化合物、聚乙烯醇、聚乙烯鱗細、羧基乙稀系S 22 200536867 15195pif.doc 合物荨的聚乙稀系咼分子化合物、軟骨素硫酸鈉、玻尿酸等的黏多醣類(mucopolysaccharides)、聚乙二醇、右旋糖酐專。其中，較佳的水溶性高分子化合物為纖維素系高分子化合物、聚乙烯系高分子化合物、聚乙二醇、玻尿酸，特別佳的化合物是羥基丙基曱基纖維素、羥基乙基纖維素、聚乙稀醇、聚乙烯Π比略烧酮、聚乙二醇、玻尿酸。上述水溶性高分子化合物的摻配量並沒有特別限制，但，一般而言，佔全體組成物之0 0001〜20質量％，較佳，0·001〜10質量％，更佳為〇 005〜5質量％。若水溶性 π分子化合物的摻配量太少，會因為擦洗目標物時的摩 $，可能會有損壞目標物的情形，摻配量若太多，黏度變得過高，會產生製劑設計上的限制。對於本發明各組成物的劑型(pharmaceutical f〇rm)、製作方去、使用方法，並無特別限定，可依照各劑型的習用方法調製，作為各組成物通常的劑型，並且依據各劑型一般的使用方法，以一般的使用量，即可發揮出色的防污性、洗淨防污性。再者，搭配本發明的高分子化合物調製上述各種組時，若調製水性組成物的話，在表面處理後即使用水沖洗，此防污劑組成物亦能賦與防污性，並且，在以水、、中 3淨程序巾，上述高分子化合物不會因沖洗而脫離，有 ^成分會吸陳目標面上，能得射賦與出色防污洗性防污劑組成物。 Τ 實施例 23 200536867 15195pif.doc 以下，雖以所表示的實驗例以及比較例說明本發明，但本發明並不限制於此些例子。 [實驗例1] 安裝有冷卻回流管、滴下漏斗、溫度計、氮氣引進管及攪拌裝置的可分離式燒瓶中，置入乙醇200g，一邊擾摔一邊導入氮氣，加熱至78°C，以3小時的時間連續加入甲基丙烯酸二曱胺基乙酯（以下簡稱DM)40.1g、曱基丙稀酸甲酉曰（以下間稱MMA)44.7g ’乙稀σ比π各烧酮（以下簡稱 VP)65.2g(總單體量中，DM含量=27質量％、總單體量中的MMA含量=30質量％、總單體量中的VP含量=43質量 %)以及乙醇35g的混合溶液，與2,2-(偶氮二(2-甲基丁腈))0.78g以及乙醇115g的混合溶液，再持續加熱3小時，得到如表1所示組成的實驗例1高分子化合物（共聚物）。 [實驗例2〜實驗例25] 除了將早體種類、播配比例換成依表1所示之組成之外，以實驗例1中所述相同的方法，可得如表1所示組成的實驗例2〜實驗例25之南分子化合物。 [實驗例26] 安裝有冷卻回流管、滴下漏斗、溫度計、氮氣引進管及攪拌裝置的可分離式燒瓶中，置入乙醇120g，一邊攪拌一邊導入氮氣，加熱至78°C，以2小時的時間連續加入 DM 11.5g、MMA 25.7g、VP 42.4g、甲氧聚單甲基丙烯酸乙二醋（methoxy poly ethyleneglycol monomethacrylate)(聚Water-soluble polymer compounds include: cellulose ancient compounds such as cellulose based, cellulose based propyl cellulose, cellulose based ethyl acetate, cellulose based, etc., polyvinyl alcohol, polyethylene scales, and carboxy vinyl S 22 200536867 15195pif.doc Polyethylene fluorene molecular compounds of the compound net, mucopolysaccharides such as sodium chondroitin sulfate, hyaluronic acid, polyethylene glycol, and dextran. Among them, preferred water-soluble polymer compounds are cellulose-based polymer compounds, polyethylene-based polymer compounds, polyethylene glycol, and hyaluronic acid. Particularly preferred compounds are hydroxypropylfluorenyl cellulose and hydroxyethyl cellulose. , Polyvinyl alcohol, Polyethylene, Biluozone, Polyethylene glycol, Hyaluronic acid. The compounding amount of the water-soluble polymer compound is not particularly limited, but generally, it accounts for 0 0001 to 20% by mass of the entire composition, preferably, 0.001 to 10% by mass, and more preferably 0005 to 5 mass%. If the compounding amount of the water-soluble π molecular compound is too small, the target object may be damaged due to the friction when scrubbing the target object. If the compounding amount is too large, the viscosity will become too high, which will cause the formulation design. limit. There are no particular restrictions on the dosage form (pharmaceutical form), preparation method, and method of use of each composition of the present invention, and it can be prepared according to the customary method of each dosage form, as the usual dosage form of each composition, and according to the general of each dosage form Using method, it can show excellent antifouling property and washing antifouling property in normal usage. In addition, when the above-mentioned various groups are prepared with the polymer compound of the present invention, if an aqueous composition is prepared, the antifouling agent composition can impart antifouling properties even after rinsing with water after surface treatment. The cleansing towels of the middle and the third, the above-mentioned polymer compounds will not be detached by rinsing, and some ingredients will absorb the target surface, and can be shot to impart excellent antifouling and antifouling composition. Example 23 200536867 15195pif.doc Hereinafter, although the present invention will be described using the experimental examples and comparative examples shown, the present invention is not limited to these examples. [Experimental Example 1] A separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen introduction tube, and a stirring device was charged with 200 g of ethanol, and nitrogen was introduced while being stirred, and heated to 78 ° C for 3 hours. 40.1 g of diethylaminoethyl methacrylate (hereinafter referred to as DM) and 44.7 g of methyl ethyl methacrylate (hereinafter referred to as MMA) were continuously added over a period of time. ) 65.2g (DM content = 27% by mass in total monomer amount, MMA content = 30% by mass in total monomer amount, VP content = 43% by mass in total monomer amount) and 35g of ethanol mixed solution, A mixed solution of 0.78 g of 2,2- (azobis (2-methylbutyronitrile)) and 115 g of ethanol was further heated for 3 hours to obtain a polymer compound (copolymer) of Experimental Example 1 having the composition shown in Table 1. ). [Experimental Example 2 to Experimental Example 25] The composition shown in Table 1 can be obtained by the same method described in Experimental Example 1 except that the types of early bodies and the distribution ratio are changed to the composition shown in Table 1. Experimental Example 2 to Experimental Example 25 South molecular compounds. [Experiment Example 26] A separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen introduction tube, and a stirring device was placed in 120 g of ethanol, and nitrogen was introduced while stirring, and heated to 78 ° C for 2 hours. Continuously add DM 11.5g, MMA 25.7g, VP 42.4g, methoxy poly ethyleneglycol monomethacrylate (poly

乙烯平均=9)(以下簡稱M-90G簡稱)10.3g(總單體量中，DM 24 2〇〇536867〇c 含量=12.8質量％、總單體量中的MMA含量=28·6質量％、總單體量中的VP含量=47.1質量％、總單體量中的M-90G 含量= 11.5質量。/〇)以及乙醇41g的混合溶液，與2,2-(偶氮二(2-曱基丁腈))〇.71g以及乙醇49.lg的混合溶液，再持續加熱4小時’經聚合反應得到共聚物。欲使共聚物之固形伤為2吳虿％ ’添加離子交換水並同時間添加im〇i/L之氣化氳水溶液以調整pH至6，裝入再生纖維製之透析管 (UC36-32-100，Viskase Companies，Inc·製），一面更換離子交換水，一面進行為期一週的透析。將透析管内的含有高分子化合物之水溶液以冷凍乾燥機乾燥，得到如表3所示組成的實驗例26之高分子化合物(精製共聚物）。 [實驗例27〜實驗例62] 除了將單體種類、摻配比例換成依表3所示之組成之外，以實驗例26中所述相同的方法，可得如表3所示組成的實驗例27〜實驗例62之高分子化合物。 [比較例1，2] 將下列市售之高分子化合物作為比較例1、比較例2 進行比較。比較例1 :聚乙烯17比略烧酮（聚乙稀吼略烧酿j K-90):巴斯夫曰本股份有限公司製。比較例2 :聚丙烯酸(Carbopol-934P):諾譽化工(Noveon) 製。 [比較例3〜比較例9] 除了將單體種類、摻配比例換成依表2所示之組成之 25Ethylene average = 9) (hereinafter abbreviated as M-90G abbreviation) 10.3 g (of the total monomer amount, the content of DM 24 200536867〇c = 12.8% by mass, and the MMA content of the total monomer amount = 28.6% by mass , VP content in total monomer amount = 47.1% by mass, M-90G content in total monomer amount = 11.5% by mass, and 41 g of ethanol mixed solution with 2,2- (azobis (2- Fluorenyl butyronitrile)) 0.71g and a mixed solution of 49.lg of ethanol, and continued to heat for 4 hours to obtain a copolymer through polymerization. To make the copolymer's solid damage 2%, add ion-exchanged water and simultaneously add imio / L gasified hydrazone solution at the same time to adjust the pH to 6, and insert it into a dialysis tube (UC36-32- 100, manufactured by Viskase Companies, Inc.), while changing ion-exchanged water, dialysis was performed for one week. The aqueous solution containing the high molecular compound in the dialysis tube was dried with a freeze dryer to obtain the high molecular compound (refined copolymer) of Experimental Example 26 having the composition shown in Table 3. [Experimental Example 27 to Experimental Example 62] Except changing the monomer type and blending ratio to the composition shown in Table 3, the same method as described in Experimental Example 26 was used to obtain the composition shown in Table 3. Polymer compounds of Experimental Examples 27 to 62. [Comparative Examples 1, 2] The following commercially available polymer compounds were compared as Comparative Example 1 and Comparative Example 2. Comparative Example 1: Polyethylene 17 Biluo Ketone (Polyethylene Diluo Jj-90): manufactured by BASF Japan Chemical Co., Ltd. Comparative Example 2: Polyacrylic acid (Carbopol-934P): manufactured by Noveon Chemical. [Comparative Example 3 to Comparative Example 9] Except changing the monomer type and blending ratio to 25 as shown in Table 2

20053 總L 外’以實驗例1中所述相同的方法，可得如表2所示組成的比較例3〜比較例9之高分子化合物。將上述實驗例1〜實驗例25以及比較例1〜比較例9之高分子化合物，以〇·〇5質量％水溶液，依照下述方法進行防污性1、防污性2以及防污性3之評估。同時，關於耐久性之評估，將上述實驗例1〜實驗例25之共聚物以0β1 貝里之水〉谷液、比較例1〜比較例9以1%質量之水溶液，依據下述方法進行評估。並且，將上述實驗例26〜實驗例 62以及比較例1〜比較例9之高分子化合物以〇〇5質量％之水溶液，依據下述方法進行防污性4、洗淨性之評價。其結果並列於表1〜表4。 <防污性1之評估方法> 於室所旦 τ胼不鏽鋼板（l〇cm(公分)xi〇cm)在濃度〇〇5 質量％高分子化合物溶液或分散液5GGmL中浸潰丨小時。取^鏽鋼板朗離子交換水清洗，用清料軟的紙吸收 ί 蛋白質之一的纖維蛋白原（fibrin〇gen)〇.6〇g溶於離。厂1 Γ主5〇〇mL中作為浸潰液浸泡不鏽鋼板，然後以30 水八。用1^溫震蘯°取出獨鋼板’以清淨錄的紙吸掉纖(ninhydrin)指示崎附著於不鏽鋼板上的準將顯色的狀態依據下列評估基準評估。讓不鏽鋼板不接觸纖維劑時的著色狀態）不 5 ·完全沒有染上顏色(顏色相當於蛋白原溶液而使用茚滿三酮指 4:幾乎沒有染上 26 200536867 15195pif.doc 3 :輕微地染上 2 :相當程度地染上 1 :極度地染上(不鏽鋼板不以高分子化合物溶液處理而接觸纖維蛋白原溶液’顏色相當於這樣的不鏽鋼板以節滿三酮指示劑染色時之著色狀態） <防污性2之評估方法> AA(乙烯甲基丙浠酸聚合物）樹脂（i〇cm X 1 〇cm)(二井.杜邦聚合化學股份有限公司①加i Polychemkals C。· Ud.)製)濃度0.05 f量％之高分子化合物溶液或分散液5GGmL，在室溫中浸潰M、時。取& EMAA 樹脂f以離子交換水清洗，用清淨柔軟的紙吸掉水分，將蛋貝之的蛋白;谷囷S#(eggwhite lysozyme)(和光純荜股份有限公司製)〇.6〇g溶於離子交換水5〇〇祉中作為浸潰液浸泡EMAA樹脂，然後以3〇〇C !小時加溫震蘯。取出 EMAA樹脂’以清淨柔軟的紙吸掉水分 ====：彻_故縣顯色的 <評估基準> ^ ί全沒㈣上純(純相#於不讓EMAA樹脂接觸蛋白溶菌酶溶液而使料滿三_示劑時的著色狀 4:幾乎沒有染上〜輕微地染上相當程度地染上極度地木上(EMAA樹脂不以高分子化合物溶液處理而 27 2 200536867 15195pif.doc 接觸蛋白溶菌酶溶液，顏色相當於這樣的emaa樹脂以節滿二酮指示劑染色時之著色狀態） <防污性3之評估方法> ϋ述防污性2評估方法中，除了以軟式隱形眼鏡_ (母日拋棄型（1DAY ACUVUE)，嬌生(灿__地ns〇n)公司製)替代EMAA樹脂，並以〇.〇5質量％紅勞素㈣水溶液作為溶_的染色劑之外，根據上述防污性2评價方法同樣的方法，_著於軟式隱觀鏡上的蛋白溶菌酶染色，並將顯色的狀態依據下列評估基準評估。 <評估基準> ° 5 ： 4 疋王/又有★上顏色(顏色相t料讓軟式隱形眼鏡接觸蛋白溶菌酶溶液而使用紅螢素水溶液時的著色狀態 *幾乎沒有染上 ~ 2 輕微地染上相當程度地染上， 1 :極度地染上(軟式隱魏鏡不以高分子化合物溶液處理而接觸蛋自溶_料，純相t於賴的軟式隱形眼鏡以紅螢素水溶液染色時之著色狀態） <耐久性之評估方法> 將幸人式隱形目艮鏡(每日拋棄型，嬌生公司製)在上述實驗例1〜貫驗例25以及比較例1〜比較例9之高分子化合物溶液(實驗例1〜實驗例25之高分子化合物01 f量％水溶液，^交例K比較例9之高分子化合物i 〇質量％)5〇_ 中以室溫浸潰1小時。取出軟式隱舰鏡並崎子交換水 28 200536867 15195pif.doc >月冼川π $永双的紙吸桿水分。將蛋白質之一的蛋白、六菌酶（和光純藥股份有限公司製)G 6Gg溶於離子交換= 5〇〇ηΛ中作為浸潰液浸泡軟式隱形眼鏡，然後以3〇它15 小時以及3G小時加溫震蘯。取出軟式隱形眼鏡，以清軟的紙吸掉水分。針對此軟式隱形眼鏡，料滿三綱^ =將附著於鏡片上的溶菌酶染色，並將顯色的 ^ 列評估基準評估。爆卜 <評估基準> k白 1全ϋ紅顏色(顏色相#料讓軟式_眼鏡接觸，谷囷谷液而使用茚滿三酮指示劑時的著色狀熊） 4 :幾乎沒有染上輕微地染上 2 相當程度地染上而:度= 染上(軟式隱形眼鏡不以高分子化合物溶液處理以節ί =^_驗，顏色相#於這_軟式隱形眼鏡 Ρ滿二酮私示劑染色時之著色狀態） <防污性4之評估方法> 將軟式隱形眼鏡(每日拋棄型，嬌生公司赞驗^ 26〜實驗例62以及比較例1〜比較例9之2 化合物濃度G.G5質量％，氯化二f i 交溫，4小時。取出軟式隱形眼鏡並以離子浸漬心=柔軟的紙吸掉水分。將軟式隱形眼鏡質量。/〇、牛血Ϊ二，(和光純樂股份有限公司製)0.12 牛血〉月蛋白素0.388質量％ (fracti〇n_v，曰本 29 200536867 15195pif.doc20053 Total L outer 'In the same manner as described in Experimental Example 1, polymer compounds of Comparative Examples 3 to 9 having the compositions shown in Table 2 were obtained. The polymer compounds of Experimental Example 1 to Experimental Example 25 and Comparative Example 1 to Comparative Example 9 described above were subjected to antifouling property 1, antifouling property 2 and antifouling property 3 in a 0.05% by mass aqueous solution according to the following method. Evaluation. At the same time, regarding the evaluation of durability, the copolymers of Experimental Example 1 to Experimental Example 25 above were evaluated as 0β1 water of berry> Valley fluid, and Comparative Example 1 to Comparative Example 9 were evaluated by the following method with a 1% mass aqueous solution. . In addition, the polymer compounds of Experimental Examples 26 to 62 and Comparative Examples 1 to 9 were subjected to a 0.05% by mass aqueous solution, and the antifouling properties 4 and the detergency were evaluated according to the following methods. The results are shown in Tables 1 to 4. < Evaluation method of antifouling property 1 > immersion in a τ 胼 stainless steel plate (10 cm (cm) x 0 cm) at a concentration of 0.05 mass% polymer compound solution or dispersion 5GGmL for 1 hour . The stainless steel plate was washed with ion-exchanged water, and the soft fiber paper was used to absorb fibrinogen (0.60 g), which was one of the proteins, and dissolved in ion. Plant 1 Γ main 500mL immersed the stainless steel plate as an immersion solution, and then with 30 water eight. The single steel plate was taken out with 1 ^ temperature shock 蘯 ° and the recorded paper was sucked off. The ninhydrin indicator was attached to the stainless steel plate. The state of color development was evaluated according to the following evaluation criteria. The coloring state when the stainless steel plate is not in contact with the fiber agent) No 5 · No coloring at all (color is equivalent to the proteinogen solution and using indanetrione finger 4: Hardly stained 26 200536867 15195pif.doc 3: Slightly stained Upper 2: Stained to a considerable extent 1: Extremely stained (Stainless steel plate is not treated with a polymer compound solution and contacts a fibrinogen solution. The color is equivalent to the coloring state of such a stainless steel plate when dyed with triketone indicators ) &Lt; Evaluation method of antifouling property 2 > AA (ethylene methylpropionic acid polymer) resin (icm x 100cm) (Nikai. DuPont Polymer Chemical Co., Ltd. ① plus i Polychemkals C. · Ud .)) 5GGmL of a polymer compound solution or dispersion with a concentration of 0.05 f%, and immersed at room temperature for M hours. Take & EMAA resin f and wash with ion-exchanged water, absorb the moisture with a clean and soft paper, and remove the egg whites from the egg whites; gluten S # (eggwhite lysozyme) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.60 g Soluble EMAA resin in ion-exchanged water at 500 ℃ as an impregnation solution, and then heated at 300 ° C for 1 hour. Take out the EMAA resin 'and absorb the moisture with a clean and soft paper ====: Toxian County ’s color < Evaluation Criteria > ^ 全全㈣上上纯 (纯相 # 于不 EMAEMA resin contact with protein lysozyme Solution to make the material full 3 _ coloring state when the indicator 4: almost no staining ~ slightly stained to a considerable extent on extreme wood (EMAA resin is not treated with a polymer compound solution and 27 2 200536867 15195 pif.doc When contacted with a protein lysozyme solution, the color is equivalent to the coloring state of such an emaa resin when stained with a diketone indicator) < Evaluation method of antifouling property 3 > Contact lens_ (1DAY ACUVUE, manufactured by Canson Co., Ltd.) instead of EMAA resin, and 0.05% by mass red laurin solution is used as a dissolving dye In addition, according to the same method as the above-mentioned evaluation method of antifouling property 2, the protein lysozyme staining on a soft spectoscope was used, and the state of color development was evaluated according to the following evaluation criteria. &Lt; Evaluation criteria > ° 5 : 4 疋王 / Are ★ color (color phase t material makes soft contact lenses Coloring state when using a luciferin aqueous solution when contacting a protein lysozyme solution * Almost no staining ~ 2 Slightly stained to a considerable extent, 1: Extremely stained (soft-type Weiwei mirror is not treated with a polymer compound solution While contacting the egg, the soft contact lenses in pure phase are colored when the red fluorescein solution is dyed) < Evaluation method of durability > Fortunate contact lenses (daily disposable, (Made by Johnson Products) In the above-mentioned experimental examples 1 to 25, and the comparative examples 1 to 9 of the polymer compound solution (the experimental examples 1 to 25 of the polymer compound 01 f% aqueous solution, ^ Example K The polymer compound i of Comparative Example 9 was immersed at room temperature in 50% for 1 hour. The soft-type hidden ship mirror was taken out and exchanged with water. 28 200536867 15195pif.doc > 月冼川 π $ 永双的纸Suction rod water. Soluble soft contact lenses by dissolving one of the proteins, six bacterial enzymes (manufactured by Wako Pure Chemical Industries, Ltd.) G 6Gg in ion exchange = 500 Λ Λ, and soaking the soft contact lenses with 15 Hours and 3G hours of heating shock. Take out the soft cover Glasses, absorb moisture with soft paper. For this soft contact lens, fill in three classes ^ = stain the lysozyme attached to the lens, and evaluate the color of the ^ column to evaluate the evaluation criteria. Pop < evaluation criteria > k white 1 full red color (color phase # material let soft contact _ glasses, glutinous gluten solution when using indan trione indicator coloring bear) 4: almost no stain slightly stained 2 considerable Degree of dyeing: Degree = dyeing (soft contact lenses are not treated with a polymer compound solution to save ^ = 验，色相 # 于此 _ soft contact lenses are dyed with a dione private display agent. ) &Lt; Evaluation method of antifouling property 4 > Soft contact lenses (daily discard type, praised by Johnson & Johnson ^ 26 ~ Experiment Example 62 and Comparative Example 1 ~ Comparative Example 9-2 2 Compound concentration G.G5 mass% , Dichloride temperature, 4 hours. Take out the soft contact lens and absorb the moisture with ion-impregnated core = soft paper. The quality of soft contact lenses. / 〇, bovine blood Ϊ 二, (made by Wako Pure Music Co., Ltd.) 0.12 bovine blood> moon protein 0.388% by mass (fracti〇n_v, Japanese 29 200536867 15195pif.doc

Nacala! Tesque 公司製）、7 _球蛋白〇 16 cohn F 2 ^ ^ Nacalai Tesque, f} . ； 9 以及鱗酸氫二納〇.〇45質量％的蛋白溶 .、里。以371丨*時加溫震蘯。取出軟式夜2ml，後軟的紙吸掉水分。針對此軟式隱形眼鏡，二^ =柔列評估基準評估。囷^^色挪顯色的狀態依據下 <評估基準> 5 70王，又有染上顏色（顏色相當於不讓軟式障形目ρ铲桩鎚蛋白溶_溶㈣接觸 4 :幾乎沒有染上輕微地染上 2 相當程度地染上而=度=1"；(軟式隱形輯不以高分子化合物溶液處理而接觸蛋白〉谷卤酶溶液，顏多相以節滿三_示繼色日讀的軟式隱形眼鏡 <洗淨性之評估方法> 〜換皮ΐί式隱形目f鏡(每日抛棄型，嬌生公_以離子交产於=帛/月=柔軟的紙吸掉水分。將軟式隱形眼鏡浸 f 了了蛋白/谷菌酶(和光純藥股份有限公司製)〇. 12質里/。、牛血清蛋白素0.388質量％伽etiGn V，日本Nacaiai esque公司製）个球蛋白讓f #%(bGvine，— F 2，々本NaCalai Tesque&司製）、氣化鈉 0.9質量％以及磷酸里 45 f量％的蛋白溶®酶溶液2ml，然後以37°C 1 30 200536867 15195pif.doc 小時加溫震盪。取&軟式隱魏鏡，以清淨綠的紙吸掉水分後，在此軟性隱形眼鏡的表面上個別滴下3ml之上述實驗例26〜實驗例62以及比較例丨〜比較例9之高分子化。合物溶液(高分子化合物濃度〇〇5質量％、氯化鈉〇.9質量 %)(每一鏡片只滴入一種高分子化合物溶液），並—面= 洗。針對此軟式隱形眼鏡’用節滿三嗣指示劑將附著於梦二上的溶菌酶染色，並將顯色的狀態依據下列評估基準= <評估基準>(Produced by Nacala! Tesque), 7-globulin 〇 16 cohn F 2 ^ ^ Nacalai Tesque, f}. 9 and dinazine hydrogen tetrahydrochloride 0.45% by mass protein. With 371 丨 *, the temperature increases. Take out the soft type 2ml, and then the soft paper absorbs moisture. For this soft contact lens, two ^ = flexible evaluation benchmark evaluation.囷 ^^ The state of the color development is based on the < Evaluation Criteria > 5 70 Kings, and there is dyeing (the color is equivalent to not dissolving the soft obstacles ρ shovel hammer protein soluble _ soluble ㈣ contact 4: almost no Slightly stained with 2 stained to a considerable extent and = degree = 1 "; (soft invisible series does not treat with polymer compound solution and contacts protein> glutenase solution, Yan multi-phase in order to save three _ shows the following color Daily-reading soft contact lenses < Evaluation method of detergency > ~ Change skin ΐ contact lenses f (daily discard type, Jiao Shenggong _ produced by ion exchange = 帛 / 月 = soft paper suck up Moisture. The soft contact lens was dipped in protein / glutaminase (manufactured by Wako Pure Chemicals Co., Ltd.) 0.112 mol / s, bovine serum protein 0.388% by mass, ethiGn V, manufactured by Nacaiai Esque, Japan. The globulin is 2 ml of f #% (bGvine, — F 2, Nakalai Tesque & Co., Ltd.), sodium mass 0.9% by mass, and 45 f% by mass of phosphate, and then at 37 ° C 1 30 200536867 15195pif.doc Hourly heating and shaking. Take & soft hidden Wei mirror, absorb water with clean green paper, 3 ml of the above-mentioned experimental example 26 to experimental example 62 and comparative example 丨 to comparative example 9 were dripped individually onto the surface of this soft contact lens. Compound solution (polymer compound concentration 0.05 mass%, sodium chloride. .9% by mass) (only one polymer compound solution is dripped into each lens), and the surface is washed. For this soft contact lens, the lysozyme attached to Mengji is stained with a full-three-dimensional indicator, and The state of color development is based on the following evaluation criteria = < Evaluation criteria >

鏡 4 完全沒錢上顏⑽貞色相當㈣制上所附著之蛋白質污物完全洗淨的狀態）料隱形眼幾乎沒有染上 “ 2 輕微地染上相當程度地染上 •極度地染上(顏色相當於使用過之敕著之蛋白質污物完全沒被去除的狀態）工眼鏡上所附Mirror 4 There is no money on the face. The color is pretty clean. The attached protein dirt is completely washed.) The contact lens is hardly stained. "2 Slightly stained. Slightly stained. Extremely stained ( The color is equivalent to the state that the used protein dirt has not been removed at all)

31 200536867 15195pif.doc 【表1】高分子化合物組成 (質量％) 重量平均分子量防污性 1 防污性 2 防污性 3 耐久性不錄鋼 EMAA 樹脂軟式隱形眼鏡 30 小時 15 小時 1 DM/MMA/VP=2 7/30/43 80,000 5 5 5 5 5 2 DM/MMA/VP=28/46/26 95,000 5 5 5 5 5 3 DM/MMA/VP=34/40/26 100,000 5 5 5 5 5 4 DM/MMA/VP=24/46/30 89,000 5 5 5 5 5 5 DMC/MMA/VP-2.5/27/70.5 78,000 4 4 5 5 5 6 DMC/EMA/VP=0<8/22/77.2 145,000 4 4 5 4 5 7 DM/MMA/BMA/VP=34/35/2/29 180,000 5 5 5 5 5 8 DM/DMC/MMA/VP 二 34/4/32/30 95,000 4 5 5 5 5 實驗例 9 DM/MMA/VP=50/26/24 120,000 4 5 5 5 5 10 DMC/MMA/VP=6.5/22.5/71 115,000 4 4 5 4 5 11 DM/DMC/MMA/VP=60/6.5/22.5/11 150,000 4 4 5 4 5 12 DM/DMC/EMA/BMAA/P=41/5.5/20/6.5/27 850,000 4 4 5 5 5 13 DM/MMA/VP=12/35/53 350,000 5 5 5 5 5 14 DM/MMA/VP=7/27/66 450,000 5 5 5 5 5 15 DM/MMA/VP=4/24/72 380,000 5 5 5 5 5 16 DM/MMA/VP=6/29/65 290,000 5 5 5 5 5 17 DMA/MMA/t-BMA/VP= 15/15/10/60 290,000 5 5 5 5 5 18 DMA/MMA/t-BMA/VP=25/10/14/51 310,000 5 5 5 5 5 19 DMA/MMA/t-BMA/VP=43/7/18/32 350,000 4 5 5 5 5 20 DMA/t-BMA/VP=55/25/20 350,000 4 4 5 5 5 21 DMAPAA/MMA/VP=7/28/65 275,000 5 5 5 5 5 22 DMAP AA/MM A/t-BMA/VP= 16/14/10/60 330,000 5 5 5 5 5 23 DMAP AA/MM A/t-BMA/VP=26/10/14/50 305,000 5 5 5 5 5 24 DMAPAA/MMA/t-BMA/VP=44/6/18/32 280,000 4 5 5 5 5 25 DMAPAA/t-BMA/VP^56/24/20 410,000 4 4 5 5 5 32 200536867 15195pif.doc 【表2】高分子化合物組成 (質量％) 重量平均分子虽防污性 1 防污性 2 防污性 3 耐久性不銹鋼 EMAA 樹脂軟式隱形眼鏡 30 小時 15 小時比較例 1 聚乙烯吡咯烷酮 (K-90) — 1 1 1 1 1 2 聚丙烯酸 — 1 1 1 1 1 3 DM/AA/MMA=25/70/5 95,000 2 1 1 1 1 4 DM/MAA/HEMA=0.1/35/64.9 70,000 2 1 1 1 1 5 MAA/AA=40/60 78,000 1 1 1 1 1 6 M-230G/AA 二 20/80 89,000 2 1 1 1 1 7 DMC/EMA/VP=0.8/22/77.2 2,000 2 1 2 1 1 8 DMC/MAA/MMA/VP=0.1/20/2/77.9 34,000 1 1 1 1 1 9 DMC/MAA/M-230G=15/82/3 22,000 1 1 1 1 1 33 200536867 15195pif.doc 表3】高分子化合物組成 (質量％) 重量平均分子量防污性 4 洗淨性 4 軟式隱形眼鏡軟式隱形眼鏡 26 DM/MMA/VP/M-90G=12.8/28.6/47.1/11.5 55,000 5 4 27 DM/MMA/VP/M-90G=6.5/23/58/12.5 48,000 5 4 28 DM/MMA/VP/M-90G=12.5/23/52.5/12 49,000 5 4 29 DM/MMA/VP/M-90G=25.5/22.5/40.5/11.5 52,000 5 3 30 DM/_A/VP/M-90G=9.8/3 L 3/41.4/17.5 58,000 5 4 31 DM/MMA/VP/M-90G=18/30.6/34.4/17 42,000 5 4 32 DM/MMA/VP/M-90G-6/38.2/33.1/22.7 48,000 5 3 33 DM/MMA/VP/M-90G=11^/37.5/28.4/22.3 51,000 5 4 34 DM/MMA/VP/M-90G=22^/36.3/19.3/21.6 60,000 5 4 35 DMAA4MA/VP/M-90G=14.7/28.7/45.1/11.5 42,000 5 4 36 DMAAlMA/VP/M-90G=6/23/58.7/12.3 53,000 5 4 37 DMA/MMA/VP/M-90G=12/23/53.3/11.7 49,000 5 4 38 DMAAtMA/VP/M-90G=25/22.5/41.2/11.3 53,000 5 3 39 DMA/MMA/VP/M-90G=9.4/31.1/42.2/17.3 55,000 5 4 40 DMAAlMA/VP/M-90G=17.6/30.3/35.3/16.8 48,000 5 4 41 DMAAlMA/VP/M-90G=5.7/38.1/33.2/2 3 57,000 5 4 42 DMA/MMA/VP/M-90G=11.3/37.8/28.6/22.3 46,000 5 4 43 DMAA4MA/VP/M-90G=22.1/36.2/20.4/21.3 51,000 5 4 44 DMC/MMA/VP/M-90G=6.7/22.7/58.5/12.1 59,000 5 3 實 45 DMC/MMA/VP/M-90G=3.2/23.6/55.6/17.6 61,000 4 4 驗 /rif 46 DMC/MMA/VP/M-90G=1.6/22.2/58.5/17.7 60,000 4 3 例 47 DM APM A/MM A/VP/M-90G=6.7/2 3 /58 /12.3 56,000 5 4 48 DMAPMA/MMA/VP/M-90G=12.6/23/52.2/12.2 42,000 5 4 49 DMAPMA/MMA/VP/M-90G=25.7/23.5/39/11.8 48,000 5 4 50 DMAPMA/MMA/VP/M-90G= 10/31.5/40.7/17.8 54,000 5 4 51 DMAPMA/MMA/VP/M-90G=18.3/30.9/33.6/17.2 57,000 5 4 52 DMAFMA/MMA/VP/M-90G=6.3/38.5/32.3/22.9 50,000 5 4 53 DM APM A/MMA/VP/M-90G= 12/3 7.8/27.6/22.6 59,000 5 4 54 DMAPMA/MMA/VP/M-90G 二23/36.6/18.6/21.8 53,000 5 4 55 DMAPAA/MMA/VP/M-90G=12.2/29.5/41.8/16.5 50,000 5 4 56 DM APAA/MMA/VP/M-90G=2 3.8/32.4/2 7.8/16.0 55,000 5 4 57 DMAPAA/MMA/VP/M-90G=23.6/24.5/36/15.9 50,000 5 3 58 DMAPAA/MMA/VP/M-90G=24.1/46.4/13.2/16.3 45,000 5 4 59 DMAPAA/MMA/VP/M-90G= 12.5/48/22.7/16.8 52,000 5 4 60 DMAPAA/MMA/VP/M-90G=6.4/48.9/27.6/17.1 54,000 5 4 61 DMAPAA/MMA/VP/M-90G=12.8/30.7/45/11.5 48,000 5 4 62 DMAPAA/MMA/VP/M-90G=22/38.2/28.5/11.3 50,000 5 331 200536867 15195pif.doc [Table 1] Polymer composition (% by mass) Weight average molecular weight Antifouling 1 Antifouling 2 Antifouling 3 Durable non-steel EMAA resin soft contact lenses 30 hours 15 hours 1 DM / MMA / VP = 2 7/30/43 80,000 5 5 5 5 5 2 DM / MMA / VP = 28/46/26 95,000 5 5 5 5 5 3 DM / MMA / VP = 34/40/26 100,000 5 5 5 5 5 4 DM / MMA / VP = 24/46/30 89,000 5 5 5 5 5 5 DMC / MMA / VP-2.5 / 27 / 70.5 78,000 4 4 5 5 5 6 DMC / EMA / VP = 0 < 8/22 / 77.2 145,000 4 4 5 4 5 7 DM / MMA / BMA / VP = 34/35/2/29 180,000 5 5 5 5 5 8 DM / DMC / MMA / VP II 34/4/32/30 95,000 4 5 5 5 5 Experimental example 9 DM / MMA / VP = 50/26/24 120,000 4 5 5 5 5 10 DMC / MMA / VP = 6.5 / 22.5 / 71 115,000 4 4 5 4 5 11 DM / DMC / MMA / VP = 60 / 6.5 / 22.5 / 11 150,000 4 4 5 4 5 12 DM / DMC / EMA / BMAA / P = 41 / 5.5 / 20 / 6.5 / 27 850,000 4 4 5 5 5 13 DM / MMA / VP = 12/35/53 350,000 5 5 5 5 5 14 DM / MMA / VP = 7/27/66 450,000 5 5 5 5 5 15 DM / MMA / VP = 4/24/72 380,000 5 5 5 5 5 16 DM / MMA / VP = 6 / 29/65 290,000 5 5 5 5 5 17 DMA / MMA / t-BMA / VP = 15/15/10/60 290,000 5 5 5 5 5 18 DMA / MMA / t-BMA / VP = 25/10/14 / 51 310,000 5 5 5 5 5 19 DMA / MMA / t-BMA / VP = 43/7/18/32 350,000 4 5 5 5 5 20 DMA / t-BMA / VP = 55/25/20 350,000 4 4 5 5 5 21 DMAPAA / MMA / VP = 7/28/65 275,000 5 5 5 5 5 22 DMAP AA / MM A / t-BMA / VP = 16/14/10/60 330,000 5 5 5 5 5 23 DMAP AA / MM A / t-BMA / VP = 26/10/14/50 305,000 5 5 5 5 5 24 DMAPAA / MMA / t-BMA / VP = 44/6/18/32 280,000 4 5 5 5 5 25 DMAPAA / t-BMA / VP ^ 56/24/20 410,000 4 4 5 5 5 32 200536867 15195pif.doc [Table 2] Composition of polymer compound (% by mass) Although the average molecular weight is antifouling 1 Antifouling 2 Antifouling 3 Durable stainless steel EMAA resin soft contact lens 30 hours 15 hours Comparative Example 1 Polyvinylpyrrolidone (K-90) — 1 1 1 1 1 2 Polyacrylic — 1 1 1 1 1 3 DM / AA / MMA = 25/70/5 95,000 2 1 1 1 1 4 DM / MAA / HEMA = 0.1 / 35 / 64.9 70,000 2 1 1 1 1 5 MAA / AA = 40/60 78,000 1 1 1 1 1 6 M-230G / AA 2 20/80 89,000 2 1 1 1 1 7 DMC / EMA / VP = 0.8 / 22 / 77.2 2,000 2 1 2 1 1 8 DMC / MAA / MMA / VP = 0.1 / 20/2 / 77.9 34,000 1 1 1 1 1 9 DMC / MAA / M-230G = 15/82/3 22,000 1 1 1 1 1 33 200536867 15195pif.doc Table 3】 Polymerization Material composition (mass%) Weight average molecular weight Antifouling property 4 Detergency 4 Soft contact lens Soft contact lens 26 DM / MMA / VP / M-90G = 12.8 / 28.6 / 47.1 / 11.5 55,000 5 4 27 DM / MMA / VP /M-90G=6.5/23/58/12.5 48,000 5 4 28 DM / MMA / VP / M-90G = 12.5 / 23 / 52.5 / 12 49,000 5 4 29 DM / MMA / VP / M-90G = 25.5 / 22.5 /40.5/11.5 52,000 5 3 30 DM / _A / VP / M-90G = 9.8 / 3 L 3 / 41.4 / 17.5 58,000 5 4 31 DM / MMA / VP / M-90G = 18 / 30.6 / 34.4 / 17 42,000 5 4 32 DM / MMA / VP / M-90G-6 / 38.2 / 33.1 / 22.7 48,000 5 3 33 DM / MMA / VP / M-90G = 11 ^ / 37.5 / 28.4 / 22.3 51,000 5 4 34 DM / MMA / VP /M-90G=22^/36.3/19.3/21.6 60,000 5 4 35 DMAA4MA / VP / M-90G = 14.7 / 28.7 / 45.1 / 11.5 42,000 5 4 36 DMAAlMA / VP / M-90G = 6/23 / 58.7 / 12.3 53,000 5 4 37 DMA / MMA / VP / M-90G = 12/23 / 53.3 / 11.7 49,000 5 4 38 DMAAtMA / VP / M-90G = 25 / 22.5 / 41.2 / 11.3 53,000 5 3 39 DMA / MMA / VP /M-90G=9.4/31.1/42.2/17.3 55,000 5 4 40 DMAAlMA / VP / M-90G = 17.6 / 30.3 / 35.3 / 16.8 48,000 5 4 41 DMAAlMA / VP / M-90G = 5.7 / 38.1 / 33.2 / 2 3 57,000 5 4 42 DMA / MMA / VP / M-90G = 11.3 / 37.8 / 28.6 / 22.3 46,000 5 4 43 DMAA4MA / VP / M-90G = 22.1 / 36 .2 / 20.4 / 21.3 51,000 5 4 44 DMC / MMA / VP / M-90G = 6.7 / 22.7 / 58.5 / 12.1 59,000 5 3 Real 45 DMC / MMA / VP / M-90G = 3.2 / 23.6 / 55.6 / 17.6 61,000 4 4 Test / rif 46 DMC / MMA / VP / M-90G = 1.6 / 22.2 / 58.5 / 17.7 60,000 4 3 Example 47 DM APM A / MM A / VP / M-90G = 6.7 / 2 3/58 /12.3 56,000 5 4 48 DMAPMA / MMA / VP / M-90G = 12.6 / 23 / 52.2 / 12.2 42,000 5 4 49 DMAPMA / MMA / VP / M-90G = 25.7 / 23.5 / 39 / 11.8 48,000 5 4 50 DMAPMA / MMA / VP / M-90G = 10 / 31.5 / 40.7 / 17.8 54,000 5 4 51 DMAPMA / MMA / VP / M-90G = 18.3 / 30.9 / 33.6 / 17.2 57,000 5 4 52 DMAFMA / MMA / VP / M-90G = 6.3 / 38.5 /32.3/22.9 50,000 5 4 53 DM APM A / MMA / VP / M-90G = 12/3 7.8 / 27.6 / 22.6 59,000 5 4 54 DMAPMA / MMA / VP / M-90G 2 23 / 36.6 / 18.6 / 21.8 53,000 5 4 55 DMAPAA / MMA / VP / M-90G = 12.2 / 29.5 / 41.8 / 16.5 50,000 5 4 56 DM APAA / MMA / VP / M-90G = 2 3.8 / 32.4 / 2 7.8 / 16.0 55,000 5 4 57 DMAPAA / MMA / VP / M-90G = 23.6 / 24.5 / 36 / 15.9 50,000 5 3 58 DMAPAA / MMA / VP / M-90G = 24.1 / 46.4 / 13.2 / 16.3 45,000 5 4 59 DMAPAA / MMA / VP / M-90G = 12.5 / 48 / 22.7 / 16.8 52,000 5 4 60 DMAPAA / MMA / VP / M-90G = 6.4 / 48.9 / 27.6 / 17.1 54,000 5 4 61 DMAPAA / MMA / VP / M-90G = 12.8 / 30.7 / 45 / 11.5 48,000 5 4 62 DMAPAA / MMA / VP / M-90G = 22 / 38.2 / 28.5 / 11.3 50,000 5 3

34 200536867 15195pif.doc 【表4】高分子化合物組成 (質量％) 重量平均分子量防汚性4 洗浄性軟式隱形眼鏡軟式隱形眼鏡 1 聚乙烯吡咯烷酮 — 2 2 2 聚丙烯酸 - 1 1 3 DM/AA/MMA=25/70/5 95,000 2 2 比 4 DM/MAA/HEMA=0.1/35/64.9 70,000 2 2 較 /ΠΙ 5 MMA/AA=40/60 78,000 1 1 例 6 M-230G/AA=20/80 89,000 2 1 7 DMC/EMA/VP=0.8/22/77.2 2,000 2 2 8 DMC/MAA/MMA/VP=0.1/20/2/77.9 34,000 1 1 9 DMC/MAA/M-230G=15/82/3 22,000 1 2 [實驗例63〜實驗例66，比較例10、11] 按照表5之組成，依習用方法調製防污劑組成物、防污沖洗劑組成物。在前述的防污性3評價方法中，除了將 0.05質量％的高分子化合物溶液或分散液替換成所得之防污劑組成物、防污沖洗劑組成物之外，用同樣的方法評估防污劑組成物、防污沖洗劑組成物。結果一併記於表5中。 35 200536867 15195pif.doc 【表5】組成（質量％) 實驗例比較例 63 64 65 66 10 11 實驗例1 0.03 — — — — — 實驗例2 一 0.03 一 — — — 高分子化實驗例3 一一 0.03 — — — 合物實驗例56 一 — — 0.03 一一比較例1 一 — — — 1.0 — 比較例2 — — — — — 1.0 鹽酸聚六曱撑雙胍 0.0001 一 0.00007 0.0001 0.0001 一泊利氣胺 — 0.011 — _ — 0.011 10%氣化节烷銨液一 — 0.1 — — — α -環糊精 — — 0.1 — — — 枯草桿菌蛋白酶A 0.005 0.005 0.005 0.005 0.005 0.005 聚氧乙烯硬化蓖麻油 60 0.1 — 0.1 — 0.1 — 聚山梨酸酯80 一 0.05 — 一 — 0.05 TETRONIC1107 0.3 0.3 0.3 0.3 0.3 0.3 NEWPOL PE68 0.5 0.5 0.5 0.5 0.5 0.5 硼酸 0.3 — 一 0.3 0.3 — 硼砂 0.05 — 一 0.05 0.05 — 氨丁三醇(tromethanol) — 0.3 — 一一 0.3 2水合磷酸二氫鈉 — — 0.08 — — — 12水合磷酸氫二鈉一一 0.5 一 — 一檸檬酸 0.05 0.05 0.05 0.05 0.05 0.05 乙二胺四乙酸鈉 0.01 0.01 0.01 0.01 0.01 0.01 氣化納 0.1 一一 0.1 0.1 — 甘油 — 0.1 一 0.1 一 0.1 甘露醇一 — 0.1 — — 一丙二醇 0.2 0.2 0.2 0.2 0.2 0.2 1-薄荷腦 0.002 0.002 0.002 0.002 0.002 0.002 L-天冬氣酸卸 0.25 0.25 0.25 0.25 0.25 0.25 氣基乙續酸 1.0 1.0 1.0 1.0 1.0 1.0 谷氨酸納 0.1 0.1 0.1 0.1 0.1 0.1 稀鹽酸適量氫氧化納適量精製水(purified-water) 剩餘部分(balance) 合計 100 pH 1 防污性3 5 5 5 5 1 1 耐久性 30小時 5 5 5 5 1 1 15小時 5 5 5 5 1 1 36 200536867 15195pif.doc 表中的縮寫表示於下： •DM:曱基丙烯酸二曱胺基乙酯 • DMA :丙烯酸二甲胺基乙酯 • DMAPAA :二甲基氨丙基丙烯醯胺 • DMAPMA :二甲基氨丙基（甲基)丙烯醯胺 • DMC :氯化甲基丙烯酸二曱基胺基乙基甲酯 • MMA :曱基丙烯酸曱酯 • EMA :曱基丙烯酸乙酯 • BMA :甲基丙烯酸正丁酯 •t-BMA:甲基丙稀酸第三丁酉旨 • VP :乙烯吡咯烷酮 •M-90G:甲氧聚單甲基丙烯酸乙二酯（甲基丙烯酸曱氧聚乙二酯)(聚乙烯平均=9)(新中村化學工業股份有限公司製） •M-230G:甲氧聚單甲基丙烯酸乙二酯（甲基丙烯酸甲氧聚乙二酯)(聚乙烯平均=23)(新中村化學工業股份有限公司製） •HEMA:甲基丙烯酸經基乙酯 • AA ··丙稀酸 • MAA :甲基丙烯酸 • TETRONIC1107 · >白洛沙姆(p〇i〇xamer)(巴斯夫曰本股份有限公司） • NEWPOL PE68 : Pluronic®型非離子介面活性劑(三洋化成股份有限公司製） 37 200536867 15195pif.doc 【圖式簡單說明】無【主要元件符號說明】無34 200536867 15195pif.doc [Table 4] Macromolecular compound composition (% by mass) Weight-average molecular weight Antifouling property 4 Detergent soft contact lens Soft contact lens 1 Polyvinylpyrrolidone — 2 2 2 Polyacrylic acid — 1 1 3 DM / AA / MMA = 25/70/5 95,000 2 2 to 4 DM / MAA / HEMA = 0.1 / 35 / 64.9 70,000 2 2 / ΠΙ 5 MMA / AA = 40/60 78,000 1 1 Example 6 M-230G / AA = 20 / 80 89,000 2 1 7 DMC / EMA / VP = 0.8 / 22 / 77.2 2,000 2 2 8 DMC / MAA / MMA / VP = 0.1 / 20/2 / 77.9 34,000 1 1 9 DMC / MAA / M-230G = 15/82 / 3 22,000 1 2 [Experimental Example 63 to Experimental Example 66, Comparative Examples 10 and 11] According to the composition in Table 5, an antifouling agent composition and an antifouling rinse agent composition were prepared according to conventional methods. In the aforementioned antifouling property 3 evaluation method, the antifouling was evaluated by the same method except that the 0.05% by mass polymer compound solution or dispersion was replaced with the obtained antifouling agent composition and antifouling rinse agent composition. Agent composition, antifouling agent composition. The results are collectively shown in Table 5. 35 200536867 15195pif.doc [Table 5] Composition (% by mass) Experimental Example Comparative Example 63 64 65 66 10 11 Experimental Example 1 0.03 — — — — — Experimental Example 2 0.03 One — — — Polymerization Experimental Example 3 One One 0.03 — — — Compound Experiment Example 56 — — — 0.03 — Comparative Example 1 — — — 1.0 — Comparative Example 2 — — — — — 1.0 Polyhexamethylene hydrochloride 0.0001-0.00007 0.0001 0.0001 Monoporinamine-0.011 — _ — 0.011 10% gasified alkane ammonium solution one — 0.1 — — — α-cyclodextrin — — 0.1 — — — Subtilisin A 0.005 0.005 0.005 0.005 0.005 0.005 Polyoxyethylene hardened castor oil 60 0.1 — 0.1 — 0.1 — Polysorbate 80 — 0.05 — One — 0.05 TETRONIC1107 0.3 0.3 0.3 0.3 0.3 0.3 NEWPOL PE68 0.5 0.5 0.5 0.5 0.5 0.5 Boric acid 0.3 — One 0.3 0.3 — Borax 0.05 — One 0.05 0.05 — tromethanol — 0.3 — one one 0.3 2 sodium dihydrogen phosphate hydrate — — 0.08 — — — 12 disodium hydrogen phosphate hydrate one one 0.5 one — monocitric acid 0.05 0 .05 0.05 0.05 0.05 0.05 Sodium ethylenediamine tetraacetate 0.01 0.01 0.01 0.01 0.01 0.01 Gasification sodium 0.1-0.1 0.1-glycerol-0.1-0.1-0.1 mannitol 1-0.1--monopropanediol 0.2 0.2 0.2 0.2 0.2 0.2 1 -Menthol 0.002 0.002 0.002 0.002 0.002 0.002 L-Aspartic acid removal 0.25 0.25 0.25 0.25 0.25 0.25 Gas-based diacetic acid 1.0 1.0 1.0 1.0 1.0 1.0 Sodium glutamate 0.1 0.1 0.1 0.1 0.1 0.1 Dilute hydrochloric acid amount Sodium hydroxide amount Purified-water balance 100 pH 1 Antifouling 3 5 5 5 5 1 1 Durability 30 hours 5 5 5 5 1 1 15 hours 5 5 5 5 1 1 36 200536867 15195pif.doc Table The abbreviations in the following are shown below: • DM: dimethylaminoethyl methacrylate • DMA: dimethylaminoethyl acrylate • DMAPAA: dimethylaminopropylacrylamide • DMAPMA: dimethylaminopropyl (Meth) acrylamide • DMC: diammonium aminoethyl methyl methacrylate chloride • MMA: ammonium methyl acrylate • EMA: ethyl ammonium acrylate • BMA: n-butyl methacrylate • t-BMA: methyl acrylic acid Purpose • VP: Vinylpyrrolidone • M-90G: Methoxypolymonomethacrylate (Methoxymethacrylate) (Polyethylene average = 9) (Made by Shin Nakamura Chemical Industry Co., Ltd.) • M-230G: methoxypolyethylene methacrylate (methacrylate methacrylate) (polyethylene average = 23) (made by Shin Nakamura Chemical Industry Co., Ltd.) • HEMA: methacrylic acid Ethyl Ethyl Acetate • AA • Acrylic acid • MAA: Methacrylic acid • TETRONIC 1107 • > Beloxam (BASF Japan) • NEWPOL PE68: Pluronic® type non-ionic interface Active agent (manufactured by Sanyo Chemical Co., Ltd.) 37 200536867 15195pif.doc [Simplified diagram] None [Description of main component symbols] None

Claims

20053·^ 十、申請專利範圍： ι一種防止蛋白質附著的高分子化合物，係由下述 (A)、（Β)以及（〇共聚而成，且重量平均分子量為 5,000〜1，〇〇〇,〇〇〇 ;其中：一（Α)為(A_l)及/或(Α_2)，（Α-1)係以下述化學式⑴所表不之含有3級胺基的單體，含量為〇·ι〜75質量％，（Α-2) 系、下述化干式(2)所表示之含有4級銨基的單體，含量為 =單m ’⑼係以下躲學式(3)衫之(曱基)丙烯酸 Γ為21〜80質量％，(c)為⑷、⑻單體以外的非離子性水溶性單體，含量為G.1〜78.9質量％，20053. ^ X. Patent application scope: ι A polymer compound for preventing protein attachment, which is formed by copolymerization of the following (A), (B), and (0), and the weight average molecular weight is 5,000 to 1,000,000. 〇〇〇; Where: (A) is (A_1) and / or (Α_2), (A-1) is a monomer containing a tertiary amine group represented by the following chemical formula ⑴, the content is 〇～ ι ～ 75% by mass, (A-2), a monomer containing a fourth-order ammonium group represented by the following dry formula (2), the content of which is equal to a single m '⑼ system (3) (Base) Acrylic acid Γ is 21 to 80% by mass, (c) is a nonionic water-soluble monomer other than fluorene and fluorene monomers, and the content is G.1 to 78.9% by mass,

(1) (在化學式（1)中，尺丨為或贿^^八飞原子次甲基八表示氧原子 1或2); ，、反數1〜4直鏈或支鏈烷基，m為〇、或2); $學式(2) R6(1) (In the chemical formula (1), the ruler is or ^^ eight flying atom methine octa represents an oxygen atom 1 or 2);, 1, 1 to 4 straight or branched chain alkyl group, m is 〇, or 2); $ Learn formula (2) R6

(ch2): R9 Nr~R R 11 X' (2) 39 200536867 15195pif.doc 烧基，R9、R1G以及R11分別表示碳數為1〜4之直鏈或支鏈烷基，η為0、1或2，X為鹵素、〇H、i/2S〇4、HS04、 1/3P04、hco2 或 CH3C02); CH2 二 C(R12)COOR13 (3) (化學式(3)中，R12為氫原子或甲基，R!3為碳數之直鏈或支鏈絲）。 6 2·—種防污劑組成物，其特徵在於包括申請專利範圍第1項所述之高分子化合物。 3·—種洗淨性防污劑組成物，其特徵在於包括利範圍第1項所述之南分子化合物。第1項所述之高分子化合物 5· —種隱形眼鏡用組成物，其料η 第i項所述之高分子化合物。徵在於包括巾請專利範圍 4.-種眼湘組成物，其特徵在於包括圍 200536867 15195pif.doc 七、指定代表圖： (一) 本案指定代表圖為：無 (二) 本代表圖之元件代表符號簡單說明：無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無(ch2): R9 Nr ~ RR 11 X '(2) 39 200536867 15195pif.doc, R9, R1G, and R11 respectively represent a linear or branched alkyl group having 1 to 4 carbon atoms, and η is 0, 1 or 2, X is halogen, 0H, i / 2S04, HS04, 1 / 3P04, hco2 or CH3C02); CH2 diC (R12) COOR13 (3) (In the formula (3), R12 is a hydrogen atom or a methyl group , R! 3 is a straight or branched chain of carbon number). 6 2 · —An antifouling agent composition characterized by including the polymer compound described in item 1 of the scope of patent application. 3. A detergent antifouling agent composition, characterized in that it comprises the south molecular compound described in the first item of the invention. Polymer compound according to item 1 ·· A composition for contact lenses, wherein the polymer compound according to item i. It is included in the patent scope 4.-Specific eye composition, which is characterized by including 200536867 15195pif.doc 7. Designated representative map: (1) The designated representative map in this case is: None (II) The component representative of the representative map Simple explanation of symbols: None 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: None