JP3866666B2 - Method for dyeing thermoplastic resin - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for dyeing thermoplastic resins (including molded products made of thermoplastic resins, the same applies hereinafter), and more particularly to a method for dyeing thermoplastic resin plastic lenses and a colored plastic lens obtained by the method. More specifically, the present invention relates to a method for dyeing a thermoplastic resin lens capable of efficiently dyeing a thermoplastic resin lens at a low temperature in a short time, and a colored plastic lens obtained by the method.
[0002]
[Prior art]
As a method for molding a plastic lens, a casting polymerization method or an injection molding method which is usually performed in the eyeglass industry is employed. As a lens obtained from an injection molding method, a lens made of polycarbonate made of bisphenol A is known. When a polycarbonate made of bisphenol A is used as a raw material, the manufacturing time of the lens can be shortened and it has good impact resistance. Therefore, many thermoplastic lenses obtained by an injection molding method have been proposed.
As a method for dyeing plastic lenses, dyeing using a disperse dye using water as a dispersion medium is generally performed. For plastic lenses that use water as a dispersion medium and are difficult to dye with disperse dyes, carrier dyes such as trichlorobenzene added to the dyeing solution, pressure dyeing, and heating organic dyes in the gas phase Sublimation and coloring methods, hard coat film staining, and the like have been proposed (see, for example, Patent Documents 1 to 5).
[0003]
However, a thermoplastic resin such as polycarbonate made of bisphenol A has a strong hydrophobic property, and normal dyeing using a disperse dye, particularly high-density dyeing is difficult.
Further, when the above-described various conventional dyeing methods are employed for thermoplastic resin lenses, there are the following problems.
Dyeing using a disperse dye with water as a dispersion medium requires dyeing at a relatively high temperature, and is difficult to apply to thermoplastic resin lenses having a low glass transition temperature.
In the carrier dyeing, since the thermoplastic resin is inferior in solvent resistance to the thermosetting resin, the carrier agent generally used in the optical plastic lens is affected by the lens surface and has transparency. Tend to be lost. In addition, conventional carriers are mainly composed of trichlorobenzene, dichlorobenzene, phenylphenol, diphenyl, methylnaphthalene, etc., and these compounds are listed as substances that are concerned about environmental pollution and adverse effects on the human body, In consideration of environmental problems, it is not preferable to use a carrier agent mainly composed of these compounds in the future.
In pressure dyeing, optical performance as a plastic lens may be lost due to pressure.
In the method of heating and sublimating organic dyes in the gas phase to color them, it is generally difficult to apply thermoplastic resins because of their poor heat resistance.
In hard coat film dyeing, it is difficult to contain a large amount of dye in the hard film, so it is difficult to dye at a high concentration, and when the film thickness is increased to contain a large amount of dye, Problems such as easy cracking in the film, distortion of the lens shape, and low film hardness occur. There are also problems such as poor light resistance compared to direct dyeing on a substrate.
[0004]
Also, the method of dissolving and dyeing the dye in the raw material of the plastic lens base material depends on the thickness of the lens, so that the central portion of the concave lens is thinner than the peripheral portion. The color of will become lighter and the surrounding area will become darker. For this reason, there is a possibility that color density may be generated in the entire lens, and in a spectacle lens having different powers on the left and right, there may be a problem that the color density is different on the left and right. Furthermore, in reality, it is impossible to produce various types of plastic lens substrates for colored optics by blending a large number of raw material liquids having different color tones and concentrations according to market needs.
Furthermore, the method of adding a compound having a large number of dyeing seats to the base material for the purpose of improving the dyeability can be put to practical use because the wear resistance and transparency of the base material are lowered when these compounds are added. Absent.
[Patent Document 1]
JP-A-11-248901 [Patent Document 2]
JP-A-4-146278 [Patent Document 3]
JP-A-4-57980 [Patent Document 4]
JP-A-9-145901 [Patent Document 5]
Japanese Patent Laid-Open No. 2001-192985
[Problems to be solved by the invention]
Under such circumstances, the present invention efficiently dyes a thermoplastic resin containing a polycarbonate resin composed of bisphenol A, which has been difficult to dye by the conventional dyeing method. A method for dyeing a thermoplastic resin that can efficiently dye a thermoplastic resin containing a polyester resin that can be dyed at a lower temperature and in a shorter time, in particular, a method for dyeing a thermoplastic resin plastic lens and its method The present invention provides a colored plastic lens to be obtained.
[0006]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, a thermoplastic resin that is difficult to dye by conventional methods, such as polycarbonate resin, or a thermoplastic resin that is dyeable but has low heat resistance, such as polyester resin, can be obtained by combining disperse dyes and monocyclic monoterpenes. It was found that the above-mentioned object can be achieved by dyeing with the use of the dye, and the present invention has been completed based on this finding.
That is, the present invention relates to a method for dyeing a thermoplastic resin in which a thermoplastic resin is immersed in a dye solution containing a disperse dye and a monocyclic monoterpene, in particular, a method for dyeing a thermoplastic resin plastic lens, and a method thereof. The present invention provides a colored plastic lens obtained by being dyed by the above method.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the method for dyeing a thermoplastic resin of the present invention, the thermoplastic resin is immersed in a dyeing solution containing a disperse dye and a monocyclic monoterpene. This dyeing method is particularly suitable as a method for producing a colored lens by dyeing a thermoplastic resin plastic lens. Hereinafter, the coloring method of the present invention will be described in detail using a thermoplastic lens as a specific example.
The thermoplastic resin plastic lens may be a plastic lens made of an injection moldable raw material. For example, a plastic lens containing a thermoplastic resin that is difficult to be dyed by conventional dyeing means such as polycarbonate resin and polyolefin resin. In addition, a plastic lens containing a thermoplastic resin that can be dyed by conventional dyeing means such as a polyester resin and a lens containing at least one raw material selected from polymer alloys made of these resins can be used.
[0008]
The polycarbonate resin is not particularly limited as long as it is a resin that can be used for a lens. Examples thereof are polymers or copolymers obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted. Specific examples include polycarbonate resins produced using 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) as a dihydroxydiaryl compound.
The polyolefin resin is not particularly limited as long as it is a resin that can be used for a lens. For example, cycloolefin polymer (trade name ZEONOR manufactured by Nippon Zeon Co., Ltd., trade name ARTON, Mitsui Chemical Co., Ltd. manufactured by JSR Corporation). ) Product name TOPAS).
The polyester resin is not particularly limited as long as it is a resin that can be used for a lens. Examples thereof include glycol-modified polyethylene terephthalate (trade name EASTER DN003 manufactured by Eastman Chemical Co., Ltd.).
Examples of the polymer alloy include an alloy of polycarbonate resin and polyolefin resin, an alloy of polyolefin resin and polyester resin, or an alloy of polycarbonate resin and polyester resin, and the trade name XYLEX (Nippon GE Plastics Co., Ltd.). Product name) EASTALLOY DA003 (manufactured by Eastman Chemical Co.).
[0009]
In the method of the present invention, a disperse dye is used as the dye. Although this disperse dye is hardly soluble in water, the plastic lens is dyed by being partially dissolved and dispersed inside the lens. Examples of the type include azo series, anthraquinone series, and nitroallylamine series. Azo-based and nitroallylamine-based materials are mainly yellow, orange, and red-based materials, and anthraquinone-based materials are mostly blue and purple-based materials.
[0010]
Typical disperse dyes in the method of the present invention include the following.
(1) Blue dyes: Diamondix Blue AC-E, Diamondix Blue RNE (CI Disperse Blue 91), Diamondix Blue GRE (CI Disperse Blue 81), Sumikaron Blue E-R ( CI Disperse Blue 91), Kayalon Polyester Blue GR-E (CI Disperse Blue 81)
(2) Red dyes: Diamond Nix Red AC-E, Diamond Shelton Fast Red R (CI Disper Thread 17), Diamond Shelton Fast Scarlet R (CI Disper Thread 7), Diamond Shelton Fast Pink R ( CI Disper Thread 4), Sumikaron Rubin SE-RPD, Kayalon Polyester Rubin GL-SE200 (CI Disper Thread 73)
[0011]
(3) Yellow dyes: Diamondix Yellow AC-E, Diamondix Yellow YL-SE (CI Disperse Yellow 42), Sumikaron Yellow SE-RPD, Diamond Shelton Fast Yellow GL (CI Disperse Yellow) 33), Kayalon Fast Yellow GL (C.I. Disperse Yellow 33), Kayalon Microester Yellow AQ-LE
(4) Orange dyes: Dianics Orange B-SE200 (C.I. Disperse Orange 13), Diamond Shelton Fast Orange GL (C.I. Disperse Orange 3), Miketone Polyester Orange B (C.I. Diss) Perth Orange 13), Sumikaron Orange SE-RPD, Sumikaron Orange SE-B (C.I. Disperse Orange 13)
(5) Purple dye: Dianics Violet 5R-SE (C.I. Disperse Violet 56), Sumikaron Violet E-2RL (C.I. Disperse Violet 28)
[0012]
In the method of the present invention, examples of the monocyclic monoterpene used together with the disperse dye include limonene, menthol, terpinene, ferrandrene, sylvestrene, pinene and terpineol, and are generally commercially available as a cleaning agent, for example, limonene. Water-soluble ones may be used, and anionic surface activity such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfosuccinate, aromatic sulfonate formalin condensate, lauryl sulfate, etc. A monocyclic monoterpene is emulsified using a nonionic surfactant such as an agent, polyoxyethyl alkyl ether, alkylamine ether, polyoxyethylene sorbitan fatty acid ester, etc., and dispersed in a dyeing bath. Good.
[0013]
In the method of the present invention, the specification ratio of the disperse dye and the monocyclic monoterpene in the dyeing liquid is not particularly limited, and may be appropriately selected according to the plastic lens to be dyed, the type of disperse dye, and the like.
The addition amount of the disperse dye in the dyeing liquid is not particularly limited, but practically, it is preferably 0.1 to 5% by weight and more preferably 0.3 to 0.5% by weight based on the total amount of the dyeing liquid.
The addition amount of the monocyclic monoterpene in the staining liquid is not particularly limited, but practically, it is preferably 0.001 to 1% by weight, and more preferably 0.01 to 0.5% by weight based on the total amount of the staining liquid. preferable.
[0014]
In the case of half dyeing, when the lens moves up and down during dyeing, the dye may adhere to the lens surface, dry, and stick. In that case, in order to prevent fixation of the dye, a surfactant may be added to the dyeing solution in a larger amount than the entire surface dyeing. By this, it is thought that the emulsified state of the monocyclic monoterpene becomes good and the fixing of the dye to the lens can be prevented. The surfactant is not particularly limited, and a conventionally known surfactant may be used, and a surfactant having a polyoxyethylene structure is particularly preferable.
The addition weight of the surfactant in the dyeing solution at the time of half dyeing is not particularly limited, but it is preferably 1.1 to 2 times as much as the whole dyeing.
[0015]
In order to dye a thermoplastic resin lens by the method of the present invention, first, a dye dispersion bath is prepared. In this dye dispersion bath, for example, a predetermined proportion of a disperse dye and a monocyclic monoterpene are added in water so that the dye concentration is about 0.1% to 5% by weight. Further, if necessary, a known dispersant conventionally used in dyeing with a disperse dye can be appropriately added. Next, the dye dispersion bath thus prepared is heated to about 70 to 100 ° C., and the optical thermoplastic resin lens for optical use is immersed in the bath for an arbitrary period of time, so that a desired colored optical fiber is obtained. The thermoplastic resin plastic lens can be obtained efficiently. The dyeing time is preferably in the range of 1 minute to 2 hours.
[0016]
The colored plastic lens of the present invention thus obtained is useful as, for example, a spectacle lens, a camera lens, a projector lens, a telescope lens, a magnifying lens, and the like.
The use of the present invention is not limited to the method for dyeing thermoplastic resin plastic lenses, and the present invention can also be applied to other molded products made of thermoplastic resin.
[0017]
【Example】
EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited at all by these examples.
In addition, the dyeing | staining density | concentration described in the Example was computed with the following formula | equation.
Dyeing density (%) = 100−transmittance (%)
[0018]
Example 1
A surfactant-containing limonene aqueous solution of Orange Cleaner 18 (manufactured by Yasuhara Chemical Co., Ltd., limonene-containing detergent) in a dyeing tank obtained by mixing 3.5 parts by weight of BPI Violet (BP dye) as a dye with 100 parts by weight of pure water 0.24 part by weight was added and mixed. A polycarbonate resin (manufactured by Teijin Ltd., trade name Panlite, polycarbonate resin made of bisphenol A) was used as the thermoplastic resin plastic lens. Dyeing was performed by immersion for 4 minutes at a dye bath temperature of 90 ° C. When the staining density was measured from the light transmittance at 525 nm, the staining density was 50%. Moreover, when dyeing was performed under the same conditions except that the staining time was 10 minutes, the staining concentration was 74%. Note that the dyeing density at 525 nm of the lens before being immersed in the dyeing tank was 9%.
[0019]
Comparative Example 1
In Example 1, the thermoplastic resin plastic lens was dyed in the same manner as in Example 1 except that the surfactant-containing limonene aqueous solution was not used. The staining density of this lens was measured from the light transmittance at 525 nm and found to be 9.5%. Since the staining density at 525 nm of the lens before being immersed in the staining tank was 9%, it was found that the lens was hardly dyed.
[0020]
Comparative Example 2
In Example 1, instead of the surfactant-containing limonene aqueous solution, the same procedure as in Example 1 was performed except that 0.08 part by weight of phthalimide / diethyl phthalate-containing carrier Melier TW (manufactured by Meisei Chemical Industry Co., Ltd.) was added. The thermoplastic resin plastic lens was dyed. In the lens after dyeing, the lens surface was destroyed and the transparency was lost.
[0021]
Comparative Example 3
In Example 1, except that 0.08 part by weight of terreyl carrier PE-550 (manufactured by Meisei Chemical Co., Ltd.), which is a dichlorobenzene / trichlorobenzene-containing carrier, was added instead of the surfactant-containing limonene aqueous solution. Staining was performed as in 1. In the lens after dyeing, the lens surface was destroyed and the transparency was lost.
[0022]
Example 2
Orange Cleaner 18 (manufactured by Yashara Chemical Co., Ltd., limonene-containing detergent) 0.08 parts by weight Neoperex G-15 (soft type sodium dodecylbenzenesulfonate, anionic surfactant, Kao Corporation) 0.01 parts by weight and Newcol 1500 (Polyoxyethylene castor oil ether, nonionic surfactant, Nippon Emulsion Co., Ltd.) 0.02 part by weight was added and mixed to prepare a surfactant-containing monocyclic monoterpene aqueous solution. This preparation solution was prepared by adding 100 parts by weight of pure water to a dyeing tank in which 3.52 parts by weight of BPI Violet (BPI dye) was mixed as a dye. A polycarbonate resin (manufactured by Teijin Ltd., trade name Panlite, polycarbonate resin consisting of bisphenol A) was used as a thermoplastic resin plastic lens, and gradient dyeing was performed at a dye bath temperature of 90 ° C. for 10 minutes. As a result, it was possible to dye a clean gradient without damaging the lens surface. When the staining density at the center of the lens was measured from the light transmittance at 525 nm, the staining density was 25%.
[0023]
Example 3
α-Pinene (manufactured by Yashara Chemical Co., Ltd.) 0.6 parts by weight, Perex OT-P (manufactured by Kao Corp., sulfosuccinic acid type anionic activator) 0.16 parts by weight, Emulgen A-90 (manufactured by Kao Corp.) Polyoxyethylene derivative) 0.16 parts by weight and Nowcol 1545 (manufactured by Sanyo Chemical Co., Ltd., polyoxyethylene castor oil ether) 0.16 parts by weight were mixed and stirred. Further, a dyeing solution was prepared by adding the mixture, 100 parts by weight of pure water, and 3.52 parts by weight of BPI Violet (BPI dye) as a dye. As the thermoplastic resin lens, polycarbonate (manufactured by Teijin Limited, trade name Panlite, polycarbonate made of bisphenol A) was used. Dyeing was performed by dipping for 10 minutes at a dye bath temperature of 90 ° C. As a result, dyeing could be performed without damaging the lens surface. When the staining density was measured from the light transmittance at 525 nm, the staining density was 27%.
[0024]
Example 4
In Example 3, dyeing was performed in the same manner as in Example 3 except that α-pinene was replaced with α-terpineol. When the staining density was measured from the light transmittance at 525 nm, the staining density was 25%.
Example 5
In Example 1, Xylex (Nippon GE Plastics Co., Ltd.) marketed as a polymer alloy of polycarbonate resin and polyester resin was used instead of polycarbonate resin as a thermoplastic resin lens. In addition, BPI Blue (BPI dye) was used instead of BPI Violet (BPI dye), and the dyeing bath temperature was set to 70 ° C. The other dyeing conditions were the same as in Example 1. When the staining density was measured from the light transmittance at 585 nm, the staining density was 30%.
[0025]
Comparative Example 4
In Example 5, a thermoplastic resin plastic lens was dyed in the same manner as in Example 5 except that the surfactant-containing limonene aqueous solution was not used. As a result, the lens was not dyed at all.
[0026]
【The invention's effect】
According to the method of the present invention, when dyeing a thermoplastic resin, in particular, a thermoplastic resin plastic lens, by dyeing with a disperse dye and a monocyclic monoterpene, a hardly dyeable thermoplastic resin, particularly a difficult dye. The dyeable thermoplastic resin optical plastic lens can be dyed to any color tone and density extremely efficiently at a low temperature and in a short time. For this reason, a colored plastic lens suitable as a spectacle lens or the like where fashionability is important can be easily manufactured at low cost. In addition, since monocyclic monoterpenes have good biodegradability, there is no concern about environmental pollution or adverse effects on the human body.

Claims (6)

  A method for dyeing a thermoplastic resin in which a thermoplastic resin is immersed in a dyeing solution containing a disperse dye and a monocyclic monoterpene, wherein the thermoplastic resin contains a polycarbonate resin made of bisphenol A. A method for dyeing thermoplastic resin.   The method for dyeing a thermoplastic resin according to claim 1, wherein the monocyclic monoterpene is at least one selected from limonene, menthol, terpinene, ferrandrene, sylvestrene, pinene and terpineol.   The method for dyeing a thermoplastic resin according to claim 1 or 2, wherein the amount of the monocyclic monoterpene is 0.001 to 1% by weight based on the total amount of the dyeing solution.   The method for dyeing a thermoplastic resin according to any one of claims 1 to 3, wherein a surfactant is added to the dyeing liquid to emulsify the monocyclic monoterpene.   The method for dyeing a thermoplastic resin according to claim 4, wherein the surfactant is a surfactant having a polyoxyethylene structure.   A method for dyeing a thermoplastic resin in which a thermoplastic resin is immersed in a dyeing liquid containing a disperse dye and a monocyclic monoterpene, wherein the thermoplastic resin is a thermoplastic resin plastic lens. Method.