WO2012027806A1 - Solvent composition for printing inks, varnishes and thinners - Google Patents
Solvent composition for printing inks, varnishes and thinners Download PDFInfo
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- WO2012027806A1 WO2012027806A1 PCT/BR2011/000217 BR2011000217W WO2012027806A1 WO 2012027806 A1 WO2012027806 A1 WO 2012027806A1 BR 2011000217 W BR2011000217 W BR 2011000217W WO 2012027806 A1 WO2012027806 A1 WO 2012027806A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
Definitions
- the present invention relates to the solvent composition for printing inks and varnishes which provide for the reduction of evaporative solvent losses and the formation of low atmosphere pollutants employing alkyl acetates such as sec-butyl acetate as well as mixtures of solvents containing synthetic or natural alcohols, glycol ethers and ketones.
- solvent compositions employed in the manufacture of inks, varnishes or thinners comprising solvents or diluents such as: Ethyl Acetate, Isopropanol, Monopropylene Glycol and Monoethylene Glycol Ether, Ethanol Diacetone alcohol, n-Butanol, iso-Butanol or mixtures thereof.
- solvents or diluents such as: Ethyl Acetate, Isopropanol, Monopropylene Glycol and Monoethylene Glycol Ether, Ethanol Diacetone alcohol, n-Butanol, iso-Butanol or mixtures thereof.
- VOCs Volatile Organic Compounds
- NOx nitrogen oxides
- the so-called low terrestrial atmosphere is the region where there is a great diversity of living beings and the presence of ozone causes severe damage to the respiratory system.
- the existence of ozone in the upper atmosphere is desirable for blocking ultraviolet radiation from the sun, but undesirable in the lower atmosphere due to ozone toxicity to humans and other living things.
- VOCs are carbon-based substances that evaporate quite easily, so most industrial solvents fit this definition. These may or may not have harmful effects on human life.
- the intensity of problems generated by VOCs depends on the type of substance, the amount emitted and the time of exposure to live.
- Volatile organic compounds are emitted from various sources, such as automobile exhaust, industrial processes, consumer products, paints and coatings, among others.
- the coatings industry contributes a small portion of VOC compound emissions and in these applications solvents account for the majority of emissions.
- VOC concept for determining the amount of solvent classified as VOC and / or the photochemical reactivity concept of the volatile fraction of the formulation based on the ozone formation potential of a given VOC under atmospheric conditions apply. NOx concentrations and concentrations.
- MIR Maximum Incremental Reactivity
- CARB California Air Resources Board
- VOCs have different photochemical reactivity producing more or less ozone.
- MIRs are not equal between solvents and the development of solvents and formulations with low MIR compounds is a necessary demand for the evolution of paint formulations.
- Absorption by the body can occur in different ways, the most important being airways (inhalation), skin (adsorption) or ingestion. In the case of paint, varnish and solvent applications, the most important is inhalation absorption.
- a common effect resulting from exposure to a sufficient amount of many organic solvents is the widespread depression of central nervous system functions, and the severity of this effect may progress with continued exposure. In the vast majority of causes of exposure, their effects can be reversed after removal of exposure. This is because the human body is capable of metabolizing and eliminating the typical amounts of solvents we are exposed to in our homes, in the workplace and others.
- TLV® Threshold Limit Values
- Time-Weighted Average which is the time-weighted average concentration for a normal worker of 8 hours a day and 40 hours a week, to which virtually all workers can be repeatedly exposed without harming their health.
- ACGIH® American Conference of Governmental Industrial Hygienists— USA
- IR hazard index
- s very solvent-rich atmosphere
- TE Evaporation Rate
- Evaporation Rate is the ratio of the 90% evaporation time of a solvent to the 90% evaporation time of the n-Butyl acetate standard solvent. That is, the higher the evaporation rate, the more volatile the solvent.
- a solvent composition has been developed for flexographic printing inks, varnishes or thinners, capable of replacing traditional market solvents or thinners, with the advantages of significantly reducing the emission of solvents into the atmosphere, reducing the potential for ozone formation in low atmosphere and less negative impact on humans.
- the invention deals with the use of solvents obtained from renewable sources and which also contribute to the reduction of the potential for environmental damage of the products employed in this market.
- the paint and varnish composition of the invention comprises an alkyl acetate formulation such as sec-butyl acetate which has an average evaporation rate and when combined with natural or synthetic alcohols and optionally with a glycol ether or a ketone exhibits stability and balanced evaporation during application significantly reducing the emission of volatile organic compounds "VOC" significantly reducing the need for solvent replacement in the application system due to evaporative losses without altering the important properties of the painting system such as stability, formation of film and solvent retention in packing.
- alkyl acetate formulation such as sec-butyl acetate which has an average evaporation rate and when combined with natural or synthetic alcohols and optionally with a glycol ether or a ketone exhibits stability and balanced evaporation during application significantly reducing the emission of volatile organic compounds "VOC" significantly reducing the need for solvent replacement in the application system due to evaporative losses without altering the important properties of the painting system such as stability, formation of film and solvent retention in packing.
- a solvent composition for paints and varnishes comprising alkyl acetates such as sec-butyl acetate, alcohols and glycol ethers has been developed, showing low VOC emission during the application process.
- the paint formulations are prepared from the combination of the sec-butyl acetate with other solvents to balance solvency and evaporation properties, which meet the requirements of drying, flowability, film leveling, mechanical strength, gloss and bleach resistance, among other requirements.
- Organic polymer films are generally produced by applying a solution or dispersion to the substrate followed by evaporation of the solvent with film formation by drying or coalescing.
- the solvent system plays a key role in controlling the solubility of the resins and the drying rate, which will therefore have a strong influence on the final properties of the coating.
- solubility of a polymer in a certain solvent is understood by semi-empirical models using so-called solubility parameters. These models consider the solubility of a molecule in a solvent from the relationship between solvent and solute solubility parameters, and the closer these values (solvent and solute) the better the system solubility. Thus, the model guides by the selection and development of systems capable of providing the solubilization of resins. Table 1 shows the solubility radius of different types of resins compared to the solubility radius provided by interaction with sec-butyl acetate. In the development work we studied these interactions and solvent compositions with the new product.
- Table 1 Required solubility radii of different resins compared to sec-butyl acetate solubility radius.
- the second relevant parameter for application development is related to the volatility or evaporation rate of the solvent, and its behavior in mixtures with other system solvents. These characteristics are also modeled from the physical properties and molecular interaction between different substances.
- Table 2 presents the properties of different solvents. Boiling point and evaporation rate characterize the product (sec-butyl acetate) in the group of medium evaporating solvents, boiling between 100 and 150 ° C.
- Table 2 Physicochemical properties of different solvents compared to sec-butyl acetate.
- a composition has been developed which can employ sec-butyl acetate found in the trade name Ultrasolve M1200 with excellent solvency power and low reactivity for low atmosphere ozone formation in combination with alcohols such as ethanol, sec-butanol and Isopentanol, It can be used in different formulations of inks, varnishes and thinners for printing as a substitute for traditional solvent formulations such as Ethyl Acetate, Propylene Glycol Monomethyl Ether, Isopropanol, Diacetone Alcohol, n-Butanol, considerably reducing the environmental impact and being end-product solvency and evaporation properties suitable for the intended applications.
- compositions for paints, varnishes or thinners may be adaptable to various types of formulations from the formulation balance to obtain the required evaporation rate and dissolution properties of the polymers employed.
- the formulations may be prepared by any usual method for mixing solvents and / or formulating paints, varnishes and thinners.
- Gains in solvent replacement due to evaporation during agitation range from 5% to 30% compared to industry standards.
- the present invention provides a composition for printing inks, varnishes or thinners, which comprises a balanced mixture of solvents based on alkyl acetates, synthetic or natural alcohols, glycol ethers and ketones capable of reducing evaporative solvent loss and low atmosphere pollutant formation.
- the composition comprises alkyl acetates of 3 to 5 carbon atoms in an amount ranging from 5 to 40% by weight. pasta. In another preferred embodiment, the composition comprises sec-butyl acetate in an amount ranging from 5 to 40% by weight. In another preferred embodiment, the composition comprises a balanced mixture of alcohol-based solvents of 2 to 5 carbon atoms with 5 to 70% by weight alcohols of linear and / or branched structures. In another preferred embodiment, the composition comprises a balanced mixture of alcohol-based solvents with 30 to 70% by weight of ethyl alcohol. In another further preferred embodiment, the composition comprises a balanced mixture of alcohol-based solvents with 5 to 50% by weight of sec-butyl alcohol.
- the composition comprises a balanced mixture of ketone-based solvents of 3 to 5 carbon atoms and 1 to 30% by weight. In another preferred embodiment, the composition comprises a balanced mixture of 1 to 40% by weight glycol ether based solvents. In another preferred embodiment, the composition comprises a balanced mixture of glycol ether based solvents with from about 1 to 40% by weight of glycol ethers derived from ethylene oxide or propene oxide.
Abstract
The present invention relates to a solvent composition for printing inks, varnishes and thinners, which contains alkyl acetates, particularly sec-butyl acetate, as well as a mixture thereof with natural or synthetic alcohols and optionally a glycol ether or ketone, said solvent composition providing an alternative solvent system with balanced evaporation, considerably decreasing VOC (volatile organic compound) emission and solvent replenishment during the process of applying same.
Description
COMPOSIÇÃO DE SOLVENTES PARA TINTAS, VERNIZES E TÍNERES DE IMPRESSÃO COMPOSITION OF SOLVENTS FOR INKS, VARNISHES AND PRINTING TINES
Campo de Aplicação Application field
A presente invenção refere-se à composição de solventes para tintas e vernizes de impressão que proporcionam a redução de perdas de solventes por evaporação e da formação de poluentes em baixa atmosfera empregando acetatos de alquila como por exemplo o acetato sec-butila bem como misturas de solventes contendo alcoóis sintéticos ou naturais, éteres glicólicos e cetonas. The present invention relates to the solvent composition for printing inks and varnishes which provide for the reduction of evaporative solvent losses and the formation of low atmosphere pollutants employing alkyl acetates such as sec-butyl acetate as well as mixtures of solvents containing synthetic or natural alcohols, glycol ethers and ketones.
Fundamentos da invenção Fundamentals of the invention
Nas literaturas e patentes dispomveis sobre o assunto é possível observar trabalhos relativos a substituição de solventes convencionais por solventes com baixa reatividade fotoquímica ou reatividade negligenciável (US 6.506.243; US 2002/0115781 ), formulações de tintas de impressão contendo ésteres e alcoóis como solvente para a obtenção de melhor controle de secagem (US 6.444.019). Porém não há trabalhos com a importância do propósito de formulações equilibradas de solventes para alcançar a diminuição de emissões de solventes durante o processo de aplicação de tintas de impressão e consequentemente a diminuição da formação de poluentes (ozônio) devido a reatividade fotoquímica dos solventes utilizados. In the available literature and patents on the subject, it is possible to observe works on the replacement of conventional solvents with solvents with low photochemical reactivity or negligible reactivity (US 6,506,243; US 2002/0115781), ink formulations containing esters and alcohols as a solvent. for better drying control (US 6,444,019). However, there is no work with the importance of the purpose of balanced solvent formulations to achieve the reduction of solvent emissions during the printing ink application process and consequently the reduction of pollutant formation (ozone) due to the photochemical reactivity of the solvents used.
A patente norte-americana US 6.506.243, "Environmentally preferred fluids and fluid blends" da ExxonMobil Chemical de maio/1999, trata e reivindica a substituição de solventes convencionais por solventes com baixa reatividade fotoquímica tais como ésteres, ésteres-álcool e carbonatos, reduzindo a formação de ozônio na troposfera e de baixa toxidade na aplicação industrial incluindo tintas de modo geral.
O pedido de patente norte-americano publicado como US 2002/0115781, "Coatings and inks based on solvents having negligible photochemical reactivity" da ARCO Chemical Tecnology de agosto/2002, trata e reivindica o uso de acetato de t-butila e outros solventes sendo benzoato de metila, trifluoracetato de metila, carbonato dimetila, pivalato de metila, t-bitanol, carbonato de propileno, benzoato de t-butila, carbonato de di-t-butila, carbonato de metil t- butila e nitroalcanos, utilizados em formulações de tintas para madeira, automotiva OEM, repintura automotiva, impressão, industrial geral, que apresentem baixo índice de VOC com base na reatividade fotoquímica. US Patent 6,506,243, ExxonMobil Chemical's Environmentally Preferred Fluids and Fluid Blends of May 1999, treats and claims the replacement of conventional solvents with low photochemical reactivity solvents such as esters, alcohol esters and carbonates, reducing ozone formation in the troposphere and low toxicity in industrial application including paints in general. US Patent Application published as US 2002/0115781, "Coatings and Inks based on solvents having negligible photochemical reactivity" from ARCO Chemical Technology of August 2002, treats and claims the use of t-butyl acetate and other solvents being methyl benzoate, methyl trifluoracetate, dimethyl carbonate, methyl pivalate, t-bitanol, propylene carbonate, t-butyl benzoate, di-t-butyl carbonate, methyl t-butyl carbonate and nitroalkanes used in wood paints, automotive OEM, automotive refinish, printing, general industrial, low VOC based on photochemical reactivity.
A patente norte-americana US 6.444.019, "Ink jet ink composition" da Videojet Technologies de setembro/2002, trata e reivindica formulações específicas de tinta de impressão ink jet para substratos não poros contendo solventes, resinas e corantes tradicionais assim como óleos secativos, não secativos e semi-secativos, com vantagens de secagem rápida sem causar entupimentos nos bicos de impressão. Videojet Technologies' US Patent 6,444,019, "Inkjet ink composition" of September 2002, treats and claims specific formulations of inkjet print ink for non-porous substrates containing traditional solvents, resins and dyes as well as drying oils. non-drying and semi-drying, with advantages of fast drying without causing clogging on the print nozzles.
O homem da técnica já conhece composições de solventes empregados na fabricação de tintas, vernizes ou tíneres, em particular as tintas de impressão flexográficas e rotográficas, compreendendo solventes ou diluentes como: Acetato de Etila, Isopropanol, Eter Glicólico do monopropilenoglicol e do monoetilenoglicol, Etanol, Diacetona álcool, n-Butanol, iso-Butanol, ou ainda suas misturas. Estes compostos, quando empregados na fabricação de tintas, vernizes ou tíneres para tintas de impressão apresentam a desvantagem de apresentarem grandes diferenças de taxas de evaporação, provocando desbalanceamento da formulação e emissão para atmosfera de solventes de alta volatilidade durante o processo de aplicação.
Tão importante quanto ao poder de solvência para uma série de aplicações dos solventes industriais pode-se citar o comportamento de evaporação na qual ocorre através da troca de calor do solvente com o meio, incluindo o substrato. Quanto menor a pressão exercida sobre a superfície de um líquido, mais fácil é a vaporização, pois as moléculas do líquido encontram menor resistência para abandoná-lo e transformar-se em vapor. A velocidade de evaporação de cada solvente é um fator essencial para o desenvolvimento de uma formulação com evaporação equilibrada, porém o grande desafio está na adaptação para atender às condições de aplicação, formação de filme, compatibilidade com a resina, estabilidade entre outras, garantindo assim a qualidade da tinta durante e após sua aplicação. The person skilled in the art is aware of solvent compositions employed in the manufacture of inks, varnishes or thinners, in particular flexographic and rotographic printing inks, comprising solvents or diluents such as: Ethyl Acetate, Isopropanol, Monopropylene Glycol and Monoethylene Glycol Ether, Ethanol Diacetone alcohol, n-Butanol, iso-Butanol or mixtures thereof. These compounds, when used in the manufacture of inks, varnishes or thinners for printing inks, have the disadvantage of presenting large differences in evaporation rates, leading to formulation unbalance and atmospheric emission of high volatile solvents during the application process. As important as the solvency power for a number of industrial solvent applications is the evaporation behavior in which it occurs through heat exchange of the solvent with the medium, including the substrate. The lower the pressure exerted on the surface of a liquid, the easier it is to vaporize, because the molecules of the liquid find less resistance to abandon it and turn into vapor. The evaporation rate of each solvent is an essential factor for the development of a balanced evaporation formulation, but the major challenge lies in adapting to suit application conditions, film formation, resin compatibility, stability and so on. ink quality during and after application.
Na presente invenção são apresentados ganhos no uso de formulações específicas de solventes em relação às perdas por evaporação na aplicação e aos impactos ambientais e humano, relacionados com a formação de ozônio na troposfera (baixa atmosfera terrestre) e os limites de exposição ao usuário. In the present invention there are presented gains in the use of specific solvent formulations in relation to evaporative losses in application and environmental and human impacts related to the formation of ozone in the troposphere (low terrestrial atmosphere) and exposure limits to the user.
A formação de ozônio na troposfera é originada da reação fotoquímica entre compostos orgânicos voláteis, chamados de VOCs (sigla em inglês para "Volatile Organic Compounds") e os óxidos de nitrogénio (NOx) presentes na atmosfera. A chamada baixa atmosfera terrestre é a região onde estão a grande diversidade de seres vivos e a presença do ozônio acarreta danos severos ao sistema respiratório. A existência de ozônio em alta atmosfera é desejável para o bloqueio da radiação ultravioleta do sol, mas indesejável na baixa atmosfera devido a toxicidade do ozônio ao ser humano e outros seres vivos.
Os VOCs são substâncias derivadas do carbono que evaporam com certa facilidade, desta forma a maioria dos solventes industriais enquadra-se nesta definição. Estes podem ou não apresentar efeitos danosos à vida humana. A intensidade de problemas gerados pelos VOCs depende do tipo de substância, da quantidade emitida e do tempo de exposição ao ser vivo. Ozone formation in the troposphere originates from the photochemical reaction between volatile organic compounds, called VOCs (Volatile Organic Compounds) and the nitrogen oxides (NOx) in the atmosphere. The so-called low terrestrial atmosphere is the region where there is a great diversity of living beings and the presence of ozone causes severe damage to the respiratory system. The existence of ozone in the upper atmosphere is desirable for blocking ultraviolet radiation from the sun, but undesirable in the lower atmosphere due to ozone toxicity to humans and other living things. VOCs are carbon-based substances that evaporate quite easily, so most industrial solvents fit this definition. These may or may not have harmful effects on human life. The intensity of problems generated by VOCs depends on the type of substance, the amount emitted and the time of exposure to live.
Os compostos orgânicos voláteis são emitidos através de várias fontes, como por exemplo, escapamentos de automóveis, processos industriais, produtos de consumo, tintas e revestimentos, dentre outros. A indústria de revestimentos contribui com uma pequena porção da emissão de compostos VOC e nestas aplicações os solventes correspondem à maioria das emissões. Volatile organic compounds are emitted from various sources, such as automobile exhaust, industrial processes, consumer products, paints and coatings, among others. The coatings industry contributes a small portion of VOC compound emissions and in these applications solvents account for the majority of emissions.
Para as formulações de tintas e vernizes são aplicáveis o conceito de VOC para determinação da quantidade de solvente classificada como VOC e/ou o conceito da reatividade fotoquímica da fração volátil da formulação, baseada no potencial de formação de ozônio de um determinado VOC sob condições atmosféricas específicas e concentrações de NOx. For paint and varnish formulations the VOC concept for determining the amount of solvent classified as VOC and / or the photochemical reactivity concept of the volatile fraction of the formulation based on the ozone formation potential of a given VOC under atmospheric conditions apply. NOx concentrations and concentrations.
O potencial de formação de ozônio é então expresso como reatividade incremental máxima ou MIR (sigla em inglês para "Maximum Incremental Reactívity"). O valor de MIR é expresso em gramas de ozônio formado por grama de VOC (g03/gVOC). Ozone formation potential is then expressed as Maximum Incremental Reactivity (MIR). The MIR value is expressed in grams of ozone formed by grams of VOC (g0 3 / gVOC).
VOCs + NO(x) + O2 + Luz→ O3 (principal poluente) + HNO3 + Compostos Orgânicos VOCs + NO (x) + O2 + Light → O3 (main pollutant) + HNO3 + Organic Compounds
Este método foi introduzido no estado da Califórnia nos EUA através do Califórnia Air Resources Board (CARB) que reconheceu grande
eficiência na redução do potencial de formação de ozônio de formulações de tintas utilizando o MIR como parâmetro. Este conceito está avançando para a regulamentação de VOCs em tintas nos EUA, de modo especial para as tintas aplicadas por sistema de pulverização. This method was introduced in the US state of California through the California Air Resources Board (CARB) which recognized large efficiency in reducing the ozone formation potential of paint formulations using MIR as a parameter. This concept is moving towards the regulation of VOCs in paint in the US, especially for spray system inks.
Os VOCs possuem reatividades fotoquímicas diferentes produzindo mais ou menos ozônio. Desta forma, os "MIRs" não são iguais entre os solventes e o desenvolvimento de solventes e formulações com compostos de baixo MIR é demanda necessária para a evolução das formulações de tintas. VOCs have different photochemical reactivity producing more or less ozone. Thus, "MIRs" are not equal between solvents and the development of solvents and formulations with low MIR compounds is a necessary demand for the evolution of paint formulations.
Entretanto, o limite de exposição aos solventes se faz necessário devido à apresentação de problemas indesejáveis à saúde humana quando absorvidos pelo organismo. Os efeitos tóxicos podem dar-se diferentemente dependendo da forma de exposição como uma irritação à área de contato ou sistemático devido à absorção do solvente no fluxo sanguíneo, podendo ser rapidamente reversíveis ou se estenderem por tempo mais prolongado dependendo do caso. However, the limit of exposure to solvents is necessary due to the presentation of undesirable human health problems when absorbed by the body. Toxic effects may occur differently depending on the form of exposure as irritation to the contact area or systemic due to the absorption of the solvent into the blood stream and may be rapidly reversible or extend over a longer period depending on the case.
A absorção pelo organismo pode acontecer de diferentes formas sendo as mais importantes por vias respiratórias (inalação), pele (adsorção) ou por ingestão. No caso de aplicações de tintas, vernizes e solventes, o mais importante é a absorção por inalação. Absorption by the body can occur in different ways, the most important being airways (inhalation), skin (adsorption) or ingestion. In the case of paint, varnish and solvent applications, the most important is inhalation absorption.
Um efeito comum decorrente da exposição a uma quantidade suficiente de muitos solventes orgânicos é a depressão generalizada das funções do sistema nervoso central, sendo que a severidade deste efeito pode progredir com a exposição contínua.
Na grande maioria das causas de exposição, seus efeitos podem ser revertidos após a remoção da exposição. Isto porque o organismo humano é capaz de metabolizar e eliminar as quantidades típicas de solventes a que estamos expostos em nossas casas, no ambiente de trabalho entre outros. A common effect resulting from exposure to a sufficient amount of many organic solvents is the widespread depression of central nervous system functions, and the severity of this effect may progress with continued exposure. In the vast majority of causes of exposure, their effects can be reversed after removal of exposure. This is because the human body is capable of metabolizing and eliminating the typical amounts of solvents we are exposed to in our homes, in the workplace and others.
A exposição do público geral a solventes através do uso normal de produtos de consumo raramente leva a efeitos nocivos. Portanto, desde que manuseados de forma recomendada e armazenados de maneira adequada, e dentro dos limites de exposição, os solventes podem ser utilizados com segurança. General public exposure to solvents through normal use of consumer products rarely leads to harmful effects. Therefore, provided that they are handled appropriately and stored properly, and within exposure limits, solvents may be used safely.
Para garantir a segurança dos funcionários, em ambientes de trabalho são recomendados limites de concentrações de solventes no ar em ambientes de trabalho na qual são chamados de "Threshold Limit Values" (TLV®). Os valores mais comuns publicados são os valores de TLV - TWA®To ensure the safety of employees, in working environments limits of solvent concentrations in the air are recommended in working environments where they are called "Threshold Limit Values" (TLV®). The most common published values are TLV - TWA® values.
^Time-Weighted Average") que é a concentração média ponderada no tempo, para um trabalhador normal de 8 horas diárias e 40 horas semanais, à qual praticamente todos os trabalhadores podem ser repetidamente expostos sem prejudicar a sua saúde. A ACGIH® {American Conference of Governmental Industrial Hygienists— EUA) é um exemplo de órgão que disponibiliza informações de TLV® para diversos compostos, sendo uma das maiores referências mundiais. ^ Time-Weighted Average "), which is the time-weighted average concentration for a normal worker of 8 hours a day and 40 hours a week, to which virtually all workers can be repeatedly exposed without harming their health. ACGIH® {American Conference of Governmental Industrial Hygienists— USA) is an example of a body that provides TLV® information for a variety of compounds, and is one of the world's largest references.
Considerando o TLV - TWA® estabelecido pela ACGIH®, é possível verificar o índice de risco de uso dos solventes. Considering the TLV - TWA® established by ACGIH®, it is possible to verify the solvent use risk index.
O IR (índice de risco) é o perigo provocado por uma atmosfera muito rica em solvente(s) e está ligado à concentração deste(s) no ar. E função entre
o TLV® e sua respectiva Taxa de Evaporação (TE). IR (hazard index) is the hazard caused by a very solvent-rich atmosphere (s) and is linked to its concentration (s) in air. And function between TLV® and its respective Evaporation Rate (TE).
A Taxa de Evaporação é a razão do tempo de evaporação de 90% de um solvente pelo tempo de evaporação de 90% do solvente padrão Acetato de n- Butila. Ou seja, quanto maior a taxa de evaporação, mais volátil é o solvente. Evaporation Rate is the ratio of the 90% evaporation time of a solvent to the 90% evaporation time of the n-Butyl acetate standard solvent. That is, the higher the evaporation rate, the more volatile the solvent.
Objetivos ou Vantagens da Invenção Objectives or Advantages of the Invention
Foi desenvolvida composição de solventes para tintas, vernizes ou tíneres para tinta de impressão flexográfica, capacitada para substituir os solventes ou diluentes tradicionais de mercado, com as vantagens da diminuição significativa na emissão de solventes para a atmosfera, diminuição do potencial de formação de ozônio em baixa atmosfera e menor impacto negativo ao ser humano. A solvent composition has been developed for flexographic printing inks, varnishes or thinners, capable of replacing traditional market solvents or thinners, with the advantages of significantly reducing the emission of solvents into the atmosphere, reducing the potential for ozone formation in low atmosphere and less negative impact on humans.
Adicionalmente a invenção trata da utilização de solventes obtidos a partir de insumos de fontes renováveis e que também contribuem para a redução do potencial de dano ao meio ambiente dos produtos empregados neste mercado. Additionally the invention deals with the use of solvents obtained from renewable sources and which also contribute to the reduction of the potential for environmental damage of the products employed in this market.
Descrição Resumida da Invenção Brief Description of the Invention
A composição para tintas e vernizes de que trata a invenção compreende uma formulação com acetato de alquila como por exemplo o acetato sec-butila que possui taxa de evaporação média e quando combinado com álcoois naturais ou sintéticos e eventualmente com um éter de glicol ou uma cetona apresenta estabilidade e evaporação equilibrada durante aplicação diminuindo significativamente a emissão de compostos orgânicos voláteis "VOC" diininuindo consideravelmente a necessidade de reposição de solventes no sistema de aplicação devido às perdas por evaporação sem alterar as propriedades importantes do sistema de pintura tais como estabilidade, formação de filme e retenção de solvente na
embalagem. The paint and varnish composition of the invention comprises an alkyl acetate formulation such as sec-butyl acetate which has an average evaporation rate and when combined with natural or synthetic alcohols and optionally with a glycol ether or a ketone exhibits stability and balanced evaporation during application significantly reducing the emission of volatile organic compounds "VOC" significantly reducing the need for solvent replacement in the application system due to evaporative losses without altering the important properties of the painting system such as stability, formation of film and solvent retention in packing.
Descrição Detalhada da Invenção Detailed Description of the Invention
Foi desenvolvida composição de solventes para tintas e vernizes compreendendo acetatos de alquila como por exemplo o acetato de sec-butila, alcoóis e éteres glicólicos, apresentando baixa emissão de VOC durante o processo de aplicação. A solvent composition for paints and varnishes comprising alkyl acetates such as sec-butyl acetate, alcohols and glycol ethers has been developed, showing low VOC emission during the application process.
O acetato de sec-butila pode ser obtido através da produção industrial por rota de esterificação direta, conforme mostrado abaixo: Sec-butyl acetate can be obtained through industrial production by direct esterification route as shown below:
Essa rota apresentou um desafio importante na inibição de reações paralelas, comuns a alcoóis secundárias nas condições normais de reação, como a geração de butenos e éteres do sec-butanol, que levariam a dificuldades em atingir as especificações e maior consumo energético em processos de purificação, além da geração de resíduos de fabricação. This route presented an important challenge in inhibiting parallel reactions common to secondary alcohols under normal reaction conditions, such as the generation of butenes and sec-butanol ethers, which would lead to difficulties in meeting specifications and higher energy consumption in purification processes. , in addition to the generation of manufacturing waste.
A efetividade das soluções foi comprovada a partir da fabricação do produto em instalações industriais, respeitadas as condições, parâmetros e características de produção desenvolvidas por professores, pesquisadores e técnicos envolvidos. The effectiveness of the solutions was proven from the manufacturing of the product in industrial facilities, respecting the conditions, parameters and production characteristics developed by the teachers, researchers and technicians involved.
As formulações de tintas são preparadas a partir da associação do
acetato de sec-butila com outros solventes visando balancear as propriedades de solvência e evaporação, que satisfazem às exigências de secagem, fluidez, nivelamento do filme, resistência mecânica, brilho e resistência ao branqueamento, dentre outros requisitos. The paint formulations are prepared from the combination of the sec-butyl acetate with other solvents to balance solvency and evaporation properties, which meet the requirements of drying, flowability, film leveling, mechanical strength, gloss and bleach resistance, among other requirements.
Os filmes de polímeros orgânicos são, em geral, produzidos a partir da aplicação de uma solução, ou dispersão, sobre o substrato, seguida de evaporação do solvente com formação do filme por secagem ou coalescência. O sistema solvente desempenha um papel fundamental no controle da solubilidade das resinas e na taxa de secagem, que terão, por consequência, forte influência nas propriedades finais do revestimento. Organic polymer films are generally produced by applying a solution or dispersion to the substrate followed by evaporation of the solvent with film formation by drying or coalescing. The solvent system plays a key role in controlling the solubility of the resins and the drying rate, which will therefore have a strong influence on the final properties of the coating.
O conhecimento do comportamento de solubilidade das resinas, formadoras de filme no sistema solvente, é essencial do ponto de vista tecnológico, e diferentes morfologias de filme têm sido obtidas variando o sistema solvente. Knowledge of the solubility behavior of film-forming resins in the solvent system is technologically essential, and different film morphologies have been obtained by varying the solvent system.
A solubilidade de um polímero, em um certo solvente é entendida por modelos semi-empíricos, utilizando os chamados parâmetros de solubilidade. Esses modelos consideram a solubilidade de uma molécula em um solvente a partir relação entre os parâmetros de solubilidade do solvente e do soluto, e quanto mais próximos forem esses valores (ôsolvente e ôsoluto) melhor será a solubilidade do sistema. Dessa forma, o modelo orienta pela seleção e desenvolvimento de sistemas capazes de propiciar a solubilização das resinas. A tabela 1 demonstra o raio de solubilidade de diferentes tipos de resinas em comparação com o raio de solubilidade proporcionado pela interação com o acetato de sec-butila. No trabalho de desenvolvimento foram estudadas estas
interações e as composições de solventes com o novo produto. The solubility of a polymer in a certain solvent is understood by semi-empirical models using so-called solubility parameters. These models consider the solubility of a molecule in a solvent from the relationship between solvent and solute solubility parameters, and the closer these values (solvent and solute) the better the system solubility. Thus, the model guides by the selection and development of systems capable of providing the solubilization of resins. Table 1 shows the solubility radius of different types of resins compared to the solubility radius provided by interaction with sec-butyl acetate. In the development work we studied these interactions and solvent compositions with the new product.
Tabela 1: raios de solubilidade requeridos de diferentes resinas comparativamente ao raio de solubilidade em acetato de sec-butila.
Table 1: Required solubility radii of different resins compared to sec-butyl acetate solubility radius.
O segundo parâmetro relevante para o desenvolvimento das aplicações, está relacionado com a volatilidade ou taxa de evaporação do solvente, e deste comportamento em misturas com outros solventes do sistema. Essas características também são modeladas a partir das propriedades físicas e de interação molecular entre diferentes substâncias. The second relevant parameter for application development is related to the volatility or evaporation rate of the solvent, and its behavior in mixtures with other system solvents. These characteristics are also modeled from the physical properties and molecular interaction between different substances.
A tabela 2 apresenta as propriedades de diferentes solventes. O ponto de ebulição e a taxa de evaporação caracterizam o produto (acetato de sec-butila) no grupo dos solventes de evaporação média, com ponto de ebulição entre 100 e 150°C. Table 2 presents the properties of different solvents. Boiling point and evaporation rate characterize the product (sec-butyl acetate) in the group of medium evaporating solvents, boiling between 100 and 150 ° C.
Tabela 2: Propriedades fisico-químicas de diferentes solventes.em comparação ao acetato de sec-butila. Table 2: Physicochemical properties of different solvents compared to sec-butyl acetate.
Composições para tintas, vernizes ou tíneres segundo a invenção podem ser adaptáveis a diversos tipos de formulações a partir do balanço das formulações para a obtenção das propriedades requeridas de velocidade de evaporação e capacidade de dissolução dos polímeros empregados. As formulações podem ser preparadas a partir de qualquer método usual para mistura de solventes e/ou formulação de tintas, vernizes e tíneres. Compositions for paints, varnishes or thinners according to the invention may be adaptable to various types of formulations from the formulation balance to obtain the required evaporation rate and dissolution properties of the polymers employed. The formulations may be prepared by any usual method for mixing solvents and / or formulating paints, varnishes and thinners.
A adequação das formulações às aplicações pretendidas é demonstrada a partir da comparação das viscosidades das formulações e da deterrninação da velocidade de evaporação do sistema solvente, a retenção dos solventes após aplicação em filmes plásticos flexíveis e a perda de solvente por evaporação durante o processo de aplicação da tinta sobre o substrato. A melhoria das formulações em relação ao impacto ambiental é verificada pelo potencial de redução da emissão de VOCs demonstrada a partir da comparação das formulações sob condições de agitação e exposição a atmosfera.
Exemplo The suitability of the formulations for the intended applications is demonstrated by comparing the viscosities of the formulations and determining the evaporation rate of the solvent system, the retention of solvents after application to flexible plastic films and the evaporative solvent loss during the application process. of paint onto the substrate. The improvement of the formulations in relation to the environmental impact is verified by the potential of reduction of VOC emission demonstrated from the comparison of the formulations under conditions of agitation and exposure to atmosphere. Example
Foi realizado experimento avaliando a aplicação do acetato de sec-butila em formulações de tíneres de diluição, utílizando-se uma tinta flexográfica padrão a base de resina Nitrocelulose e Poliuretano, com objetivo de obter um tíner de maior equilíbrio na evaporação proporcionando a diminuição de perda de solventes e consequente diminuição na reposição de solvente durante a aplicação da tinta. An experiment was carried out to evaluate the application of sec-butyl acetate in dilution thinner formulations, using a standard flexographic ink based on Nitrocellulose and Polyurethane resin, aiming to obtain a thinner evaporation equilibrium, reducing the loss. and consequent decrease in solvent replacement during paint application.
1. Formulações de tíneres de diluição avaliados (Tabela 3): 1. Evaluated dilution thinner formulations (Table 3):
Tabela 3: Tíneres para diluição de tinta de impressão flexográfica Table 3: Flexographic Printing Ink Dilution Thinners
Foram realizados testes de laboratório a fim de verificar e quantificar a evaporação de solventes durante o processo de uso da tinta no processo de pintura por impressão. As amostras para testes foram geradas através da diluição da tinta padrão com os respectivos tíneres de diluição para a viscosidade de 20 segundos em viscosímetro copo Zahn 2 à temperatura de 25°C
Tabela 4: Parâmetros da tinta após diluição Laboratory tests were performed to verify and quantify the evaporation of solvents during the ink use process in the printing painting process. Test samples were generated by diluting the standard paint with the respective dilution thinners to the 20 second viscosity in a Zahn 2 glass viscometer at 25 ° C. Table 4: Ink Parameters After Dilution
As amostras foram submetidas à agitação (disco tipo cowles, 700 rpm) por 5 horas, em vaso aberto, provocando a evaporação dos solventes. Posteriormente foram determinadas as quantidades de solventes perdidos por evaporação e analisadas as características da tinta após aplicação, conforme abaixo: The samples were agitated (cowles disc, 700 rpm) for 5 hours in an open vessel, causing the evaporation of solvents. Subsequently, the amount of solvents lost by evaporation was determined and the characteristics of the paint after application were analyzed, as follows:
Tabela 5: Parâmetros da tinta após diluição e agitação por 5 horas em vaso aberto Table 5: Ink parameters after dilution and shaking for 5 hours in open pot
3. Outros resultados de desempenho (Tabela 6) 3. Other performance results (Table 6)
Tabela 6: Parâmetros da tinta após diluição Table 6: Ink Parameters After Dilution
Numa realização preferencial, a composição compreende acetatos de alquila de 3 a 5 átomos de carbono em uma quantidade na faixa de 5 a 40% em
massa. Numa outra realização preferencial, a composição compreende o acetato de sec-butila em uma quantidade na faixa de 5 a 40% em massa. Numa outra realização preferencial, a composição compreende uma mistura balanceada de solventes fundamentados em álcoois de 2 a 5 átomos de carbono com 5 a 70% em massa de álcoois com estruturas lineares e/ou ramificadas. Numa outra realização preferencial, a composição compreende uma mistura balanceada de solventes fundamentados nos álcoois com 30 a 70% em massa do álcool etílico. Numa outra realização também preferencial, a composição compreende uma mistura balanceada de solventes fundamentados nos álcoois com 5 a 50% em massa do álcool sec-butílico. Em outra realização preferencial, a composição compreende uma mistura balanceada de solventes fundamentados em cetonas de 3 a 5 átomos de carbono e com 1 a 30% em massa. Em outra realização preferencial, a composição compreende uma mistura balanceada de solventes fundamentados nos éteres glicólicos com 1 a 40 % em massa. Em outra realização preferencial, a composição compreende uma mistura balanceada de solventes fundamentados nos éteres glicólicos com cerca de 1 a 40% em massa de éteres glicólicos derivados do óxido de eteno ou óxido de propeno.
In a preferred embodiment, the composition comprises alkyl acetates of 3 to 5 carbon atoms in an amount ranging from 5 to 40% by weight. pasta. In another preferred embodiment, the composition comprises sec-butyl acetate in an amount ranging from 5 to 40% by weight. In another preferred embodiment, the composition comprises a balanced mixture of alcohol-based solvents of 2 to 5 carbon atoms with 5 to 70% by weight alcohols of linear and / or branched structures. In another preferred embodiment, the composition comprises a balanced mixture of alcohol-based solvents with 30 to 70% by weight of ethyl alcohol. In another further preferred embodiment, the composition comprises a balanced mixture of alcohol-based solvents with 5 to 50% by weight of sec-butyl alcohol. In another preferred embodiment, the composition comprises a balanced mixture of ketone-based solvents of 3 to 5 carbon atoms and 1 to 30% by weight. In another preferred embodiment, the composition comprises a balanced mixture of 1 to 40% by weight glycol ether based solvents. In another preferred embodiment, the composition comprises a balanced mixture of glycol ether based solvents with from about 1 to 40% by weight of glycol ethers derived from ethylene oxide or propene oxide.
Claims
1. Composição para tintas, vernizes ou tíneres para impressão, caracterizada por compreender uma mistura de balanceada de solventes fundamentados em acetatos de alquila, alcoóis sintéticos ou naturais, éteres glicólicos e cetonas capazes de proporcionar a redução de perdas de solventes por evaporação e da formação de poluentes em baixa atmosfera. Composition for printing inks, lacquers or thinners, characterized in that it comprises a balanced mixture of solvents based on alkyl acetates, synthetic or natural alcohols, glycol ethers and ketones capable of reducing evaporative solvent loss and formation. of pollutants in low atmosphere.
2. Composição de acordo com a reivindicação 1, caracterizada por compreender acetatos de alquila de 3 a 5 átomos de carbono em uma quantidade na faixa de 5 a 40% em massa. Composition according to Claim 1, characterized in that it comprises alkyl acetates of 3 to 5 carbon atoms in an amount ranging from 5 to 40% by mass.
3. Composição de acordo com a reivindicação 1 e 2, caracterizada por compreender o acetato de sec-butila em uma quantidade na faixa de 5 a 40% em massa Composition according to Claim 1 and 2, characterized in that it comprises sec-butyl acetate in an amount ranging from 5 to 40% by weight.
4. Composição de acordo com a reivindicação 1, caracterizada por compreender uma mistura balanceada de solventes fundamentados em alcoóis de 2 a 5 átomos de carbono com 5 a 70% em massa de alcoóis com estruturas lineares e/ou ramificadas. Composition according to Claim 1, characterized in that it comprises a balanced mixture of alcohol-based solvents of 2 to 5 carbon atoms with 5 to 70% by weight of alcohols having straight and / or branched structures.
5. Composição de acordo com a reivindicação 1, caracterizada por compreender uma mistura balanceada de solventes fundamentados nos alcoóis com 30 a 70% em massa do álcool etílico. Composition according to Claim 1, characterized in that it comprises a balanced mixture of alcohol-based solvents with 30 to 70% by weight of ethyl alcohol.
6. Composição de acordo com a reivindicação 1, caracterizada por compreender uma mistura balanceada de solventes fundamentados nos alcoóis com 5 a 50% em massa do álcool sec-butílico. Composition according to Claim 1, characterized in that it comprises a balanced mixture of alcohol-based solvents with 5 to 50% by weight of sec-butyl alcohol.
7. Composição de acordo com a reivindicação 1, caracterizada por compreender uma mistura balanceada de solventes fundamentados em cetonas de 3 a 5 átomos de carbono e com 1 a 30% em massa. Composition according to Claim 1, characterized in that it comprises a balanced mixture of ketone-based solvents of 3 to 5 carbon atoms and 1 to 30% by weight.
8. Composição de acordo com a reivindicação 1, caracterizada por compreender uma mistura balanceada de solventes fundamentados nos éteres glicólicos com 1 a 40 % em massa. Composition according to Claim 1, characterized in that it comprises a balanced mixture of ether-based solvents. glycols with 1 to 40% by mass.
9. Composição de acordo com a reivindicação 1, caracterizada por compreender uma mistura balanceada de solventes fundamentados nos éteres glicólicos com cerca de 1 a 40% em massa de éteres glicólicos derivados do óxido de eteno ou óxido de propeno. Composition according to Claim 1, characterized in that it comprises a balanced mixture of glycol ether based solvents with from about 1 to 40% by weight of glycol ethers derived from ethylene oxide or propene oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI1003090 BRPI1003090A2 (en) | 2010-08-31 | 2010-08-31 | composition for inks, varnishes and print cartridges |
| BRPI1003090-5 | 2010-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012027806A1 true WO2012027806A1 (en) | 2012-03-08 |
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ID=45772023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2011/000217 WO2012027806A1 (en) | 2010-08-31 | 2011-07-13 | Solvent composition for printing inks, varnishes and thinners |
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| Country | Link |
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| BR (1) | BRPI1003090A2 (en) |
| WO (1) | WO2012027806A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| BR102013004891A2 (en) * | 2013-02-28 | 2014-11-18 | Oxiteno Sa Ind E Comercio | AUTOMOTIVE SOLVENT INK DILUTION COMPOSITION AND ITS USE |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578117A (en) * | 1983-06-22 | 1986-03-25 | Sakura Color Products Corp. | Erasable ink composition |
| US4740549A (en) * | 1985-07-16 | 1988-04-26 | Toyo Soda Manufacturing Co., Ltd. | Ink composition for writing board |
| US20020115781A1 (en) * | 1997-02-20 | 2002-08-22 | Arco Chemical Technology, L.P. | Coatings and inks based on solvents having negligible photochemical reactivity |
| US6506243B1 (en) * | 1998-05-05 | 2003-01-14 | Exxonmobil Chemical Patents Inc. | Environmentally preferred fluids and fluid blends |
| US20090246377A1 (en) * | 2008-03-31 | 2009-10-01 | Videojet Technologies Inc. | Thermal ink jet ink composition |
| BRPI0703529A2 (en) * | 2007-09-05 | 2009-10-06 | Oxiteno Sa Ind E Comercio | Balanced solutions of oxygenated solvents with physicochemical characteristics similar to propylene glycol monomethyl ether and ethylene glycol monoethyl ether |
| CN101698763A (en) * | 2009-10-26 | 2010-04-28 | 河南省南街村(集团)有限公司油墨厂 | Benzene-free plastic rotogravure composite ink |
| BRPI0903531A2 (en) * | 2009-09-21 | 2011-05-24 | Oxiteno Sa Ind E Comercio | composition for paints, varnishes or paint |
-
2010
- 2010-08-31 BR BRPI1003090 patent/BRPI1003090A2/en not_active Application Discontinuation
-
2011
- 2011-07-13 WO PCT/BR2011/000217 patent/WO2012027806A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578117A (en) * | 1983-06-22 | 1986-03-25 | Sakura Color Products Corp. | Erasable ink composition |
| US4740549A (en) * | 1985-07-16 | 1988-04-26 | Toyo Soda Manufacturing Co., Ltd. | Ink composition for writing board |
| US20020115781A1 (en) * | 1997-02-20 | 2002-08-22 | Arco Chemical Technology, L.P. | Coatings and inks based on solvents having negligible photochemical reactivity |
| US6506243B1 (en) * | 1998-05-05 | 2003-01-14 | Exxonmobil Chemical Patents Inc. | Environmentally preferred fluids and fluid blends |
| BRPI0703529A2 (en) * | 2007-09-05 | 2009-10-06 | Oxiteno Sa Ind E Comercio | Balanced solutions of oxygenated solvents with physicochemical characteristics similar to propylene glycol monomethyl ether and ethylene glycol monoethyl ether |
| US20090246377A1 (en) * | 2008-03-31 | 2009-10-01 | Videojet Technologies Inc. | Thermal ink jet ink composition |
| BRPI0903531A2 (en) * | 2009-09-21 | 2011-05-24 | Oxiteno Sa Ind E Comercio | composition for paints, varnishes or paint |
| CN101698763A (en) * | 2009-10-26 | 2010-04-28 | 河南省南街村(集团)有限公司油墨厂 | Benzene-free plastic rotogravure composite ink |
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| BRPI1003090A2 (en) | 2012-05-29 |
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