KR0127771B1 - Preparation process of microencapsulated photochromic composition - Google Patents

Abstract

This agent, useful as manufacturing water ink is made. Thus,i)0.1-1 wt.% Spyro compd.(1) and 0.01-1 wt.% additives are melted in oil to give soln.(a) which maintains at 60-70 deg. C, ii)10-14 wt.% gelatine is melted in 58.8-71.8 wt.% water to give soln.(b). soln.(a) and soln(b) are added with 2-6 wt. % resin, 0.1-1% dulling agent,a ultraviolet stabiliser, and an antioxidant. In formulaR1 = alkoxy, halogen atom, x = C,N y = O, S, b = benzene,naphthalene, hetero ring compd., a = benzene, naphthalene.

Description

Method for preparing a capsule photochromic composition

Field of invention

The present invention relates to a method for producing a capsule photochromic composition.

In particular, the present invention relates to a method of preparing a capsular photochromic composition for increasing dispersibility and stability in water.

More particularly, the present invention relates to a method for preparing a capsule photochromic composition suitable for use in the preparation of a composition such as an aqueous ink using water as a dispersant.

Background of the Invention

Since the photovariable shape can directly feel the change, many researches have been conducted on photochromic agents and their phenomena that exhibit such properties.

Materials having these characteristics can be used as components in the production of coating compositions, optical recording media, coating of fibers, various accessories, and the like.

Photochromic compounds include tungsten halides, which are widely used as photosensitizers, organic compounds such as spiropyran, spiroxazine, azo compounds, and diarylethene, and tungsten. Inorganic compounds such as compounds, and the like.

Among these, spiropyran, spiroxazine, and diarylethene show photochromic phenomena by ring opening / closing reaction, azo compounds show photovariable phenomena by cis / trans isomerization, and silver halides and tungsten compounds are oxidized. It is known to exhibit photochromic phenomena by the reduction / reduction reaction.

Although spirooxazines are more stable than spiropyrans, the spiro compounds are very poor in stability, difficult to synthesize, and difficult to obtain high purity compounds. It is widely used because it has a very fast photoresponse effect.

However, these spiro compounds and other organic photochromic agents are not only stable in themselves, but also have a low solubility in water due to their large molecular size compared to other organic compounds. It is also difficult to disperse in water.

However, paints and inks, which are widely used in daily life, are preferably an aqueous medium, and in industrial use such as coating on fibers, it is required to be used by dividing in an aqueous medium such as water.

There may be various chemical methods for stabilizing organic compounds such as spiro-based compounds. Representative examples thereof include a method of forming an organic thin film by including an alkyl group of a long chain, dimerization of organic compounds, and a method of suspending a pendant group to a polymer material.

European Patent Application No. 88117147.4, filed Oct. 14, 1988, describes a spiro-based photochromic material and a thin coating of it on a plastic film. However, the coating of photochromic agents on plastic films, as in this application, is true in spite of the fact that spiro-based compounds are more stable than other photochromic agents. It is only a coating and does not increase the stability of the photochromic agent.

In addition, the dimerization method is not appropriate for the structure of the spiro-based compound in the case of the spiro-based compound, and the hanging of the pendant group to the polymer material is different in color change range and discoloration time of the photochromic depending on the characteristics of the polymer material as the parent material This makes it difficult to make stabilized systematic compounds.

U.S. Patent No. 5,017,225, issued to Nakanishi et al. On May 21, 1991, describes a microencapsulated photochromic material, a process for preparing the same, and an aqueous ink composition prepared therefrom, but (1) boiling at 40 to 160 ° C. Mixing of solvent and photochromic material having solubility of 15 wt% or less in point and 20 ℃ water, (2) emulsifying in aqueous solution of gelatin, (3) coating with aqueous solution of gum arabic, (4) adjusting pH Post cooling, (5) adding glutaraldehyde, (6) prolonged curing at low temperatures, and (7) daily heating and stirring at 40 ° C., which include many processes for microencapsulation of photochromic materials. In addition, there is a disadvantage in that the manufacturing time is very long, and although the solvent used has a high boiling point, it uses a toxic solvent such as methyl isobutyl ketone or toluene having high medium pressure. In addition, since all solvents are removed by vaporization so that only trace amounts remain from the capsule, there is a big problem in environmental degradation as well as deterioration of the working environment.

Accordingly, the present inventors solved the above problems and completed the present invention by coating a micro-encapsulating spiro-based compound which is a photochromic agent with a resin for coating together with an ultraviolet stabilizer, an antioxidant, an oxygen quencher, a high temperature color decreasing agent and a sensitizer. .

It is an object of the present invention to provide a method for preparing a microcapsule type photochromic composition.

Summary of the Invention

The present invention prepares Solution A in which a spiro compound, which is 0.1 to 1% by weight of a photochromic agent, is heated and dissolved in 16 to 20% by weight of oil together with 0.01 to 1% by weight of an additive and the like and maintained at a temperature of 60 to 70 ° C. At the same time to prepare a solution B in which 10 to 14% by weight gelatin in a separate container warmed and dissolved in 58.8 to 71.8% by weight of water and maintained at a temperature of 70 to 75 ℃, using a mechanical stirrer While stirring the solution B at 3,000 to 8,000 rpm, the solution A was added dropwise to the solution B at a rate of 3 to 7 ml / sec to form an emulsion, followed by 2 to 6% by weight of the coating on the obtained emulsion solution while stirring for 10 minutes. The resin is added to coat the emulsified particles with a resin, followed by further stirring for about 5 minutes to be coated with the coating resin to obtain an encapsulated photochromic composition.

The photochromic agent (I) used in the present invention is a substance which is usually colored and discolored by absorption and emission of light energy, and is preferably a spiro-based compound.

Wherein R ₁ is hydrogen, alkoxy, halogen atom or trifluoromethyl such as methoxy or ethoxy group, R ₂ is hydrogen or alkyl group such as methyl or ethyl group, R ₃ is hydrogen, dimethylamine or diethylamine Amines such as piperidine or molpholine and the like, R ₄ is hydrogen, alkoxy or halogen atom such as methoxy or ethoxy, X is carbon (spiropyrane) or nitrogen (spiroxazine) Y is oxygen or sulfur, A is various aromatic ring compounds such as benzene or naphthalene, and B is various aromatic ring compounds or heterocyclic compounds such as benzene or naphthalene.

Description of Embodiments of the Invention

The present invention heats and dissolves a spiro-based compound, which is a photochromic agent having a structural formula (I) of 0.1 to 1% by weight, in an oil of 16 to 20% by weight with 0.01 to 1% by weight of an additive or the like. While preparing solution A maintained at a temperature of 60 to 70 ° C, while maintaining a temperature of 70 to 75 ° C by heating and dissolving 10 to 14% by weight of gelatin in 58.8 to 71.8% by weight of water in a separate container. Prepare B, add the solution A dropwise to the solution B at a rate of 3 to 7 ml / sec using a mechanical stirrer while stirring the solution B at 3,000 to 8,000 rpm, and then form an emulsion. 2 to 6% by weight of the coating resin was added to the obtained emulsion solution with stirring for a minute, and then the emulsified particles were coated with a resin, followed by further stirring for about 5 minutes to obtain the encapsulated photochromic composition. It is characterized by fullness.

Of course, a homogenizer or a sonicator may be used instead of the mechanical stirrer.

The photochromic agent (I) used in the present invention is a substance which is usually colored and discolored by absorption and emission of light energy, and is preferably a spiro-based compound. Such photochromic agent (I) is described in detail in European Patent Application No. 88117147.4, filed October 14, 1988.

Wherein R ₁ is hydrogen, an alkoxy group such as methoxy or ethoxy group, halogen atom or trifluoromethyl, R ₂ is hydrogen or alkyl group such as methyl or ethyl group, R ₃ is hydrogen, dimethylamine or diethyl Amines such as amines, piperidine or molpholine, R ₄ is hydrogen, alkoxy or halogen atoms such as methoxy or ethoxy, X is carbon (spiropyrane) or nitrogen (spirooxazine) , Y is oxygen or sulfur, A is various aromatic ring compounds such as benzene or naphthalene, and B is various aromatic ring compounds or heterocyclic compounds such as benzene or naphthalene.

However, the photochromic agent (I) prepared as described in European Patent Application No. 88117147.4 is quite unstable on its own, and its dispersibility and stability to water are very low, which makes it very difficult to apply it as it is to an actual product. .

The capsule manufacturing oil may be oil widely used for industrial purposes, such as castor oil, palm oil or soybean oil, and preferably di-iso-propyl-naphthalene having high chemical stability such as thermal stability and chemical resistance. Although iso-propyl-naphthalene (trade name KMO-113) may be used, the present invention is not limited to the above oils, and those skilled in the art may select other suitable oils.

In the above, the additive may be appropriately selected depending on the physical properties of the encapsulated photochromic composition to be obtained, and may be generally selected from the group consisting of UV stabilizers, antioxidants, oxygen quenchers, anti-hot colorants and sensitizers. have.

In the above, UV stabilizers, antioxidants, oxygen quencher, high temperature deterioration inhibitors and sensitizers can be purchased commercially, preferably the UV stabilizers Tinuvine 144 (Tinuvine 144), Tinuvin from Ciba-Geigy 622, Tinuvin 765 or Cyansorb3346 on American cyanamide or UV-Check AM 101, 105, 126 and 205 from DuPont's Rylox NBC or Perocorp The antioxidant may be Irganox 1010 (Irganox 1010). Oxygen quencher in the above can be Cyansorb UV-1084 (Cyasorb UV-1084) of American Cyanamide, Irga Stop 2002 of Shiva-Geigi or Rylex NBC of Dupont, The sensitizer may be Mark LA-57 from Adeka Argus Chemical, LS-2000 from Smithsolve (LS-200) or LS-2001.

In the above, the high temperature deterioration inhibitor is for preventing the photochromic agent from deteriorating color development at high temperature, and preferably, hexafluoro-2-propanol or bisphenol A, bisphenol A, Phenolic compounds such as Bisphenol B) and Bisphenol S can be used, which are readily available from chemical companies around the world.

In general, when obtaining a composition which can be widely used, 0.1 to 1% by weight of UV stabilizer, 0.1 to 1% by weight of antioxidant, 0.1 to 1% by weight of oxygen quencher, 0.1 to 1% by weight of high temperature Anti-pigmentation agents and sensitizers of 0.1 to 1% by weight may be used.

The encapsulated photochromic composition obtained by the method as described above may be used as a raw material of an ink or a paint together with a stabilizer such as a surfactant or gum arabic as it is prepared.

In addition, a solution obtained by dissolving 60% by weight of a separate resin hardener in about 50 ° C. with respect to 100% by weight of the coating resin was added dropwise to the encapsulated photochromic composition obtained as described above with agitation to form a capsule. It is also possible to further cure the resin for capsule production.

In the coating resin, resins such as melamine resin, urea resin, epoxy resin and urethane resin may be used. Preferably, epoxy resin and urethane resin may be used.

The resin curing agent is a curing agent for curing the resin used as the coating resin, these are commercially available curing agents, those skilled in the art can be used by selecting a suitable curing agent for the resin to be used It is.

In addition, when the epoxy resin is used as the coating resin in the above, preferably an amine-based curing agent such as EK-U (EK-U) may be used as a curing agent, it can also be purchased commercially.

Next, a method of manufacturing a capsule photochromic composition according to the present invention will be described with reference to specific examples.

Example

Prepare solution A in which 3 g of a spiro-based compound as a photochromic agent (I) was heated and dissolved in 135 g of oil together with 0.6 g of an additive, and maintained at a temperature of 60 to 70 ° C., and 500 g of 90 g of gelatin was placed in a separate container. Solution B was prepared, which was heated and dissolved in water and kept at a temperature of 70 to 75 ° C. Using a mechanical stirrer capable of rotating at least 10,000 rpm or more, the solution B was added dropwise to the solution B at a rate of 5 ml / sec while stirring the solution B at 3,000 to 8,000 rpm, and an emulsion was obtained while continuing stirring for 10 minutes. 30 g of a coating resin was added to the emulsion solution to coat the emulsified particles with a resin, followed by further stirring for about 5 minutes. Next, a solution of 18 g of resin curing agent dissolved in water at about 50 ° C. was added dropwise to the encapsulated photochromic composition obtained as described above with gentle stirring to further cure the coating resin to form a capsule. Water evaporated during the reaction was replenished with water at approximately 70-75 ° C. to maintain the initial volume.

After the reaction was completed, a small amount of cold water was added to make the total solution volume 600 ml to obtain a capsule photochromic composition having a solid content of 0.5%. As a result of the analysis, the solid content obtained by completely evaporating the water, it was confirmed that the coating resin and the curing agent occupy 40% of the total solid content.

The capsular photochromic composition obtained in this way is very stable as the state of the solid content dried | evaporated by the evaporation of all the water | moisture content of a medium, or it is disperse | distributed, and can be formed with various forms of a paint, an ink, a pigment, etc.

Although described in detail only with respect to the embodiments described above, it will be apparent to those skilled in the art that modifications and variations can be made within the spirit and scope of the invention, and such changes or modifications are attached to the appended claims. It should be limited by scope.

Claims (4)

A spiro-based compound, which is a photochromic agent having the following structural formula (I) of 0.1 to 1% by weight, is heated and dissolved in 16 to 20% by weight of oil with 0.01 to 1% by weight of an additive and the like and maintained at a temperature of 60 to 70 ° C. Prepare Solution A prepared at the same time, prepare Solution B in which 10-14% by weight of gelatin was heated and dissolved in 58.8-71.8% by weight of water in a separate container and maintained at a temperature of 70-75 ° C, using a mechanical stirrer. While stirring the solution B at 3,000 to 8,000rpm, the solution A was added dropwise to the solution B at a rate of 3 to 7ml / sec to form an emulsion, followed by stirring for 10 minutes to 2 to 6% by weight of the emulsion solution After the coating resin was added to coat the emulsified particles with the resin, the mixture was further stirred for about 5 minutes to be coated with the coating resin to obtain an encapsulated photochromic composition. The method of the composition. Wherein R ₁ is hydrogen, alkoxy, halogen atom or trifluoromethyl such as methoxy or ethoxy, R ₂ is hydrogen or alkyl group such as methyl or ethyl group, R ₃ is hydrogen, dimethylamine or diethylamine Amines such as piperidine or molpholine and the like, R ₄ is hydrogen, alkoxy or halogen atom such as methoxy or ethoxy, X is carbon (spiropyrane) or nitrogen (spiroxazine) Y is oxygen or sulfur, A is various aromatic ring compounds such as benzene or naphthalene, and B is various aromatic ring compounds or heterogill compounds such as benzene or naphthalene. The method of claim 1, wherein the additive is Tinuvine 144, Tinuvin 622, Tinuvin 765 or Cyansorb 3346 (Cyasorb3346) from American Cyanamide or Rylox from DuPont. NBC) or UV stabilizer such as UV-Check AM 101, 105, 126 and 205 of ferrocorporation, antioxidant such as Irganox 1010, Cyansolve UV-1084 from American Cyanamide Oxygen quencher, such as Cyasorb UV-1084, Irgastab2002 from Ciba-Geigi or Rylex NBC from Dupont, Hexafluoro-2-propanol Or high temperature color reduction inhibitors such as bisphenol A, bisphenol B, and phenolic compounds such as bisphenol S, Mark LA-57 from Adeka Argus Chemical, Smi Solves company's LS-2000 (LS- 2000) or a sensitizer, such as LS-2001. The capsule-type photochromic agent according to claim 2, wherein the additive is formed by mixing an ultraviolet stabilizer, an antioxidant, an oxygen quencher, a high temperature color deterioration inhibitor, and a sensitizer in a ratio of 1: 1: 1: 1. Method of Preparation of the Composition. A solution obtained by dissolving 60% by weight of a separate amine-based resin hardener in water at about 50 ° C based on 100% by weight of a coating resin such as melamine resin, urea resin, epoxy resin, urethane resin, etc. A method for producing a capsule photochromic composition, characterized in that the coating resin to form a capsule by dropwise addition to the encapsulated photochromic composition obtained as described above is slowly stirred.