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TR201708077A2 - Hydrophilic Coating Solution with Functional Nanoparticle and Production Method - Google Patents

Hydrophilic Coating Solution with Functional Nanoparticle and Production Method Download PDF

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TR201708077A2
TR201708077A2 TR2017/08077A TR201708077A TR201708077A2 TR 201708077 A2 TR201708077 A2 TR 201708077A2 TR 2017/08077 A TR2017/08077 A TR 2017/08077A TR 201708077 A TR201708077 A TR 201708077A TR 201708077 A2 TR201708077 A2 TR 201708077A2
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coating solution
production method
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hydrophilic coating
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TR2017/08077A
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Turkish (tr)
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Çeli̇k Hümeyra
Özkoç Güralp
Beste Özcan Özden
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Gueralp Oezkoc
Magnano Teknoloji Ticaret Anonim Sirketi
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Abstract

Buluş, özellikle medikal sektöründe üriner, gastrointestinal (endoskopi, kolonoskopi vb.) ve kardiyovasküler kateterler; kılavuz teller, implantlar, stentler, enjektörler ve membranlar gibi vücut içi uygulamalarda kullanılan birçok tıbbi cihaz ve aletlerin yüzeylerine yüksek kayganlık özelliğinin kazandırılması amacıyla en az bir hidrofilik polimer ve/veya monomer, başlatıcı, solvent ve biyo uyumlu fonksiyonel nanoparçacık POSS (polihedral oligomerik silseskioksan) içeren hidrofilik kaplama solüsyonu ve üretim yöntemi ile ilgilidir.In particular, the invention relates to urinary, gastrointestinal (endoscopy, colonoscopy, etc.) and cardiovascular catheters in the medical sector; at least one hydrophilic polymer and / or monomer, initiator, solvent and biocompatible functional nanoparticle POSS (polyhedral oligomeric silsescioxane) for the purpose of imparting high lubricity to the surfaces of many medical devices and instruments used in in-body applications such as guide wires, implants, stents, syringes and membranes. hydrophilic coating solution and the method of manufacture.

Description

TARIFNAME Fonksiyonel Nanoparçacik Içeren Hidrofilik Kaplama Solüsyonu ve Üretim Yöntemi Teknik Alan Bulus,f0nksiyonel nanoparçacik içeren hidrofilik kaplama solüsyonu olarak kullanilacak ürünlerve bu ürünlerin üretim yöntemi ile ilgilidir. DESCRIPTION Hydrophilic Coating Solution Containing Functional Nanoparticles and Production Method Technical Area The invention will be used as a hydrophilic coating solution containing functional nanoparticles. products and the production method of these products.

Bulus, özellikle medikal sektöründe üriner, gastrointestinal (endoskopi, kolonoskopi vb.) ve kardiyovasküler kateterler; kilavuz teller, implantlar, stentler, enjektörler ve membranlar gibi vücut içi uygulamalarda kullanilan birçok tibbi cihaz ve aletlerin yüzeylerine yüksek kayganlik özelliginin kazandirilmasi amaciyla hidrofilik polimer ve/veya monomer, baslatici, solvent ve biyo uyumlu fonksiyonel nanoparçacik POSS (polihedral oligomerik silseskioksan) içeren hidrofilik kaplama solüsyonu ve üretim yöntemi ile ilgilidir. The invention is especially useful in the medical sector for urinary, gastrointestinal (endoscopy, colonoscopy, etc.) and cardiovascular catheters; such as guide wires, implants, stents, syringes, and membranes. High lubricity to the surfaces of many medical devices and instruments used in intra-body applications. hydrophilic polymer and/or monomer, initiator, solvent and containing biocompatible functional nanoparticle POSS (polyhedral oligomeric silsesquioxane) It relates to the hydrophilic coating solution and production method.

Teknigin Bilinen Durumu Günümüzde kaplamalar birçok endüstriyel uygulamalarda oldugu gibi dekoratif veya koruma amaçli kullanilmaktadirlar. Medikal cihazlarda ise cihazin fonksiyon veya performansinda gerekli gelistirmelerin saglanmasi amaçli kullanilmaktadir. Medikal cihazlarin üretiminde kullanilan malzemelerin çogu düsük yüzey enerjisine sahip hidrofobik malzemelerden olusmaktadir. 8qu ortamlarda yeteri kadar islanmayan bu cihazlar vücut içi uygulamalarda kullanildigindasürtünmeden kaynakli yirtilma, delinme, kanamaya sebep olma gibi travmatik komplikasyonlar ve iltihaplanmalara sebep 0Iabilmektedir.Olusan bu problemlerin çözümüne yönelik gelistirilen en kesin çözüm ise doku ile direkt temas edecek, cihazin vücut içinde hareketini kolaylastiracak ve ayni zamanda biyouyumluluga sahip bir kaplama uygulanmasidir. State of the Art Today, coatings are decorative or protective as in many industrial applications. are used for the purpose. In medical devices, the function or performance of the device It is used to provide necessary improvements. In the production of medical devices Most of the materials used are hydrophobic materials with low surface energy. is formed. These devices, which do not get wet enough in 8qu environments, are used in intra-body applications. traumatic injuries such as tearing, perforation, bleeding caused by friction when used It can cause complications and inflammation. The most precise solution developed for It is the application of a coating that will facilitate its movement and at the same time have biocompatibility.

Hidrofilik polimer kaplama olarak da bilinen bu kaplamalar farkli yollarla yüzeye uygulanmaktadirlar. Daldirma ile kaplama en sik kullanilan yöntemlerdendir. Sprey ve film kaplama bir diger kaplama metotlarindandir. Bu islemlerin yani sira yaygin olarak kullanilmamakla birlikte, özellikle yassi yüzeyler için kimyasal buharla kaplama (CVD) ve serigrafi (silk screening) metotlari da tercih edilebilmektedir. Kaplama metodlarinin çogu kurutma ve kürleme (curing) olmak üzere iki asamadan olusmaktadir. Kürleme islemi ise isi ve ultraviyole (UV) gibi radyasyon ile gerçeklestirilmektedir [1-5]. sürtünmeli hidrofilik bir kaplama katsayisina sahip olan kaplanmis alt tabaka ve bunu yapmak için bir yöntem' baslikli patentlerde kateter ve prezervatif örneklerinin Polivinilpirolidon- Poliüretan interpolimeri ile kaplandigi görülmektedir. Bu çalismada, kaplama prosesi iki asamada gerçeklesmis ve karisima zincir uzaticilar eklenmistir. Ancak elde edilen bulgular bu yöntem ile üniform bir kaplama yapilamadigini ve istenen özelliklerin kaplamaya saglanamadigini göstermistir. These coatings, also known as hydrophilic polymer coatings, can be applied to the surface in different ways. they are implemented. Coating by dipping is one of the most commonly used methods. spray and film coating is another coating method. In addition to these operations, it is widely Although not used, chemical vapor coating (CVD) and screen printing (silk screening) methods can also be preferred. Most coating methods It consists of two stages, namely drying and curing. The curing process is heat and It is carried out with radiation such as ultraviolet (UV) [1-5]. coated substrate having a frictional hydrophilic coating coefficient and to do so Polyvinylpyrrolidone- It is seen that it is coated with polyurethane interpolymer. In this study, the coating process realized in stages and chain extenders were added to the mixture. However, these findings It is stated that a uniform coating cannot be made with this method and that the desired properties cannot be applied to the coating. has shown that it is not available.

US4642267 yayin numarali 'Hidrofilik polimer harmani' baslikli patentte termoplastikpoliüretan, polivinilpirolidon ve/veya poli(N-vinillaktam) karisimlari hazirlanmis ve solüsyonlar vinil, epoksi ve poliüretan yüzeylerine kaplanmistir. Ardindan kaplanan yüzeyler islatilmis ve sürtünme testinde sürtünme katsayisinin oldukça düstügü belirlenmistir. In the patent with the title 'Hydrophilic polymer blend', publication number US4642267 Thermoplastic polyurethane, polyvinylpyrrolidone and/or poly(N-vinylactam) mixtures were prepared and solutions are coated on vinyl, epoxy and polyurethane surfaces. Subsequently coated surfaces It was wetted and it was determined that the coefficient of friction was quite low in the friction test.

US4977901 yayin numarali 'Çapraz baglanmamis kristalize polimer kaplamalara sahip olan malzeme* baslikli patentte farkli molekül agirligina sahip poli(vinil alkol) su ve/veya dimetilsülfoksit içerisinde çözündürülmüs ve kilavuz tele kaplanmistir. Çapraz baglanmamis bu kaplama firinlarda kurutulmus ve kristallinite incelenmistir. Elde edilen bulgular daha az kristaliniteye sahip kaplamanin su emiliminin daha yüksek oldugunu, sürtünmenin azaldigi dolayisiyla kayganligin arttigini göstermistir. Publication number US4977901 'With coatings of non-cross-linked crystalline polymer In the patent titled material*, poly(vinyl alcohol) water and/or dissolved in dimethylsulfoxide and coated on the guide wire. not cross linked This coating was dried in ovens and the crystallinity was investigated. Findings are less The water absorption of the coating with crystallinity is higher, friction is reduced. therefore, it showed that the slipperiness increased.

POSS (polihedral oligomerik silseskioksan) olarak adlandirilan yeni nesil takviye malzemeleri silika (SIOz) ve silikon (stiO) arasinda, moleküler boyutlari yaklasik olarak 1-3nm olan küresel sekilli hibrit nanoyapilardir. Bununla birlikte silika ve diger konvansiyonel dolgulardanfarkli olarak, herhangi bir POSS molekülü kendisini polimerler, biyolojik sistemler veya yüzeyler ile uyumlu hale getiren organik gruplar içerir. Bu özellik POSS'un harmanlandigi polimer zincir ile kovalent olarak tepkimeye girmesini de mümkün kilmaktadir[6]. Siradan organik bilesiklerin tersine, uçucu organik bilesikler salmadiklari için kokusuz ve çevre dostu olarak bilinmektedirler[7,8].POSSiun sahip oldugu genis ve esnek kimyasal yapisal özellikler sebebiyle polimer yapisina dahil edilme asamasinda hem kopolimerizasyon, hem asilama hem de harmanlama teknigine imkan saglamaktadir. New generation reinforcement materials called POSS (polyhedral oligomeric silsesquioxane) between silica (SIOz) and silicon (stiO) with molecular dimensions of approximately 1-3 nm. spherical shaped hybrid nanostructures. However, silica and other conventional Unlike fillers, any POSS molecule can self-assemble into polymers, biological systems. or contains organic groups that make it compatible with surfaces. This feature is where POSS is blended. It also makes it possible to react covalently with the polymer chain[6]. Ordinary Odorless and environmentally friendly as they do not release volatile organic compounds, unlike organic compounds They are known as [7,8]. The wide and flexible chemical structural properties of POSS Both copolymerization, grafting and grafting during the inclusion stage of the polymer structure It also allows the blending technique.

POSS kaplamalari ve katki maddeleri ve aynisini yapma yöntemleri, baslikli patent malzemelerin yüzey performansini arttirmak için kaplamalar alaninda faydali flüorlu polihedral oligomerik silseskioksan ("F-POSS") kopolimerleri ve terpolimerleri ve bu gibi kopolimerler ve terpolimerler yapmak için yöntemler de açiklanmaktadir. Burada açiklanan bilesimlerin örnek teskil tarzlari, normalde yeterince kararli veya dayanikli homojenlige sahip olmayacak olan flüorinatli, halojenli veya diger katki maddeleri içeren formülasyonlarin stabilitesini ve ömrünü iyilestirmede yararli olabilir. epoksisiklohekziI-POSS kullanilarak UV ile kürlenebilen kaplama formülasyonlari hazirlanmistir. Kaplama formülasyonlari POSS, silikon nanoparçaciklari, silan ve fotobaslatici içermektedir. Hazirlanan bu solüsyonlar cam üzerine kaplanmis ve örneklerin statik indentasyonkirilma dayanimi,çatlama dayanimi, çizik ve asinmalara karsi dayanimi ve nem dayanikliligi incelenmistir. POSS coatings and additives and methods of replicating, patent entitled Fluorinated polyhedral useful in the field of coatings to improve the surface performance of materials oligomeric silsesquioxane ("F-POSS") copolymers and terpolymers and such copolymers and Methods for making terpolymers are also disclosed. Example of the compositions described here forms of formation, which would normally not have sufficiently stable or durable homogeneity. stability and longevity of formulations containing fluorinated, halogenated or other additives. It may be useful for improvement. UV-curable coating formulations using epoxycyclohexyl-POSS has been prepared. Coating formulations POSS, silicon nanoparticles, silane and photoinitiator contains. These prepared solutions were coated on glass and the samples were static. indentation-breaking resistance, cracking resistance, resistance to scratches and abrasions and moisture durability has been studied.

Mevcut patentlerde POSS kullanilarak hazirlanmis kaplamalarin hidrofilik özelligi incelenmemistir. Ozellikle vücut içi uygulamalarda kullanilmak maksadiyla çalisilmis herhangi Uriner, gastrointestinal (endoskopi, kolonoskopi vb.) ve kardiyovasküler kateterler, kilavuz teller, implantlar, stentler, enjektörler ve membranlar gibi birçok medikal cihaz vücut içine yerlestirilirken veya çikartilirken, vücuttan herhangi bir sivinin drenajini saglarken yüzeylerinin bir kayganlastirici ile kaplanmasina ihtiyaç duymaktadirlar. Ayrica bu kayganlik yerlestirme ve çikarma esnasinda yumusak doku hasarini minimize etmek için gereklidir. Hidrofilik kaplamalar cihazin hasta vücuduna yerlestirilmesinden önce, bir süre su veya baska bir sivi ile islatilarak düsük sürtünme özelliklerine ulasmis kaygan yüzey kaplamalaridir.Hidr0filik kaplamalar çogu zaman malzeme (substrat) yüzeyine tutunmayarak asinma egilimi sergilemekte ve bunun sonucu olarak kullanim esnasinda kayganliklarini yitirmektedirler. Hydrophilic property of coatings prepared using POSS in existing patents has not been examined. Any product that has been studied especially for use in intra-body applications. Urinary, gastrointestinal (endoscopy, colonoscopy, etc.) and cardiovascular catheters, guideline Many medical devices such as wires, implants, stents, syringes and membranes are inserted into the body. surface while being inserted or removed, allowing drainage of any fluid from the body. they need to be coated with a lubricant. In addition, this slippery installation and It is necessary to minimize soft tissue damage during removal. hydrophilic coverings with water or other liquid for some time before placing the device on the patient's body. They are slippery surface coatings that have reached low friction properties by being wetted with coatings tend to wear by not clinging to the material (substrate) surface most of the time. and as a result, they lose their lubricity during use.

Kaplama solüsyonlarinin malzeme yüzeyine uygulanmasinda hidrofilik kat ile malzeme yüzeyi arasinda baglanma saglamak için ekstradanprimer kaplamalar kullanilmaktadir. Material surface with hydrophilic layer in the application of coating solutions to the material surface Extra primary coatings are used to provide bonding between

Sonuç olarak yukarida anlatilan olumsuzluklardan dolayi ve mevcut çözümlerin konu hakkindaki yetersizligi nedeniyle ilgili teknik alanda bir gelistirme yapilmasi gerekli kilinmistir. As a result, due to the above-mentioned negativities and existing solutions Due to the inadequacy of the subject, it was necessary to make an improvement in the related technical field.

Bulusun Kisa Açiklamasi Bulus, mevcut durumlardan esinlenerek olusturulup yukarida belirtilen olumsuzluklari çözmeyi amaçlamaktadir. Brief Description of the Invention The invention is created by being inspired by current situations and aims to solve the above-mentioned problems. aims.

Bulusun öncelikli amaci, özellikle medikal sektöründe üriner, gastrointestinal (endoskopi, kolonoskopi vb.) ve kardiyovasküler kateterler; kilavuz teller, implantlar, stentler, enjektörler ve membranlar gibi vücut içi uygulamalarda kullanilan birçok tibbi cihaz ve aletlerin yüzeylerine uygulanmasi için hidrofilik kaplama solüsyonu elde edilmesini saglamaktir. The primary purpose of the invention is to treat urinary, gastrointestinal (endoscopy, colonoscopy etc.) and cardiovascular catheters; guide wires, implants, stents, injectors and surfaces of many medical devices and instruments used in intra-body applications such as membranes. It is to provide a hydrophilic coating solution for application.

Bulusun bir amaci, yüksek kayganligin yani sira yüksek asinma dayanimina sahip hidrofilik kaplama solüsyonu gelistirmektir. An object of the invention is to provide hydrophilic materials with high wear resistance as well as high lubricity. Developing a coating solution.

Bulusun bir diger amaci, malzeme(substrat) yüzeyine hidrofilik kaplama solüsyonunun uygulanmasi için herhangi bir primer kaplamaya ihtiyaç duyulmadan,içerdigi POSS sayesinde hidrofilik katin direkt malzeme yüzeyine uygulabilirligini saglamasidir. Another object of the invention is to apply hydrophilic coating solution to the material (substrate) surface. without the need for any primer coating, thanks to the POSS it contains. This is because it enables the hydrophilic layer to be applied directly to the material surface.

Bulus ayrica, POSS ilavesi ile hidrofilik kaplamanin kürleme zamaninin daha kisa sürelere çekilebilmesini amaçlamaktadir. The invention also shows that the curing time of the hydrophilic coating can be shortened by the addition of POSS. intended to be withdrawn.

Bulus, yukarida anlatilan amaçlarin yerine getirilmesi için, medikal sektöründe yer alan tibbi cihaz ve aletlerin yüzeylerinin kaplanmasinda kullanilmak üzere hidrofilik kaplama solüsyonu olup, özelligi; en az bir hidrofilik polimer ve/veya monomer, polihedral oligomerik silseskioksan, solvent ve baslatici ihtiva etmektedir. In order to fulfill the above-described purposes, the invention is used by medical professionals in the medical sector. hydrophilic coating solution for use in coating the surfaces of devices and instruments and its feature is; at least one hydrophilic polymer and/or monomer, polyhedral oligomeric silsesquioxane, Contains solvent and initiator.

Bulus, yukarida anlatilan amaçlarin yerine getirilmesi için, medikal sektöründe yer alan tibbi cihaz ve aletlerin yüzeylerinin kaplanmasinda kullanilmak üzere hidrofilik kaplama solüsyonu üretim metodu olup, özelligi; a) hidrofilik polimer ve/veya monomerin solvent içine karistirilmasi, b) elde edilen solüsyona POSS (polihedral oligomerik silseskioksan) eklenerek karistirilmasi, c) elde edilen solüsyona baslaticinin eklenerek karistirilmasi, islem adimlarini ihtiva etmektedir. In order to fulfill the above-described purposes, the invention is used by medical professionals in the medical sector. hydrophilic coating solution for use in coating the surfaces of devices and instruments It is a production method and its feature is; a) mixing the hydrophilic polymer and/or monomer into the solvent, b) by adding POSS (polyhedral oligomeric silsesquioxane) to the resulting solution. mixing, c) mixing by adding initiator to the resulting solution, It contains transaction steps.

Bulusun yapisal ve karakteristik özellikleri ve tüm avantajlari asagida verilen detayli açiklama sayesinde daha net olarak anlasilacaktir. Bu nedenle degerlendirmenin de bu detayli açiklama göz önüne alinarak yapilmasi gerekmektedir. The structural and characteristic features of the invention and all its advantages are described in detail below. will be understood more clearly. Therefore, this detailed explanation of the evaluation is also should be taken into account.

Bulusun Anlasilmasina Yardimci Olacak Sekiller Sekil 1. Bulus konusu hidrofilik kaplama solüsyonu ile kaplanan substrat ile kaplamasiz substratin sürtünme kuvvetlerinin kiyaslanmasinin grafiksel gösterimidir. Figures to Help Understand the Invention Figure 1. The substrate coated with the hydrophilic coating solution of the invention and uncoated It is a graphical representation of the comparison of the frictional forces of the substrate.

Sekil 2. Bulus konusu hidrofilik kaplama solüsyonu ile kaplanan substratin tekrarlanan testler ile sürtünme kuvvetlerinin degisiminin grafiksel gösterimidir. Figure 2. Repeated tests of the substrate coated with the hydrophilic coating solution of the invention It is a graphical representation of the variation of friction forces with

Bulusun Detayli Açiklamasi Bu detayli açiklamada, bulus konusu hidrofilik kaplama solüsyonu ve üretim yöntemi ile tercih edilen formülasyonlari, sadece konunun daha iyi anlasilmasina yönelik olarak ve hiçbir sinirlayici etki olusturmayacak sekilde açiklanmaktadir. Detailed Description of the Invention In this detailed explanation, the hydrophilic coating solution of the invention and the production method and the preferred The formulations presented here are only for a better understanding of the subject and without any It is explained in a way that does not have a restrictive effect.

Bulus, ozellikle medikal sektöründe üriner, gastrointestinal (endoskopi, kolonoskopi vb.) ve kardiyovasküler kateterler; kilavuz teller, implantlar, stentler, enjektörler ve membranlar gibi vücut içi uygulamalarda kullanilan birçok tibbi cihaz ve aletlerin yüzeylerine yüksek kayganlik özelliginin kazandirilmasi amaciyla en az bir hidrofilik polimer ve/veya monomer, baslatici, solvent ve biyo uyumlu fonksiyonel nanoparçacik POSS (polihedral oligomerik silseskioksan) içeren hidrofilik kaplama solüsyonu ve üretim yöntemi ile ilgilidir. The invention is especially useful in the medical sector for urinary, gastrointestinal (endoscopy, colonoscopy, etc.) and cardiovascular catheters; such as guide wires, implants, stents, syringes, and membranes. High lubricity to the surfaces of many medical devices and instruments used in intra-body applications. at least one hydrophilic polymer and/or monomer, initiator, solvent and biocompatible functional nanoparticle POSS (polyhedral oligomeric silsesquioxane) It is related to the hydrophilic coating solution containing the hydrophilic coating and the production method.

Bulus konusu hidrofilik kaplama solüsyonu ile poliesterüretan, polieterüretan, nylon, poli(eter- bIok-amit), poli(etilen teraftalat), poli(vinil klorür), dogal kauçuk, sentetik kauçuklar, poliester- polieter kopolimerleri, polikarbonat vb. organik malzemeler(substratlar)kaplanabilmektedir. With the hydrophilic coating solution of the invention, polyesterurethane, polyetherurethane, nylon, poly(ether- bio-amide), poly(ethylene terephthalate), poly(vinyl chloride), natural rubber, synthetic rubbers, polyester- polyether copolymers, polycarbonate etc. organic materials (substrates) can be coated.

Tablo 1ide, bulus konusuhidrofilik kaplama solüsyonunu olusturan hammaddeler ve bu hammaddelerin agirlikça kullanim oranlari verilmektedir. In Table 1, the raw materials that make up the inventive hydrophilic coating solution and this The weight usage rates of the raw materials are given.

Tablo1: Hidrofilik kaplama solüsyonu için hammadde ve kullanim oranlari Agirlikça Agirlikça lçerik (%) (%) Solvent 78,9 Hidrofilik polimer 20 1-30 ve/veya monomer (Polivinilpirolidon) Baslatici 1 Fonksiyonel nanoparçacik 0,1 0,1-5 TOPLAM 100 Bulus kapsaminda hidrofilik polimer ve/veya monomer, POSS ve baslaticinin solvent içinde çözünmesiyle solüsyon hazirlanmasi saglanmaktadir. Solüsyon oda sicakliginda hazirlanabildigi gibi 40°Ciye kadar isitilarak da hazirlanabilmekt edir. Solüsyon tamamen seffaf hale gelene kadar karistirilmalidir. Elde edilen solüsyon istenilensubstrat yüzeyine uygulanmalidir. Yüzeye uygulanmada tercih edilen yöntem olarak daldirma yöntemi kullanilmaktadir. Solüsyonun substrat yüzeyine uygulanmasinda sprey, film kaplama, buharla kaplama, serigrafi gibi baska metotlarda kulanilabilir. Substrat yüzeyine uygulanmis solüsyon tercih edilen ultraviyole (UV) kürleme metodu ile hidrofilik kaplama halini almaktadir. Diger kürleme seçenekleriisitma, sogutma, kurutma gibi fiziksel metotlar olabilirken, isi ve radyasyon gibi kimyasal metotlar da olabilir. Table1: Raw material and usage rates for hydrophilic coating solution by weight by weight Content (%) (%) Solvent 78.9 Hydrophilic polymer 20 1-30 and/or monomer (Polyvinylpyrrolidone) Initiator 1 Functional nanoparticle 0.1 0.1-5 TOTAL 100 In the scope of the invention, the hydrophilic polymer and/or monomer, POSS and initiator are dissolved in the solvent. Solution preparation is provided by dissolving it. The solution is at room temperature It can be prepared by heating up to 40°C as well as being prepared. The solution is completely transparent should be mixed until it becomes The resulting solution is applied to the desired substrate surface. should be applied. Immersion method as the preferred method of application to the surface is used. In the application of the solution to the substrate surface, spray, film coating, steam It can be used in other methods such as coating, screen printing. Solution applied to the substrate surface It takes the form of hydrophilic coating with the preferred ultraviolet (UV) curing method. Other While curing options can be physical methods such as heating, cooling, drying, heat and radiation chemical methods as well.

Bulus konusu hidrofilik kaplama solüsyonunu üretiminde kullanilan hammaddelerin özellikleri asagida verilmektedir. The properties of the raw materials used in the production of the hydrophilic coating solution of the invention are given below.

Solvent genis kullanim alanina sahip sivi halindeki bir maddedir. Söz konusu bulus solüsyon veya dispersiyon gibi sivi bir ortami kapsayan hidrofilik kaplama formülasyonlarini içermektedir. Sivi ortami olusturacak solvent olarak metanol, etanol, propanol vebütanol gibi alkoller veya bunlarin karisimlari, aseton, metil etil keton, tetrahidrafuran, dikolorometan, tolüen veya su seçilebilmektedir. Bulus konusu hidrofilik kaplama solüsyonununda agirlikça agirlikça %78,9 oraninda etanol kullanilmaktadir. Solvent is a liquid substance with wide usage area. The said invention solution or hydrophilic coating formulations involving a liquid medium such as a dispersion. contains. As solvent to create a liquid environment, such as methanol, ethanol, propanol and butanol alcohols or mixtures thereof, acetone, methyl ethyl ketone, tetrahydrafuran, dichloromethane, toluene or water may be chosen. Weight of the hydrophilic coating solution of the invention 78.9% of ethanol is used by weight.

Hidrofilik polimer veya monomer kisaca suyu seven molekül zincirleri veya molekül olarak adlandirilmaktadir. Hidrofilik bir molekül veya bir molekülün hidrofilik bir bölümü tipik olarak yük kutuplasmasi gösterir ve hidrojen bagi kurma yetenegi vardir, böylece yag ve diger hidrofobik çözücülere kiyasla suda çözünmeye daha müsaittir. Hidrofilik moleküller polar moleküller olarak da bilinmektedirler. Hydrophilic polymer or monomer briefly as water-loving molecular chains or molecules is named. Typically, a hydrophilic molecule or a hydrophilic portion of a molecule exhibits charge polarity and has the ability to form hydrogen bonds, thus allowing oil and other It is more amenable to water solubility than hydrophobic solvents. hydrophilic molecules polar They are also known as molecules.

Bulus konusu kaplama solüsyonuna hidrofilik özellik katan polimer ve/veya monomer; poli(vinil alkol), polivinilpirolidon, poli(etilen oksit), akrilik asit ve metakrilikasitin homo- ve kopolimerleri, maleik anhidrit bazli kopolimerler, poli(karboksilik asit), selüloz, heparin, poli(etilen glikol), kitosan, hyaluronik asit, kitin ve polilaktinler içeren gruplar arasindan birey veya kombinasyonlar seçilebilmektedir. Bulus konusu hidrofilik kaplama solüsyonununda agirlikça formülasyonunda agirlikça %20 oraninda PoliviniIpirolidon(PVP)kuIIanilmaktadir. Polymer and/or monomer that adds hydrophilic properties to the coating solution of the invention; poly(vinyl homo- and copolymers of alcohol), polyvinylpyrrolidone, poly(ethylene oxide), acrylic acid and methacrylic acid, copolymers based on maleic anhydride, poly(carboxylic acid), cellulose, heparin, poly(ethylene glycol), individual or from groups containing chitosan, hyaluronic acid, chitin and polylactins. combinations can be selected. Weight of the hydrophilic coating solution of the invention Polyvinylpyrrolidone (PVP) is used at a rate of 20% by weight in its formulation.

Fonksiyonel nanoparçacik POSS (polihedral oligomerik silseskioksan) seramik ve organik malzemeler arasindaki bosluga köprü olusturan nano yapili bir kimyasaldir. POSS, mekanik özelliklerden ödün vermeksizin ürün performansini gelistirir ve çok çesitli endüstrilerde kullanilir. POSS silika (SiOz) ve silikon (R28IO) arasinda, moleküler boyutlari yaklasik olarak 1-3nm olan küresel sekilli hibrit nano yapidadir. Bununla birlikte silika ve diger konvansiyonel dolgulardan farkli olarak, herhangi bir POSS molekülü kendisini polimerler, biyolojik sistemler veya yüzeyler ile uyumlu hale getiren organik gruplar içerir. Bu 'özellik POSSiun harmanlandigi polimer zincir ile kovalent olarak tepkimeye girmesini de mümkün kilmaktadir. Siradan organik bilesiklerin tersine, uçucu organik bilesikler salivermedikleri için kokusuz ve çevre dostu olarak bilinmektedirler. Possiun sahip oldugu genis ve esnek kimyasal yapisal özellikler sebebiyle polimer yapisina dahil edilme asamasinda hem kopolimerizasyon, hem asilama hem de harmanlama teknigine imkan saglamaktadir. Bulus konusu hidrofilik kaplama solüsyonununda agirlikça %0,1-5 oraninda POSS kullanilabilmektedir.Bulusun tercih edilen formülasyonundaagirlikça %0,1 oraninda POSSkullanilmaktadir. Functional nanoparticle POSS (polyhedral oligomeric silsesquioxane) for ceramic and organic It is a nano-structured chemical that bridges the gap between materials. POSS, mechanical improves product performance without sacrificing features and is used in a wide variety of industries. used. Between POSS silica (SiO2) and silicon (R28IO), their molecular dimensions are approximately It is a spherical hybrid nano structure of 1-3nm. However, silica and other conventional Unlike fillers, any POSS molecule can self-assemble into polymers, biological systems. or contains organic groups that make it compatible with surfaces. This 'feature' is where POSS is blended. It also makes it possible to react covalently with the polymer chain. ordinary organic odorless and environmentally friendly as they do not release volatile organic compounds they are known. Due to the wide and flexible chemical and structural properties of the possi both copolymerization, grafting and It allows the blending technique. In the hydrophilic coating solution of the invention, POSS can be used at a rate of 0.1-5% by weight. POSS is used at a rate of 0.1% by weight in its formulation.

Baslatici polimerizasyon reaksiyonunu baslatan maddedir. Fotobaslaticilar, isik absorplayan ve reaktif baslatici radikalleri olusturan, UV ile polimerizasyon sistemlerinin en önemli bilesenleridir. Bulus kapsaminda formülasyonlarda kullanilan baslatici Tip 1 fotobaslaticilar (benzoin eterler, benzil ketaller, oi-diaIkoksiasetofenonlar, d-hidroksialkilfenonlar, d-amino alkilfenonlar, asilfosfinoksitler gibi), Tip 2 fotobaslaticilar (benzofenonlar/aminler, tiyoksantonlar/aminler gibi) ve peroksitler (hidrojen peroksit, benzoil peroksit ve kümen hidroperoksit) içeren gruplar arasindan seçilebilmektedir.Bulus konusu hidrofilik kaplama solüsyonununda agirlikça %O,5-20 oraninda baslatici kullanilabilmektedir.Bulusun tercih edilen formülasyonundaagirlikça %1 oraninda hidrojen peroksitkullanilmaktadir. The initiator is the substance that initiates the polymerization reaction. Photoinitiators, light absorber and reactive initiator radicals, the most important of the UV polymerization systems are components. Initiator Type 1 photoinitiators used in formulations within the scope of the invention (benzoin ethers, benzyl ketals, oi-diaIkoxyacetophenones, d-hydroxyalkylphenones, d-amino such as alkylphenones, acylphosphinoxides), Type 2 photoinitiators (benzophenones/amines, such as thioxantones/amines) and peroxides (hydrogen peroxide, benzoyl peroxide and cumene) hydrophilic coating of the invention. 0.5-20% by weight of initiator can be used in the solution of the invention. Hydrogen peroxide is used at a rate of 1% by weight in its formulation.

Deneysel prosedürde oda sicakliginda,Tablo 1*de belirtilen tercih edilen miktarlarda,hidrofilik polimer Polivinilpirolidon(PVP)soIvent olarak kullanilan etanol içine karistirilmistir. Elde edilen solüsyona POSS eklenerek karistirilmaya devam edilmistir. Karisima baslatici olarak hidrojen peroksit eklenmis ve seffaf bir solüsyon elde edilene kadar karistirilmistir. Ardindan kaplanmak istenen substrat solüsyona daldirilmis ve çikarilarak belirli sürelerde UV isinlara maruz birakilmistir. Kürlenme asamasinda önemli olan husus çapraz bag reaksiyonunun tamamlanmasidir. Böylelikle yüzeye tutunan kaplama kuvvet altinda siyrilmadan özelliklerini korumaktadir. Son asamada elde edilen hidrofilik kaplamali örnekler sürtünme testine tabi tutulmus ve sürtünme kuvvetleri belirlenmistir. Bu dogrultuda kaplanan kateterler bir dakika boyunca su içinde bekletilmis ve takiben 500 gramlik bir yük uygulanarak iki kauçuk ped arasindan toplamda 20 kez çekilmistir. In the experimental procedure, at room temperature, in the preferred amounts specified in Table 1, hydrophilic The polymer Polyvinylpyrrolidone(PVP) was mixed into ethanol, which was used as solvent. Obtained POSS was added to the solution and mixing was continued. Hydrogen as mixing initiator peroxide was added and mixed until a clear solution was obtained. then be covered The desired substrate is immersed in the solution and removed and exposed to UV rays for certain periods. has been abandoned. The important point in the curing stage is that the cross-link reaction is completion. Thus, the coating that adheres to the surface does not peel off under force. protects. Hydrophilic coated samples obtained in the final stage are subjected to friction test. and friction forces were determined. Catheters coated in this direction Two rubber pads were soaked in water for a length of time and then a 500 gram load was applied. It has been drawn 20 times in total.

Hazirlanan hidrofilik solüsyon ile kaplanmis substratin ve kaplanmamis substratin kayganliklari sürtünme testleri ile belirlenmistir. Bu amaçlakapli örnek ard arda 10 kez yük altinda çekilmis ve sürtünme kuvvetleri elde edilmistir. Sekil 1'de bulus konusu hidrofilik kaplama solüsyonu ile kaplanan substrat ile kaplamasiz substratin sürtünme kuvvetlerinin kiyaslanmasini göstermektedir. Yüzeyinde hidrofilik kaplama solüsyonu bulunan örnegin sürtünme kuvvetinin, kaplamasiz örnegin sürtünme kuvvetine kiyasla ortalama 20 kat azaldigi tespit edilmistir. The substrate coated with the prepared hydrophilic solution and the uncoated substrate. The lubricity was determined by friction tests. For this purpose, the coated sample is loaded 10 times in succession. and friction forces were obtained. In Figure 1, the subject of the invention is hydrophilic. the frictional forces of the substrate coated with the coating solution and the uncoated substrate. shows the comparison. For example with hydrophilic coating solution on the surface The friction force is reduced by an average of 20 times compared to the friction force of the uncoated sample. has been detected.

Kaplamanin yüzeye tutunmasi ise ard arda tekrar edilen testler ile belirlenmistir. Sekil 2'de bulus konusu hidrofilik kaplama solüsyonu ile kaplanan substratin tekrarlanan testler ile sürtünme kuvvetlerinin degisimini göstermektedir. Kaplamali substratlara ait 10 çekmenin sonunda elde edilen egrilerin ayni trende sahip oldugu ve kuvvet degerlerinin benzer oldugu görülmüstür. Bu bulgu kaplamanin substrat yüzeyinden ayrilmadigini ve homojen oldugunu göstermektedir. The adhesion of the coating to the surface was determined by repeated tests. in Figure 2 by repeated tests of the substrate coated with the hydrophilic coating solution of the invention. shows the variation of friction forces. 10 shrinkage of coated substrates that the curves obtained at the end have the same trend and the force values are similar. has been seen. This finding indicates that the coating does not separate from the substrate surface and is homogeneous. shows.

Yapilan sürtünme testleri sonucunda POSS parçaciginin reaksiyonu hizlandirarak kürlenme zamanini kisalttigi görülmüstür. As a result of the friction tests, the reaction of the POSS particle accelerates and cures. It has been seen that it shortens the time.

KAYNAKLAR Universitesi Mühendislik Fakültesi, 2008,s. 1-3. RESOURCES University Faculty of Engineering, 2008, p. 1-3.

PolymerThinFiImsby Spin CoatingMethod.(M. Sc. Thesis), Gazi Universitylnstitute of Science, 2010,Ankara. 4,977,901., U.S.: Minnesota MiningandManufacturingCompany. PolymerThinFiImsby Spin CoatingMethod.(M. Sc. Thesis), Gazi University Institute of Science, 2010, Ankara. 4,977,901., U.S.: Minnesota MiningandManufacturing Company.

Thesis),RyersonUniversityChemicalEngineering,2010,Canada. 17; 403. Thesis), RyersonUniversityChemicalEngineering,2010,Canada. 17; 403.

Fonksiyonel Nanoparçacik Içeren Hidrofilik Kaplama Solüsyonu ve Üretim Yöntemi Bulus, Özellikle medikal sektöründe 'üriner, gastrointestinal (endoskopi, kolonoskopi vb.) ve kardiyovasküler kateterler; kilavuz teller, implantlar, stentler, enjekt'orler ve membranlar gibi vücut içi uygulamalarda kullanilan birçok tibbi cihaz ve aletlerin yüzeylerine y'uksek kayganlik özelliginin kazandirilmasi amaciyla en az bir hidrofilik polimer ve/veya monomer, baslatici, solvent ve biyo uyumlu fonksiyonel nanoparçacik POSS (polihedral oligomerik silseskioksan) içeren hidrofilik kaplama solüsyonu ve üretim yöntemi ile ilgilidir. Hydrophilic Coating Solution Containing Functional Nanoparticles and Production Method The invention, especially in the medical sector, 'urinary, gastrointestinal (endoscopy, colonoscopy, etc.) and cardiovascular catheters; such as guide wires, implants, stents, injectors, and membranes High lubricity on the surfaces of many medical devices and instruments used in intra-body applications. at least one hydrophilic polymer and/or monomer, initiator, solvent and biocompatible functional nanoparticle POSS (polyhedral oligomeric silsesquioxane) It is related to the hydrophilic coating solution containing the hydrophilic coating and the production method.

Sürtünme Kuweti (N) Uzunluk (mm) Kaplamasiz substrat ----- Kaplamali substrat Sürtünme Kuweti (N) Uzunluk (mm) Friction Force (N) Length (mm) Uncoated substrate-----Coated substrate Friction Force (N) Length (mm)

Claims (1)

ISTEMLER Medikal sektöründe yer alan tibbi cihaz ve aletlerin yüzeylerinin kaplanmasinda kullanilmak 'üzere hidrofilik kaplama solüsyonu olup, özelligi; en az bir hidrofilik polimer ve/veya monomer, polihedral oligomerik silseskioksan, solvent ve baslatici içermesidir. Istem 1re uygun hidrofilik kaplama solüsyonu olup, özelligi; agirlikça %1-30 oraninda hidrofilik polimer ve/veya monomer, %O,1-5 oraninda polihedral oligomerik silseskioksan, Istem 1'e uygun hidrofilik kaplama solüsyonu olup, özelligi; bahsedilen hidrofilik polimer ve/veya monomerin; poli(vinil alkol), polivinilpirolidon, poli(etilen oksit), akrilik asit ve metakrilikasitin homo- ve kopolimerleri, maleik anhidrit bazli kopolimerler, poli(karboksilik asit), selüloz, heparin, poli(etilen glikol), kitosan, hyaluronik asit, kitin ve polilaktinler içeren gruptan seçilen bir birey veya kombinasyonlar olmasidir. Istem 1'e uygun hidrofilik kaplama solüsyonu olup, özelligi; bahsedilen solventin; metanol, etanol, propanol ve bütanol gibi alkoller veya bunlarin karisimlari, aseton, metil etil keton, tetrahidrafuran, dikolorometan, tolüen veya su olmasidir. Istem 1'e uygun hidrofilik kaplama solüsyonu olup, özelligi; bahsedilen baslaticinin; Tip 1 fotobaslaticilar,Tip 2 fotobaslaticilar veya peroksitler olmasidir. Istem 5'e uygun hidrofilik kaplama solüsyonu olup, özelligi;bahsedilen Tip 1 fotobaslaticilar; benzoin eterler, benzil ketaller, oi-dialkoksiasetofenonlar, oi- hidroksialkilfenonlar, oi-amino alkilfenonlar, asilfosfinoksitlerdir. Istem 51e uygun hidrofilik kaplama solüsyonu olup, özelligi;bahsedilen Tip 2 fotobaslaticilar; benzofenonlar/aminler, tiyoksantonIar/aminlerdir. Istem 5'e uygun hidrofilik kaplama solüsyonu olup, özelligi; bahsedilen peroksitler; hidrojen peroksit, benzoil peroksit ve kümen hidroperoksittir. Medikal sektöründe yer alan tibbi cihaz ve aletlerin yüzeylerinin kaplanmasinda kullanilmak 'üzere hidrofilik kaplama solüsyonu üretim metodu olup, özelligi; a) hidrofilik polimer ve/veya monomerin solvent içine karistirilmasi, d) elde edilen solüsyona polihedral oligomerik silseskioksan eklenerek karistirilmasi, e) elde edilen solüsyona baslaticinin eklenerek karistirilmasi, islem adimlarini içermesidir. Istem 95a uygun `üretim metodu olup, özelligi; agirlikça %1-30 oraninda hidrofilik polimer ve/veya monomer, %O,1-5 oraninda polihedral oligomerik silseskioksan, %60-95 oraninda solvent ve %O,5-20 oraninda baslatici içermesidir. Istem 9'a uygun 'üretim metodu olup, özelligi; bahsedilen hidrofilik polimer ve/veya monomerin; poli(vinil alkol), polivinilpirolidon, poli(etilen oksit), akrilik asit ve metakrilikasitin homo- ve kopolimerleri, maleik anhidrit bazli kopolimerler, poli(karboksilik asit), selüloz, heparin, poli(etilen glikol), kitosan, hyaluronik asit, kitin ve polilaktinler içeren gruptan seçilen birey veya kombinasyonlar olmasidir. Istem 9'a uygun 'üretim metodu olup, özelligi; bahsedilen solvent; metanol, etanol, propanol ve b'utanol gibi alkoller veya bunlarin karisimlari, aseton, metil etil keton, tetrahidrafuran, dikolorometan, tol'üen veya sudur. Istem 9'a uygun 'üretim metodu olup, özelligi; bahsedilen baslaticinin; Tip 1 fotobaslaticilar,Tip 2 fotobaslaticilar veya peroksitler olmasidir. Istem 13'e uygun 'üretim metodu olup, özelligi; bahsedilen Tip 1 fotobaslaticilar; benzoin eterler, benzil ketaller, o-dialkoksiasetofenonlar, d-hidroksialkilfenonlar, d-amino alkilfenonlar, asilfosfinoksitlerdir. Istem 13'e uygun `üretim metodu olup, özelligi; bahsedilen Tip 2 fotobaslaticilar; benzofenonlar/aminler, tiyoksantonIar/aminlerdir. Istem 13'e uygun üretim metodu olup, özelligi; bahsedilen peroksitler; hidrojen peroksit, benzoil peroksit ve kümen hidroperoksittir. Istem 9ia uygun `üretim metodu olup, özelligi; özelligi; bahsedilen solüsyonun oda sicakliginda ya da 40“Ciye kadar isitilarak hazirlanmasidir. Istem 9'a uygun üretim metodu olup, özelligi; bahsedilen solüsyonun tamamen seffaf hale gelene kadar karistirilmasidir.REQUIREMENTS It is a hydrophilic coating solution to be used in the coating of the surfaces of medical devices and instruments in the medical sector. comprising at least one hydrophilic polymer and/or monomer, polyhedral oligomeric silsesquioxane, solvent and initiator. It is a hydrophilic coating solution in accordance with claim 1, its feature is; It is a hydrophilic coating solution according to Claim 1, with 1-30% hydrophilic polymer and/or monomer by weight, 0.1-5% polyhedral oligomeric silsesquioxane. said hydrophilic polymer and/or monomer; poly(vinyl alcohol), polyvinylpyrrolidone, poly(ethylene oxide), homo- and copolymers of acrylic acid and methacrylic acid, copolymers based on maleic anhydride, poly(carboxylic acid), cellulose, heparin, poly(ethylene glycol), chitosan, hyaluronic acid, chitin and an individual or combinations selected from the group consisting of polylactins. It is a hydrophilic coating solution according to claim 1, its feature is; said solvent; alcohols such as methanol, ethanol, propanol and butanol or mixtures thereof, acetone, methyl ethyl ketone, tetrahydrafuran, dichloromethane, toluene or water. It is a hydrophilic coating solution according to claim 1, its feature is; said initiator; Type 1 photoinitiators, Type 2 photoinitiators or peroxides. It is a hydrophilic coating solution in accordance with claim 5, and its feature is the mentioned Type 1 photoinitiators; benzoin ethers, benzyl ketals, oi-dialkoxyacetophenones, oi-hydroxyalkylphenons, oi-amino alkylphenons, acylphosphinoxides. It is a hydrophilic coating solution in accordance with claim 51, and its feature is the mentioned Type 2 photoinitiators; benzophenones/amines, thioxantones/amines. It is a hydrophilic coating solution according to claim 5, its feature is; said peroxides; hydrogen peroxide, benzoyl peroxide and cumene hydroperoxide. It is a hydrophilic coating solution production method to be used in the coating of the surfaces of medical devices and instruments in the medical sector, and its feature is; a) mixing the hydrophilic polymer and/or monomer into the solvent, d) adding polyhedral oligomeric silsesquioxane to the obtained solution, e) mixing by adding the initiator to the obtained solution, and processing steps. It is a production method in accordance with Claim 95, and its feature is; It contains 1-30% hydrophilic polymer and/or monomer by weight, 0.1-5% polyhedral oligomeric silsesquioxane, 60-95% solvent and 0.5-20% initiator. It is a 'production method' in accordance with claim 9, and its feature is; said hydrophilic polymer and/or monomer; poly(vinyl alcohol), polyvinylpyrrolidone, poly(ethylene oxide), homo- and copolymers of acrylic acid and methacrylic acid, copolymers based on maleic anhydride, poly(carboxylic acid), cellulose, heparin, poly(ethylene glycol), chitosan, hyaluronic acid, chitin and individual or combinations selected from the group consisting of polylactins. It is a 'production method' in accordance with claim 9, and its feature is; said solvent; alcohols such as methanol, ethanol, propanol and b'utanol or mixtures thereof are acetone, methyl ethyl ketone, tetrahydrafuran, dichloromethane, toluene or water. It is a 'production method' in accordance with claim 9, and its feature is; said initiator; Type 1 photoinitiators, Type 2 photoinitiators or peroxides. It is a 'production method' in accordance with claim 13, and its feature is; said Type 1 photoinitiators; benzoin ethers, benzyl ketals, o-dialkoxyacetophenones, d-hydroxyalkylphenones, d-amino alkylphenones, acylphosphinoxides. It is a production method in accordance with claim 13, and its feature is; said Type 2 photoinitiators; benzophenones/amines, thioxantones/amines. It is a production method in accordance with claim 13, and its feature is; said peroxides; hydrogen peroxide, benzoyl peroxide and cumene hydroperoxide. It is the `production method' in accordance with claim 9, and its feature is; feature; is the preparation of the said solution at room temperature or by heating it up to 40°C. It is a production method according to claim 9, its feature is; said solution is mixed until it becomes completely transparent.
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