JPH0820076A - Colored plastic article and manufacturing method thereof - Google Patents

Abstract

PURPOSE:To obtain a large quantity of uniform and stable colored plastic articles, for example, colored plastic lenses by forming a colored layer by using an ink jet method employing a continuous head. CONSTITUTION:In a plastic article wherein a colored layer is provided on a plastic base material, the colored layer is formed by using an ink jet method employing a continuous head. Coloration can be applied to a plastic base material impossible to color by a conventional ink jet method and the plastic article having various merits can be obtained. For example, a continuous head having a plurality of ink jet nozzles arranged thereto in a row is arranged above the lens set on a moving stage and the timing of the movement of the lens and the ejection of ink is taken to apply an arbitrary hue and pattern to the lens.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a colored plastic article and a method for producing a colored plastic article. In particular, it relates to a plastic article, particularly a plastic lens, having a colored layer coated with an ink by an inkjet method having a continuous type head.

[0002]

2. Description of the Related Art Among plastic articles, in recent years, plastic lenses are easy to mold, are light and difficult to break, and can be easily colored by coloring. It has come to be widely used as an application lens. Above all, the merit that it can be easily colored by coloring is fashionable,
It is preferred as a lens for eyeglasses from the viewpoint of light-shielding properties, and it is said that 70% or more of the plastic lenses for eyeglasses are colored and put on the market.

For these reasons, it has become necessary to color plastic lenses in various colors uniformly, in large quantities, and stably. The conventional plastic lens coloring method is a so-called dipping coloring method (dispersion coloring method in which a disperse dye is dispersed in water together with a surfactant to prepare a coloring liquid, the coloring liquid is heated, and the plastic lens is immersed in the heating coloring liquid. Method) is mainly used.

As an alternative method to the above-mentioned dipping method, for example, a method proposed in Japanese Patent Publication No. 35-1384 to sublimate an organic pigment to color a plastic lens, and Japanese Patent Application Laid-Open No. 56-153321 and Japanese Patent Application Laid-Open No. 56-1593
No. 76 and JP-A-1-277814, there is a method of coloring a plastic lens by sublimating a sublimable dye.

[0005]

Conventionally, the lens is colored mainly by the dipping method because of the simplicity of the apparatus and the ease of work. However, the conventional method of coloring a plastic lens, the immersion method of immersing a plastic lens substrate in a coloring liquid is a disperse dye concentration in the coloring liquid, an amount of a coloring aid,
It is difficult to obtain a large amount of uniform and stable colored plastic lenses because the color tone is likely to change largely due to the temperature of the coloring liquid, the variation in coloring property of the plastic lens substrate, and the like.

In the dipping method, a coloring liquid must be provided for each color, and the amount of waste liquid is considerably large. Therefore, the cost for waste liquid treatment is high and the waste liquid can be discharged due to environmental protection problems. Is also a problem. Furthermore, JP-A-56
In the vapor phase coloring method using a solid colorable dye in JP-A-153321 and JP-A-56-159376, since a block-shaped solid dye is used, the dye cannot be uniformly heated on the lens surface, and it is difficult to adjust the coloring density. There is such a problem. In the coloring method of Japanese Patent Laid-Open No. 1-277814, the atmosphere at the time of coloring must be evacuated, which requires a work such as evacuating the inside of the apparatus, which increases the number of manufacturing steps and increases the cost. There was a problem that work efficiency was poor.

The present invention solves the problems of the conventional methods for coloring plastic lenses described above, and provides a coloring method for obtaining a large amount of uniform and stable colored plastic articles, for example, colored plastic lenses. To aim.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have attempted to improve this based on the conventional method of coloring a plastic lens. For example, in the dipping method, an attempt was made to solve the problems by changing the composition of the coloring liquid and adjusting the heating conditions and the like in the vapor phase coloring method. As a result, it was possible to improve the tinting property slightly, but earnest research was conducted in order to manufacture a higher quality tinted lens. Therefore, the present inventor attempts to solve the conventional problems by using a completely new coloring method that is not bound by the concept of the conventional lens coloring method, and to manufacture a high-quality colored lens that has never existed before. It was

Therefore, the application of the ink jet method, which has been conventionally used for printing or printing on flat paper or fiber, to the application of a dye to the surface of a curved plastic lens substrate was examined. Then, the plastic lens was colored using the conventional inkjet method and the conventional ink. As a result, there is a new problem that the ink is not easily fixed to the lens surface and the ink is easily peeled off, which is not in printing or printing on paper or fiber using the conventional inkjet method. The present inventor has further researched,
The coloring conditions, the material of the lens substrate, the surface shape, etc. were examined.
As a result, the conventional inkjet method has been used for printing or printing on paper, fiber, etc., so that it is impossible to color a plastic material that has not been colored by the conventional inkjet method unless the dye or ink is improved. I understood. As a result of research, they have found that it is possible to obtain a plastic article that can be colored even on a plastic substrate that could not be colored by the conventional inkjet method and that has various advantages. It has also been found that pigmentation allows the desired color to be reproduced with good reproducibility and allows the plastic to be colored rapidly and uniformly. Furthermore, we tried to make the best use of the characteristics of the inkjet method having a continuous type head capable of high-speed coloring.

Therefore, in the present invention, firstly, "a plastic article having a colored layer on a plastic substrate is characterized in that the colored layer is a layer applied by an inkjet method having a continuous type head. Plastic article (claim 1) ". Further, there is provided "a plastic article (claim 2), wherein the plastic substrate according to claim 1 is a plastic lens substrate". Further, "a method for producing a plastic article, characterized in that a base material made of plastic is prepared, and ink is applied on the plastic base material by an inkjet method having a continuous type head to form a colored layer (claim Item 3) ”is provided. Also,
"A method for producing a plastic article or a plastic article, characterized in that the ink according to claims 1, 2, and 3 is an ink containing a direct dye, an acid dye, a reactive dye, a disperse dye, and a cationic dye as a pigment (claim 4 )"I will provide a.
In addition, "a plastic article or a method for producing a plastic article (claim 5) according to claim 4, characterized in that a film is formed on the base material made of the plastic by a resin into which the dye easily penetrates. provide. Further, there is provided "a manufacturing method (claim 6) characterized in that an ink obtained by removing the inorganic salt in the ink according to claim 4 is used. In addition, "a plastic article or a method for producing a plastic article (claim 7), characterized in that the ink according to claims 1, 2, and 3 is obtained by adding a soluble resin to a water-soluble or high-boiling solvent (claim 7)" provide. Also,
“The ink according to claim 4 is a phthalocyanine-based ink, an azo-based ink,
A plastic article or a plastic article characterized by being an ink in which an organic pigment such as a quinacridone type, a slene type, or a quinophthalone type, and an inorganic pigment such as carbon black, titanium oxide-coated mica, ultramarine blue, white carbon, or zinc oxide is a dye. Manufacturing method (claim 8) ". Further, there is provided "a plastic article or a method for producing a plastic article (claim 9), characterized in that the particle diameter of the pigment according to claim 8 is 0.3 µm or less."

[0011]

The ink jet method used in the present invention has a continuous type head. In the present invention, a nozzle head in which two or more, preferably three or four, plural inkjet nozzles are arranged in a row is installed on the lens, and the lens is set on the moving stage to move the lens and eject the ink. It was possible to apply an arbitrary color tone and pattern on the lens in a timely manner. Needless to say, the coating can be performed even if the nozzle head is moved or both are moved.

The coloring of the spectacle lens has a wide variation in color, density, presence / absence of gradation, and the like. According to the present invention, the color desired by the customer is measured, or stored in advance as colorimetric data in a computer, and the data is measured for each nozzle of three or four colors of yellow, magenta, cyan and black. Of the print data and stored in the memory corresponding to the nozzles in time series. After all the data is stored, the lens stage is moved, ink dots are sprayed from each nozzle based on the print data at the timing, and application is performed on the lens. As a result, the colored lens desired by the customer can be manufactured with good reproducibility and speed.

The ink used in the present invention uses a dye such as a direct dye, an acid dye, a reactive dye, a disperse dye, and a cationic dye, and in order to obtain nozzle clogging and ejection stability, removal of inorganic salts from the ink Ink is used.
In addition to the dye, an ink containing a pigment as a coloring material is also used. Examples of these pigments include organic pigments such as phthalocyanine-based, azo-based, quinacridone-based, slene-based, and quinophthalone-based pigments, and inorganic pigments such as carbon black, titanium oxide-coated mica, ultramarine blue, white carbon, and zinc oxide. Since the nozzle must discharge from a small hole of 10 to 100 μm, the particle size of the pigment also needs to be considerably small, needs to be 0.3 μm or less, and preferably 0.1 μm or less. This value is not only to prevent nozzle clogging, but also to consider that when a lens is used as the base material, when it is colored on the lens, it does not cause significant fogging due to light scattering by particles. Is.

In the present invention, the material to be colored is plastic, and the ink for paper that is normally used has problems in dot shape and ink fixability. Therefore, the ink fixability on the plastic substrate is improved. Therefore, by adding a water-soluble resin or a resin soluble in a high-boiling-point solvent to the ink, the fixability of the ink on the plastic substrate is improved and gradation printing is also possible. Further, by using a pigment as a colorant, it becomes possible to manufacture a colored lens having excellent light resistance.

Considering the penetrability of an ink containing a dye as a pigment into a plastic substrate, selection of the dye becomes important, but at the same time, it is possible to coat a resin film which allows the dye to easily penetrate. I went. The resin film used in the present invention is preferably a thermoplastic resin or a thermosetting resin. To illustrate these resins,
Examples of the resin include polyamide, phenol resin, butyral resin, melamine resin, polyvinyl alcohol, cellulose resin, alkyd, acrylic resin, epoxy resin, urethane resin, polyester and silicone resin. These resins can be used as one kind, but it is also possible to mix several kinds and further to use a copolymer.

Of these resins, particularly by coating a resin film made of polyurethane containing polyisocyanate and polyol as the main components, not only the effect as a coloring layer of the dye but also the impact resistance of the lens is improved. It is also possible to combine the effect of doing. Further, the plastic lens molding used in the present invention, polymethylmethacrylate and its copolymer, acrylonitrile-styrene copolymer, polycarbonate, cellulose acetate, polyvinyl chloride, polyethylene terephthalate, epoxy resin, unsaturated polyester resin, A plastic lens molded product made of a polyurethane resin and a diethylene glycol bisallyl carbonate polymer.

[0017]

Example 1 An example of the present invention will be described below.
In this example, a diethylene glycol bisallyl carbonate polymer was used as the base material. Diethylene glycol bisallyl carbonate polymer, Mik
Eton Polyester Yellow GL
(Mitsui Isobaric Chemical Co., Ltd., Disperse Yell
ow 33), Miketon Polyester
Red FL (Mitsui Isobaric Chemical Co., Ltd., Dispers
e Red 72), Miketon Polyest
er Blue TGSF (Mitsui Isobaric Chemical Co., Ltd., D
An ink prepared by dissolving a dye of isperse Blue 214) in 1% by weight of each of methyl ethyl ketone and adding 2% by weight of an acrylic resin as a resin component is used at a continuous type inkjet printer at 2 mm / mi.
n was continuously colored to form a colored layer. The dye was diffused into the lens by heating the lens in an oven at 130 ° C. for 1 hour, and a good colored lens with almost no unevenness was obtained. For scratch resistance and antireflection, an organic silicon hard coat (manufactured by Nikon Corporation) was coated by dipping, and heated at 110 ° C. for 4 hours to cure. On top of that, an inorganic multilayer thin film composed of SiO ₂ , Al ₂ O ₃ and TiO ₂ was formed by vacuum evaporation. The colored lens produced in this manner had good color reproducibility, and the color variation was small, and the color difference was within 1.

[0018]

Example 2 In this example, Example 1 was used as a base material.
The same polymer was used. MIC as an organic pigment on diethylene glycol bisallyl carbonate polymer
ROPIGMO YELLOW AM-YW2 (manufactured by Orient Chemical Industry Co., Ltd.), MICROPIGMO RED
AM-RD2 (manufactured by Orient Chemical Industry Co., Ltd.), MICR
An ink prepared by dissolving OPIGMO BLUE AM-BE4 (manufactured by Orient Chemical Industry Co., Ltd.) in 1% by weight of methyl ethyl ketone and adding 2% by weight of a urethane resin as a resin component is used for an inkjet printer of a continuous system to have a thickness of 2 mm. / Min continuous printing,
A colored layer was formed. 130 the lens in the oven
A colored coating layer is formed by heating at ℃ for 1 hour. Further, for scratch resistance and antireflection, an organic silicon hard coat (manufactured by Nikon Corporation) is applied by dipping, and 110 ℃ for 4 hours. It was heated and cured. An inorganic multilayer thin film similar to that of Example 1 was formed thereon by vacuum vapor deposition. The colored lens thus produced had good color reproducibility, and a good colored lens with almost no unevenness could be manufactured. Further, when a light resistance test was performed on this lens using a xenon fade meter, almost no change in color difference was observed even after 600 hours had elapsed. The result is shown in FIG.

[0019]

Example 3 In this example, the same polymer as in Examples 1 and 2 was used as the substrate. Diethylene glycol bisallyl carbonate polymer is coated with a resin film made of polyurethane whose main component is polyisocyanate and polyol as a primer, and the temperature is 100 ° C.
It was heat-cured for 1 hour. From the top of the finished lens, as a dye, as a dye, Miketon Polyester Ye
low GL (Mitsui Isobaric Chemical Co., Ltd., Disper
se Yellow 33), Miketon Pol
yester Red FL (manufactured by Mitsui Isobaric Chemical Co., Ltd.,
Disperse Red 72), Miketon
An ink prepared by dissolving a dye of Polyester Blue TGSF (manufactured by Mitsui Isobaric Chemical Co., Inc., Disperse Blue 214) in 1% by weight each of methyl ethyl ketone and adding 2% by weight of an acrylic resin as a resin component is a continuous method. The continuous printing of 2 mm / min was carried out by the inkjet printer of. By heating the lens in an oven at 130 ° C. for 1 hour, the dye diffused into the coating layer and the inside of the substrate, and a good colored lens with almost no unevenness was obtained. Furthermore, for scratch resistance and antireflection, an organic silicon hard coat (manufactured by Nikon Corporation) was coated by dipping, and heated at 110 ° C. for 4 hours to be cured. Then, an inorganic multilayer thin film similar to those in Examples 1 and 2 was attached by vacuum vapor deposition. The colored lens produced in this manner had good color reproducibility, and a good colored lens with almost no unevenness was obtained. Furthermore, when an impact resistance test was conducted, it was possible to clear the FDA standard.

[0020]

As described above, in the coloring of a substrate made of a plastic according to the present invention, for example, a plastic lens, it is possible to suppress color variations due to deterioration of a dye over time and to achieve good color reproducibility. There is no need for color correction due to intuition, and color management can be performed by computer color matching. Furthermore, the inkjet method not only reduces the cost of the ink because the ink is ejected only to a necessary portion, but also can solve the problem of environmental problems such as waste liquid treatment. In addition, it became possible to automate the lens coloring process that was manually performed.

Since the head of the present invention is of the continuous type, it can be colored at a high speed, and the time required for the coloring step in the manufacturing process of the plastic article can be shortened and the cost can be reduced. Further, since the continuous type head is capable of continuously ejecting ink, the tip of the nozzle is not dried and it is easy to adjust the ink ejecting condition. Further, since it is possible to use an organic solvent as the ink solvent, it is possible to broaden the range of selection of the ink to be used. For example, when applied to the production of colored lenses, various types of colored lenses can be prepared. .

[Brief description of drawings]

FIG. 1 is a spectral distribution curve according to light resistance of a colored plastic lens prepared according to Example 2.

[Explanation of symbols]

1 ... Spectral distribution curve before light resistance 2 ... Spectral distribution curve after 600 hours exposure with xenon fade meter

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Claims (9)

[Claims] 1. A plastic article having a colored layer on a plastic substrate, wherein the colored layer is a layer applied by an inkjet method having a continuous type head. 2. A plastic article, wherein the plastic substrate according to claim 1 is a plastic lens substrate. 3. A method for producing a plastic article, comprising preparing a base material made of plastic, and applying an ink on the plastic base material by an inkjet method having a continuous type head to form a colored layer. . 4. A plastic article or a method for producing a plastic article, wherein the ink according to any one of claims 1, 2, and 3 is an ink containing a direct dye, an acid dye, a reactive dye, a disperse dye, or a cationic dye as a pigment. . 5. The plastic article or the method for producing a plastic article according to claim 4, wherein a film is formed on the base material made of the plastic, from the resin into which the dye easily penetrates. 6. A method for producing, wherein the ink obtained by removing the inorganic salt in the ink according to claim 4 is used. 7. A plastic article or a method for producing a plastic article, wherein the ink according to any one of claims 1, 2, and 3 is a water-soluble or high-boiling solvent to which a soluble resin is added. 8. The ink according to claim 4, wherein the ink is a phthalocyanine-based, azo-based, quinacridone-based, organic pigment such as slene-based, quinophthalone-based or the like, and an inorganic such as carbon black, titanium oxide-coated mica, ultramarine blue, white carbon, or zinc oxide. A method for producing a plastic article or a plastic article, which is an ink containing a pigment as a dye. 9. The particle diameter of the pigment according to claim 8 is 0.3 μm.
A plastic article or a method for producing a plastic article characterized by the following: