Keton/aldehit reçinelerinin mürekkep hazırlanmasında kullanımı
Use of keton/aldehyde resins for ink preparation
Yazar: ZEYNEP KÖKNAROĞLU
Danışman: PROF. DR. NİLGÜN KIZILCAN
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Yüksek Lisans, 2015
Konu: Kimya = Chemistry ; Kimya Mühendisliği = Chemical Engineering
Dizin: Flekso baskı = Flexo printing ; Matbaa mürekkepleri = Printing inks ; Ofset baskı = Offset printing ; Tifdruk baskı = Gravure printing

Özet:
Bu çalışmada Türkiye ve Dünyada flekso ve rotogravür baskı sistemlerinde kullanılan solvent bazlı matbaa mürekkeplerinin ham maddelerinden olan, ticari kodla satılan ancak kimyasal yapısı bilinmeyen ketonik reçinenin NMR, FT-IR, DSC analizleri yapıldı.
Elde edilen sonuçlara göre siklohekzanon formaldehit reçinenin özelliklerine benzerlik gösterdiği anlaşılmıştır. Siklohekzanon formaldehit reçinesi sentezlendi. Sentezlenen siklohekzanon formaldehit reçinenin FT-IR, NMR analizleri yapılmıştır. 
Mürekkep ve boya endüstrisinde ketonik reçine ile parlaklık, adhezyon, pigment ıslatıcılığı gibi alanlarda paralel görevde kullanılan teknik bilgi formunda aldehit reçine olduğu belirtilen Laropal A81'in NMR ve FT-IR analizleri yapılarak, laboratuarda sentezlediği siklohekzanon  formaldehit reçinesi ve ticari olarak satışı yapılan ketonik reçineden mürekkep verniği ve mürekkep hazırlanmış ve standart testleri yapılarak performans karşılaştırılmaları yapılmıştır.
Reçinelerin mürekkep üretiminde kullanılabilmesi için baskı sistemine uygun özellik gösterebilmeleri gerekmektedir. Bunun için reçinelerin çeşitli solventlerde çözünmesi incelenmiştir. Ayrıca, vernik testinde,  %50lik reçine ve Izo propil alkol çözeltileri hazırlanarak, çözünürlük hızları incelenmiştir. Hazırlanan verniklerin ASTM standartlarına göre, D1200-10 viskozite, D523 parlaklık, F 2496 çizilme, D3359-97 adhezyon testleri yapılmıştır. 
Solvent bazlı flekso ve rotogravür mürekkeplerinde ana bağlayıcı olarak Nitro selüloz (NC) veya poliamid (PA) reçine kullanılır. Keton aldehit reçineleri performans arttırıcı katkı reçinesi olarak kullanılır. Laropal A 81'in mürekkep formülasyonunda ticari ketonik reçine ve deneysel olarak üretilen CFR ile kıyaslaması yapılırken, poliamid bazlı mürekkepler tercih edilmiştir. ASTM standartlarına göre, adezyon, viskozite, çizilme ve parlaklık testleri yapılmıştır. 
Sonuç olarak, ticari olarak ülkemizde mürekkep sektöründe tüketilen UK 100/500 keton reçinenin, siklohekzanon formaldehit reçine olduğu tespit edilmiştir. Üretilen CFR 'nin endüstriyel analizlerinde, ticari reçine ile viskozite dışında farklılık olmadığı tespit edilmiştir. Sentezlenen reçine, viskozite düşüklüğünden dolayı, daha çok flekso baskı sırasında mürekkep viskozitesini düşürücü amaçla kullanılan vernik üretimi için uygundur. Diğer yandan Laropal A 81'in ketonik reçineye göre çizilme direncinin daha iyi, parlaklığının ve viskozitenin daha düşük olduğu tespit edilmiştir. Böylece, sentezlediğimiz ketonik reçinenin ve piyasadaki rakiplerinin solvent bazlı flekso mürekkeplerindeki görev ve fonksiyonları incelenmiştir.

Abstract:
Packaging and ink industries are interested in eachother. Innovations in the packaging industry affect the production of ink and printing directly. In our country, ink production is developing with the packaging industry. Packaging is the technology of enclosing or protecting products for distribution, storage, sale, and use. Packaging also refers to the process of design, evaluation, and production of packages. It can be described as a coordinated system of preparing goods for transport, warehousing, logistics, sale, and end use which contains, protects, preserves, transports, informs, and sells. In many countries it is fully integrated into government, business, institutional, industrial, and personal use. On the other hand, printing is a process for reproducing text and images using a master form or template. The earliest examples include cylinder seals and other objects such as the Cyrus Cylinder and the Cylinders of Nabonidus. The earliest known form of woodblock printing came from China dating to before 220 A.D. Later developments in printing include the movable type, first developed by Bi Sheng in China. The printing press, a more efficient printing process for western languages with their more limited alphabets, was developed by Johannes Gutenberg in the fifteenth century. 
Printing systems used in packaging materials, production technologies are analyzed at four groups; Letterpress printing, flexographic printing, rotogravure printing, the offset printing system.
Printing inks must be transported from a reservoir and then in a printing-process-specific manner onto the substrate. The inks must dry or cure on the substrate. Here, differentiation is basically made between physical (absorption, evaporation) and chemical drying (oxidation, radiation curing) procedures.Very often a combination of the drying processes is applied. Solidification drying represents a special characteristic whereby inks are fluid in a hot state and then solid after cooling, for instance, hot embossing . The ink must have good adhesion to the substrate.
There are four types ink is used in printing systems. These are water based, solvent based, oil-based inks and UV curing ink. The raw materials forming of ink are determined the printing surface and the print type.
In the water-based ink, solid content is about 45 to 35%. The solids are dispersed in water. It is not flammable, environmentally friendly. There are pigments for water-based ink (organic, inorganic), binder (styrene acrylate, solutions ...), solvents (water, alcohols, glycols ...), ingredients (waxes, defoamers, cross -link the fillers ..) are used.
Water-based inks are usually used on only paper / cardboard surfaces. Water-based inks used in flexographic printing systems suitable drying rate of the printing speed. Because water is the solvent of the ink type and the evaporation speed is slower compared to other organic solvents. 
In solvent-based ink, solid content is around 20-25%, and this contribution is soluble in the solvent. In solvent-based inks, There are pigments (organic and inorganic), binder (nitrocellulose, polyamide, polyvinyl butyral ...), solvent (IPA, ethanol, ethyl acetate, glycol ether, ...), additives (wax, plasticizer, cross-linker ... ) is used. Evaporation and drying are quickly, are flammable, is ideal for film and foil printing, can be dried with hot and dry air at high speed. Also, In solvent-based inks are used for both flexo and rotogravure printing type.
UV inks are the latest technology. There is no need drying, no gas and liquid waste. It is liquid until exposed to UV radiation even though made up of solids. Density is stable, has excellent ink stability. Colors are bright and soft. The disadvantages are that these inks cost more than conventional printing inks, dryer design is at a high technical level, increased ink handling demands for reasons of health and safety.
The UV-cured inks, remains open to development is a new technology. The use of solvent-based inks are available in a wide area. Its evaporation rates is higher than Water based but slower curing time than UV curing ink,  non-environmentalists, but is the most common type of ink all over the world.
There are four main ingredients that make up the ink. These are binder (resin), pigments, solvents and additives. As the main binder is generally in Turkey and abroad nitrocellulose and polyamide resins are used. Furthermore, various additives resins are used to increase the for the adhesion to the surface, brightness and scratch resistance.
Ketonic resins, solvent-based flexographic or rotogravure printing inks used in the printing system is an additive used in addition to the main binder resin or PE resin NC. Brightness provides significant contributions to the pigment wetting and adhesion system.
In Turkey, Ketonic resins are used as additive resin to increase system functions. All ketonic resins are imported products. So, it gives no information about chemical structure of ketonic resin type. 
It is aimed to produce and compare all functions of our own ketonic resin the chemical structure of the imported ketonic resin, under laboratory conditions. Also, the generated CF resins and commercial ketonic resins with aldehyde resins used in the market were compared in the current PE ink formulations.
In this study, NMR, FT-IR, DSC analysis of ketonic resin were performed which is sold as commercial codes and unknown chemical structure, is used  one of the important raw materials in flexographic and fotogravure printing systems around the world and Turkey. Also, ıt was also measured OH value of commercial resin.
According to the obtained results was found to be similar to the characteristics of cyclohexanone-formaldehyde resin. Therefore, cyclohexanone-formaldehyde resins was synthesized. Synthesis of cyclohexanone formaldehyde resin FT-IR, NMR analyzes were performed. Also, ıt was also measured OH value of the two resins too.
It was performed of NMR, FT-IR analyzes of Laropal A81 which is in the same function and usages with ketonic resin at the some different areas like brightness, adhesion, pigment wetting in ink and paint industry. Also Laropal A 81 is compared of functions with cyclohexanone-formaldehyde resins which is synthesized  on  laboratory conditions and sales as commercial resin in PA ink formulations. 
The setting of the consistency of a printing ink has a decisive influence on the productivity and quality of a print job. The consistency can be classified into various individual properties and should be adjusted to match specific printing presses, substrates, printing subjects, speed, and so forth, as optimally as possible.
In ink tests, There are some important tests that applied on surface that used for ink. These are viscosity, brightness, adhesion and scratch tests that makes ink high quality. 
In solvent based ınk ındustry for flexographic or rotographic printing system, There are two main resin for using which is polyamide or nitrocelulose. Other resins which is keton or aldehit resins are using as resin additives. It is important that resin additives have high quality makes inks at high quality. It must be suitable of resins for printing inks and printing systems in order to be right to be high quality which is required. Solubility in various solvents for this resin was examined. Further, in the test varnish,  resin and iso propyl alcohol solution was prepared as 50%, solubility rate was examined. The prepared varnishes are tested  according to ASTM standards  D1200-10 viscosity, D523 brightness, F 2496 scratch, D3359-97adhesion tests.
While Laropal A 81 is compared to other ketonic resins in ink formulations, It is prepared in polyamide resin based inks. Also according to ASTM standards brightness, adhesion, viscosity and a scratch tests are performed .
As a result, there is no difference expect viscosity between commercially ketonic resin which is consuming in Turkey and around the world and  CFR which is producing on laboratory conditions. Synthesis of the resin due to low viscosity, suitable for the production of more flexographic varnish used for the purpose of lowering the viscosity of the ink during printing. On the other hand, scratch resistance of Laropal A 81 is better than CFR but viscosity and brightness of Laropal A 81 are lower than CFR. Thus, duties and functions of ketonic resin and ıts competitors in the market have had examined.