WO2015140968A1 - Ink composition for hydrous contact lenses - Google Patents
Ink composition for hydrous contact lenses Download PDFInfo
- Publication number
- WO2015140968A1 WO2015140968A1 PCT/JP2014/057596 JP2014057596W WO2015140968A1 WO 2015140968 A1 WO2015140968 A1 WO 2015140968A1 JP 2014057596 W JP2014057596 W JP 2014057596W WO 2015140968 A1 WO2015140968 A1 WO 2015140968A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- ink composition
- soluble organic
- contact lens
- lens
- Prior art date
Links
Classifications
-
- 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
- C09D11/30—Inkjet printing inks
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Definitions
- the present invention relates to an ink composition for a hydrous contact lens, and more particularly to an ink composition that can be suitably used for coloring a hydrous contact lens by ink jet printing.
- ophthalmic lenses such as a hydrous contact lens
- a desired character is written or a pattern is drawn by coloring a part thereof.
- coloring of the ophthalmic lens is often performed by ink jet printing, and various studies have been made on the coloring method of the ophthalmic lens by the ink jet printing and the manufacturing method of the ophthalmic lens. Yes.
- an ink composition containing a polymerizable component such as a polymerizable colorant (pigment) is used, and the ink composition is discharged onto the lens surface; Then, a method of fixing a colorant (pigment) on the lens surface by performing heat treatment or irradiating ultraviolet rays to polymerize the ink composition (see Patent Document 1 and Patent Document 2), 2) The ink composition is discharged onto the lens surface, and then heat-treated as necessary to infiltrate the ink composition containing the colorant (pigment) into the lens and fix the colorant (pigment) in the lens.
- a method of coloring an ophthalmic lens by ink jet printing 1) an ink composition containing a polymerizable component such as a polymerizable colorant (pigment) is used, and the ink composition is discharged onto the lens surface; Then, a method of fixing a colorant (pigment) on the lens surface by performing heat treatment or irradiating ultraviolet rays to polymerize the ink composition (
- the ink composition used therein When coloring an ophthalmic lens by ink jet printing, if the ink composition used therein is easy to dry, the ink composition dries in the nozzle of the ink jet printing apparatus, resulting in nozzle clogging. The ink composition may not be effectively discharged from the nozzle.
- the object to be colored is a hydrous contact lens
- the ink composition is adhered to the surface of the hydrous contact lens by ink jet printing and colored by allowing the ink composition to penetrate into the lens
- the hydrous contact lens The present inventors who have been engaged in technical development relating to coloring of various ophthalmic lenses such as the above recognize that the following matters should be noted regarding the ink composition. Specifically, in order to effectively infiltrate the ink composition discharged (attached) onto the surface of the water-containing contact lens into the lens, the water-containing contact lens to which the ink composition is attached is heated.
- the solvent component in the ink composition evaporates particularly during the heating described above, and the penetration of the ink composition into the lens effectively proceeds.
- an auxiliary agent made of a polymer compound is often added to an ink composition to be used for inkjet printing so that it can be stably ejected from the head of an inkjet printing apparatus. Since the auxiliary agent is a polymer, the auxiliary agent is bulky, and the auxiliary agent inhibits the penetration of the ink composition into the lens, and as a result, the water-containing contact lens may not be effectively colored.
- the ink composition may come into contact with the cornea, thereby causing eye damage.
- an ink composition containing a polymerizable component or composed of a polymerizable component its physical properties are likely to change due to a change with time or a change in the surrounding environment.
- polymerization is performed in the head of an inkjet printing apparatus.
- the nozzle is clogged, and the ink composition may not be effectively discharged from the nozzle.
- the present invention has been made in the background of such circumstances, and the problem to be solved is that the ink is stably discharged from the head of the ink jet printing apparatus when subjected to ink jet printing.
- the occurrence of clogging of the head due to drying of the ink composition is effectively suppressed, and the target portion of the lens can be effectively colored. It is an object of the present invention to provide an ink composition for a hydrous contact lens that can effectively penetrate into a conductive contact lens.
- the present invention provides: a) a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more; b) a molecular weight of 1000 or less; And a water-soluble organic thickening agent having a boiling point of 100 ° C. or higher, and a weight reduction rate when heat treatment is performed at 60 ° C. for 85 hours: LOD is 30% or less.
- the gist of the composition is an ink composition for lenses.
- the water content is 0 to 10% by weight.
- the ink composition for a hydrous contact lens of the present invention is composed of a compound having no radically polymerizable group having a carbon-carbon double bond.
- the water-soluble organic solvent is N-methyl-2-pyrrolidone, propylene carbonate, dimethyl sulfoxide, 1,3-dimethyl- It is one or more selected from imidazolidinone and triethyl phosphate.
- the water-soluble organic thickener is 2-pyrrolidone, ⁇ -caprolactam, propylene glycol, glycerol, ethylene glycol, diethylene glycol. , One or more selected from triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 2-methyl-2,4-pentanediol.
- the water-containing contact lens ink composition of the present invention has the following advantages: 1)
- the water-soluble organic solvent is N-methyl-2-pyrrolidone, and the water-soluble organic thickener is 2-pyrrolidone.
- the water-soluble organic solvent is propylene carbonate, the water-soluble organic thickener is diethylene glycol, and 3) the water-soluble organic solvent is propylene carbonate, and the water-soluble organic thickener is propylene glycol. This is also a desirable mode.
- the contact angle with respect to the hydrous contact lens to be colored is 70 to 90 °.
- the ink composition for a hydrous contact lens according to the present invention includes a predetermined water-soluble organic solvent and a predetermined water-soluble organic thickener, and is further subjected to a heat treatment at 60 ° C. for 85 hours. Weight reduction ratio at the time: It is prepared so that LOD is 30% or less.
- the ink composition of the present invention is capable of effectively penetrating into the water-containing contact lens to be colored, the target portion of the lens can be advantageously colored. There is also little risk of the ink composition remaining on the lens surface after processing. Therefore, in the hydrous contact lens colored using the ink composition of the present invention, the occurrence of eye damage caused by the ink composition can be effectively suppressed.
- the ink composition for a hydrous contact lens according to the present invention (hereinafter also simply referred to as an ink composition) is a) a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more. And b) a water-soluble organic thickener having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more as an essential component.
- the solvent constituting the ink composition of the present invention is a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more, preferably 150 ° C. or more.
- a water-soluble organic solvent is used to dissolve or disperse the colorant in the same manner as various solvents used in conventional ink compositions.
- the coloring treatment for the water-containing contact lens is usually performed on the water-containing contact lens (hereinafter also referred to as a lens precursor) in a dry state (non-swelled state).
- a lens precursor water-containing contact lens
- An ink composition is attached to the surface of a hydrous contact lens (lens precursor) in a dry state (non-swelled state), the ink composition is allowed to penetrate into the lens precursor, and the colorant in the composition is used as the lens precursor.
- the organic solvent also penetrates into the lens precursor together with the colorant. Due to the nature of contact lenses that are mounted on the cornea, if an organic solvent remains in the lens, it may cause various eye damages. It is necessary to remove the organic solvent remaining inside.
- the lens precursor that has been subjected to the coloring treatment is subjected to a hydration treatment and swollen to obtain the intended hydrous contact lens. Therefore, when a water-soluble organic solvent is used as a solvent constituting the ink composition, the organic solvent in the lens precursor is effectively eluted during the hydration treatment, and is effectively removed outside the lens. Thus, there is an advantage that a separate organic solvent removal process is not required.
- water-soluble organic solvents particularly those having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more can be used for the head by drying the ink composition during ink jet printing. Occurrence of clogging is effectively suppressed, and furthermore, drying of the ink composition (evaporation of the solvent) is advantageously suppressed during heating in the coloring process described later, and the colorant contained in the ink composition is reduced. It is possible to stably penetrate the lens precursor.
- the weight reduction rate (LOD: loss on drying) of the ink composition described later can be reduced to 30% or less.
- any water-soluble organic solvent may be used as long as it has a viscosity of 10 cp or less at 25 ° C. and a boiling point of 100 ° C. or more as described above. Is possible.
- the water-soluble organic solvent one or two or more kinds selected from N-methyl-2-pyrrolidone, propylene carbonate, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, and triethyl phosphate are used. N-methyl-2-pyrrolidone and / or propylene carbonate are preferably used.
- the water-soluble organic thickener used in the ink composition of the present invention has a molecular weight of 1000 or less and a boiling point of 100 ° C. or more. More specifically, the molecular weight is 1000 or less and the boiling point is 100 ° C. or higher, 1) a liquid having a viscosity of 10 to 1000 cp at 25 ° C., or 2) a solid at 25 ° C.
- a thickener has been added to the ink composition used for inkjet printing so that the ink composition can be stably ejected from the inkjet head.
- High molecular weights such as (PEG), polyvinylpyrrolidone (PVP), and copolymers of acrylic monomers are common.
- PEG polyvinylpyrrolidone
- PVP polyvinylpyrrolidone
- copolymers of acrylic monomers are common.
- such a high-molecular-weight thickener is blended in the ink composition, and the water-containing contact lens (lens precursor) in a dry state (non-swelled state) is colored using the ink composition.
- the high molecular weight thickener does not effectively penetrate into the lens precursor, and the ink composition remains on the surface of the lens precursor, and the desired portion of the lens precursor is not colored.
- the ink composition remaining on the surface of the lens precursor may come into contact with the cornea to cause eye damage.
- the viscosity of the ink composition is required even after the ink composition droplets land on the lens surface. . That is, if the viscosity of the ink composition is too low, the droplet of the ink composition lands on the lens surface and then sags with time. As a result, the ink composition is formed at the target portion of the lens.
- a water-soluble organic thickener having a boiling point of 100 ° C. or higher is used. By doing so, drying of the ink composition can be advantageously suppressed.
- a water-soluble organic thickener having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more is used.
- any water-soluble organic thickener may be used as long as it has a molecular weight of 1000 or less and a boiling point of 100 ° C. or more as described above. It is possible.
- the water-soluble organic thickener 2-pyrrolidone, ⁇ -caprolactam, propylene glycol, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5- One or more selected from pentanediol and 2-methyl-2,4-pentanediol are preferably used, and particularly preferably 2-pyrrolidone, ⁇ -caprolactam, propylene glycol, glycerol, One or two or more selected from ethylene glycol and diethylene glycol are used.
- the blending ratio (use ratio) of the water-soluble organic solvent and the water-soluble organic thickener described above depends on the type of the water-soluble organic solvent and the water-soluble organic thickener used.
- the water-soluble organic solvent: water-soluble organic thickener 1: 9 to 9: 1 (weight ratio) is usually used, respectively.
- the following combinations can be exemplified.
- N-methyl-2-pyrrolidone is used as the water-soluble organic solvent
- 2-pyrrolidone is used as the water-soluble organic thickener
- the water-soluble organic solvent (N-methyl-2-pyrrolidone) and the water-soluble organic thickener are used.
- propylene carbonate is used as the water-soluble organic solvent and diethylene glycol is used as the water-soluble organic thickener, 100 weight of the total amount of the water-soluble organic solvent (propylene carbonate) and the water-soluble organic thickener (diethylene glycol) It is preferable to use propylene carbonate in a proportion of 20 to 90 parts by weight and diethylene glycol in a proportion of 10 to 80 parts by weight, respectively.
- propylene carbonate is used as the water-soluble organic solvent and propylene glycol is used as the water-soluble organic thickener
- the total amount of the water-soluble organic solvent (propylene carbonate) and the water-soluble organic thickener (propylene glycol) It is preferable to use propylene carbonate in a proportion of 60 to 90 parts by weight and propylene glycol in a proportion of 10 to 40 parts by weight with respect to 100 parts by weight, respectively.
- a colorant is used together with the above-described water-soluble organic solvent and water-soluble organic thickener as in the case of conventional ink compositions.
- various colorants conventionally used in ink compositions can be used as long as they do not impair the object of the present invention, but are not particularly pigments insoluble in organic solvents, What are referred to as dyes are advantageously used.
- dyes so-called non-polymerizable dyes (non-polymerizable dyes) that do not have a radically polymerizable group having a carbon-carbon double bond in the molecule are particularly preferably used.
- Non-polymerizable dyes include the following compounds represented by the color index (C.I.), specifically, C.I. I. 26100, C.I. I. 47005, C.I. I. 61520, C.I. I. 61565, C.I. I. 47020, C.I. I. 60505, C.I. I. 12740, C.I. I. 18950, C.I. I. 60725, C.I. I. 47000, C.I. I. 12770 etc. can be illustrated.
- C.I. color index
- the blending ratio of the above-described colorant in the ink composition of the present invention is appropriately determined according to the printing method, the type of the hydrous contact lens that is the printing object, etc.
- Total amount of the above-mentioned water-soluble organic solvent and water-soluble organic thickener 0.02 to 10 parts by weight, preferably 0.02 to 5 parts by weight, more preferably 0.02 to 2 parts per 100 parts by weight. It will mix
- water-containing contact lens ink composition In the water-containing contact lens ink composition according to the present invention, other components used in preparing the conventional contact lens ink composition are used as long as the effects of the present invention are not impaired.
- such other component is preferably a compound having no radically polymerizable group having a carbon-carbon double bond.
- the above-described water-soluble organic solvent, water-soluble organic thickener and colorant are also preferably compounds having no radically polymerizable group having a carbon-carbon double bond.
- an ink composition containing a compound having a radically polymerizable group having a carbon-carbon double bond tends to change its physical properties due to changes with time or changes in the surrounding environment. For example, polymerization can occur within the head of an ink jet printing apparatus. As a result, nozzle clogging occurs, and the ink composition may not be effectively discharged from the nozzle.
- the water-containing contact lens ink composition according to the present invention is prepared in the same manner as in the conventional contact lens ink composition.
- the water-soluble organic solvent, the water-soluble organic thickener and the colorant described above are used as necessary.
- the other components are mixed by a conventionally known method.
- the blending ratio of each component is determined so that the weight reduction ratio: LOD when the heat treatment is performed at 60 ° C. for 85 hours: LOD is 30% or less.
- LOD weight reduction ratio
- the ink composition of the present invention can effectively prevent clogging of the head due to drying of the ink composition when used in ink jet printing, and will be described later.
- drying of the ink composition evaporation of the solvent
- the ink composition effectively penetrates into the lens precursor.
- the weight reduction rate of the ink composition is calculated by the following equation after heat treatment at 60 ° C. for 85 hours.
- the ink composition of the present invention is preferably prepared so that the water content is 0 to 10% by weight. However, if the water content exceeds 10% by weight, it is difficult to make the above-mentioned weight reduction rate: LOD (loss on drying) 30% or less, and an ink composition that has landed on the lens precursor in ink jet printing. This is because there is a risk that the liquid droplets formed from the liquid will sag with time, and as a result, the resulting colored portion (characters, patterns, etc.) may be blurred.
- LOD loss on drying
- the ink composition of the present invention is preferably prepared so that the contact angle with respect to the water-containing contact lens (lens precursor) to be colored is 70 to 90 °.
- a printing process coloring process
- an ink composition having a contact angle with respect to the water-containing contact lens that is a coloring target is less than 70 ° is used as a lens precursor.
- the liquid droplets made of the landed ink composition cause liquid dripping, and as a result, a printed portion (colored portion) having high resolution cannot be obtained.
- the contact angle with respect to the water-containing contact lens means the ink composition at the apex of the lens surface of the dry (non-swelled) water-containing contact lens (lens precursor) to be colored. It means what forms a droplet of an object and is measured on such a droplet, i.e. measured according to the droplet method.
- the water-containing contact lens ink composition of the present invention can be used for various conventionally known lenses as long as it is a water-containing contact lens, and particularly preferably used for silicone hydrogel lenses. Is possible.
- the printing process (coloring process) for the water-containing contact lens using the water-containing contact lens ink composition according to the present invention is advantageously performed according to the following procedure.
- the ink composition for a hydrous contact lens according to the present invention is attached to the surface of a precursor (lens precursor) of a hydrous contact lens in a dry state (non-swelled state).
- a method of attaching the ink composition to the surface of the lens precursor a conventionally known method such as a method of applying a liquid ink composition to the surface of the lens precursor can be used.
- examples of the method for applying the ink composition to the surface of the lens precursor include a pad printing method, a screen printing method, and a method using an ink jet printing apparatus.
- an ink jet printing apparatus from the viewpoint of easily printing a desired pattern of characters, numbers, iris patterns and the like (hereinafter collectively referred to as characters in this paragraph).
- the ink jet printing apparatus sprays a liquid ink composition on the lens surface as very fine droplets, and the droplets that have landed on the surface form one dot, and a desired collection of dots is formed. Are formed.
- characters or the like in which small dots are gathered at high density give a sharp contrast and exhibit excellent visibility.
- the size of droplets, the point where droplets land, etc. can be accurately controlled by a computer, etc., and characters can be changed by changing the computer program.
- the coating method using the ink jet printing apparatus has an excellent advantage that the productivity is very high and a constant high quality printing can be performed. Furthermore, according to the ink jet printing apparatus, the applied droplets are fine, and the amount of droplets is small compared to the interface area when landed on the lens, so that it can easily penetrate into the lens precursor more quickly. Become. Therefore, in addition to the above-described advantages, the ink jet printing apparatus can further reduce the deposition of colorant on the lens surface and the generation of residues, and allow the colorant to penetrate into the lens. Is also a very advantageous method.
- a typical ink jet printing apparatus is composed of an ink composition supply system and an ejection device composed of a nozzle equipped with a piezoelectric element such as a piezoelectric element.
- the ink composition is generated by vibration generated by applying a voltage to the piezoelectric element. It has a mechanism for discharging an object as fine droplets from a nozzle.
- Any ink jet printing apparatus can be suitably used as long as it can eject desired droplets.
- the nozzles may be single or plural.
- the time required for adhering the ink composition of the present invention to the surface of the lens precursor will vary depending on the method of contacting the ink composition, the printing area, its shape, etc., for example, an ink jet printing apparatus Usually, it is about several seconds to 10 minutes.
- the lens precursor to which the ink composition of the present invention is adhered is subjected to a heat treatment.
- the water-soluble organic solvent, the water-soluble organic thickener and the colorant constituting the ink composition effectively penetrate into the lens precursor.
- the heat treatment is preferably carried out at a heating temperature of 90 to 130 ° C., generally for a few seconds to 1 minute, preferably for a heating time of about 5 to 30 seconds. If the heating temperature is too low or the heating time is too short, the effect of the heat treatment may not be enjoyed, while if the heating temperature is too high or the heating time is too long, the lens precursor will be deformed, This is because there is a risk of deterioration. Note that the heat treatment in the present invention can be performed according to any conventionally known method for heating a contact lens.
- the lens precursor subjected to the above treatment when the lens precursor subjected to the above treatment is subjected to a hydration treatment according to a conventional method, the lens precursor absorbs water (swells), while the water-soluble organic solvent in the lens precursor and The water-soluble organic thickener is effectively eluted to the outside of the lens precursor, so that a water-containing contact lens in which a desired portion is colored is obtained.
- the compounds marked with “(*)” are water-soluble organic solvents having a viscosity of 10 cp or less at 25 ° C. and a boiling point of 100 ° C. or more in the present invention.
- the compound to which “(**)” is attached is a “water-soluble organic thickener having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more” in the present invention.
- Example 1 to Example 19 According to the composition shown in Table 1 and Table 2 below, 19 types of ink compositions for hydrous contact lenses were prepared (Examples 1 to 19). For each ink composition, the weight loss rate (LOD) and the contact angle were measured or calculated according to the following method. The obtained weight loss rate (LOD) and contact angle are shown in Table 1 and Table 2 below.
- Each ink composition according to Examples 1 to 19 was attached to a predetermined portion of the surface of a dry (non-swelled) silicone hydrogel lens (Asmofilcon A) using a piezo ink jet printing apparatus. Immediately thereafter, the lens was irradiated with far-infrared rays for 20 seconds with a far-infrared heater (manufactured by Noritake Company Limited, trade name: SCH-110, input voltage: 100 V, power capacity: 400 W). The temperature of the lens surface immediately after the end of irradiation was measured with a non-contact thermometer (manufactured by Anritsu Keiki Co., Ltd., trade name: Dual Thermo AR-1500), and was about 100 ° C. When the lens temperature is allowed to reach room temperature and then the surface of the lens is visually observed, in all of the ink compositions according to Examples 1 to 19, the colorant penetrates into the lens and causes bleeding. It was confirmed that the lens was colored.
- Silicone hydrogel lenses in a dry state (non-swelled state) using the ink compositions according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7 according to the same method as in Examples 1 to 19 The coloring process was implemented with respect to (Asmofilcon A). When the surface of the lens after such treatment was visually observed, it was observed that in all of the ink compositions according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7, bleeding occurred in the colored portion. It was.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Eyeglasses (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The purpose of the present invention is to provide an ink composition for hydrous contact lenses, the ink composition being a composition that is discharged stably from the head of an inkjet printing apparatus when used for inkjet printing while effectively limiting the occurrence of clogging of the head due to drying of the ink composition and also being capable of effectively coloring intended areas of the lens and of effectively penetrating into the hydrous contact lens that is the object being colored. The ink composition for hydrous contact lenses is configured: so as to comprise a) a water-soluble organic solvent with a viscosity at 25°C of 10 cp or less and a boiling point of 100°C or higher, and b) a water-soluble organic thickener with a molecular weight of 1000 or less and a boiling point of 100°C or higher; and so that the weight loss rate LOD when heat treatment is performed at 60°C for 85 hours is 30% or less.
Description
本発明は、含水性コンタクトレンズ用インク組成物に係り、特に、含水性コンタクトレンズをインクジェット印刷によって着色する際に好適に用いられ得るインク組成物に関するものである。
The present invention relates to an ink composition for a hydrous contact lens, and more particularly to an ink composition that can be suitably used for coloring a hydrous contact lens by ink jet printing.
従来より、含水性コンタクトレンズを始めとする各種の眼用レンズにおいては、その一部に着色を施すことにより、所望とする文字を記したり、或いは模様を描くこと等が行なわれている。このような眼用レンズに対する着色は、インクジェット印刷によって実施されることが多く、従来より、インクジェット印刷による眼用レンズの着色方法や、眼用レンズの製造方法等について、様々な研究が為されている。
Conventionally, in various types of ophthalmic lenses such as a hydrous contact lens, a desired character is written or a pattern is drawn by coloring a part thereof. Such coloring of the ophthalmic lens is often performed by ink jet printing, and various studies have been made on the coloring method of the ophthalmic lens by the ink jet printing and the manufacturing method of the ophthalmic lens. Yes.
ここで、インクジェット印刷によって眼用レンズを着色する方法としては、１）重合性着色剤（色素）等の重合性成分を含むインク組成物を用いて、かかるインク組成物をレンズ表面に吐出し、その後、加熱処理を施したり、或いは、紫外線を照射して、インク組成物を重合させることにより、レンズ表面に着色剤（色素）を定着させる方法（特許文献１、特許文献２を参照）や、２）インク組成物をレンズ表面に吐出し、その後、必要に応じて加熱処理を施し、着色剤（色素）を含むインク組成物をレンズ内に浸透させ、レンズ内に着色剤（色素）を定着させる方法（特許文献３を参照）等が、広く知られている。
Here, as a method of coloring an ophthalmic lens by ink jet printing, 1) an ink composition containing a polymerizable component such as a polymerizable colorant (pigment) is used, and the ink composition is discharged onto the lens surface; Then, a method of fixing a colorant (pigment) on the lens surface by performing heat treatment or irradiating ultraviolet rays to polymerize the ink composition (see Patent Document 1 and Patent Document 2), 2) The ink composition is discharged onto the lens surface, and then heat-treated as necessary to infiltrate the ink composition containing the colorant (pigment) into the lens and fix the colorant (pigment) in the lens. Such a method (see Patent Document 3) is widely known.
インクジェット印刷によって眼用レンズを着色する場合、そこで用いられるインク組成物が乾燥しやすいものであると、インクジェット印刷装置のノズル内においてインク組成物が乾燥し、その結果、ノズルの目詰まりが生じて、ノズルよりインク組成物が効果的に吐出されない恐れがある。
When coloring an ophthalmic lens by ink jet printing, if the ink composition used therein is easy to dry, the ink composition dries in the nozzle of the ink jet printing apparatus, resulting in nozzle clogging. The ink composition may not be effectively discharged from the nozzle.
また、着色対象が含水性コンタクトレンズであって、含水性コンタクトレンズの表面にインクジェット印刷によってインク組成物を付着せしめ、かかるインク組成物をレンズ内に浸透させることによって着色する場合、含水性コンタクトレンズ等の様々な眼用レンズの着色に関する技術開発に長年に亘って従事してきた本発明者等は、インク組成物に関して、以下に述べる事項に注意すべきであると認識している。具体的には、含水性コンタクトレンズ表面に吐出された（付着せしめられた）インク組成物を、レンズ内へ効果的に浸透させるためには、インク組成物が付着した含水性コンタクトレンズを加熱することが好ましいところ、インク組成物が乾燥しやすいものであると、上述の加熱の際に、特にインク組成物中の溶媒成分が蒸発し、レンズ内へのインク組成物の浸透が効果的に進行しない恐れがある。また、インクジェット印刷に供されるインク組成物には、インクジェット印刷装置のヘッドから安定的に吐出され得るように、一般に、高分子化合物からなる助剤が添加される場合が多いが、使用される助剤は高分子であるが故に嵩高く、かかる助剤がインク組成物のレンズ内への浸透を阻害し、その結果、含水性コンタクトレンズを効果的に着色することが出来ない恐れがある。更に、表面にインク組成物が残留した状態にある含水性コンタクトレンズを眼に装着すると、インク組成物が角膜と接触することにより、眼障害を引き起こす恐れもある。
In the case where the object to be colored is a hydrous contact lens, and the ink composition is adhered to the surface of the hydrous contact lens by ink jet printing and colored by allowing the ink composition to penetrate into the lens, the hydrous contact lens The present inventors who have been engaged in technical development relating to coloring of various ophthalmic lenses such as the above recognize that the following matters should be noted regarding the ink composition. Specifically, in order to effectively infiltrate the ink composition discharged (attached) onto the surface of the water-containing contact lens into the lens, the water-containing contact lens to which the ink composition is attached is heated. Preferably, when the ink composition is easy to dry, the solvent component in the ink composition evaporates particularly during the heating described above, and the penetration of the ink composition into the lens effectively proceeds. There is a fear of not. In general, an auxiliary agent made of a polymer compound is often added to an ink composition to be used for inkjet printing so that it can be stably ejected from the head of an inkjet printing apparatus. Since the auxiliary agent is a polymer, the auxiliary agent is bulky, and the auxiliary agent inhibits the penetration of the ink composition into the lens, and as a result, the water-containing contact lens may not be effectively colored. Furthermore, when a water-containing contact lens with the ink composition remaining on the surface is attached to the eye, the ink composition may come into contact with the cornea, thereby causing eye damage.
一方、重合性成分を含む、乃至は重合性成分より構成されるインク組成物にあっては、その物性が経時変化や周辺環境の変化によって変化し易く、例えば、インクジェット印刷装置のヘッド内において重合が開始し、その結果、ノズルの目詰まりが生じて、ノズルよりインク組成物が効果的に吐出されない恐れがある。
On the other hand, in an ink composition containing a polymerizable component or composed of a polymerizable component, its physical properties are likely to change due to a change with time or a change in the surrounding environment. For example, polymerization is performed in the head of an inkjet printing apparatus. As a result, the nozzle is clogged, and the ink composition may not be effectively discharged from the nozzle.
ここにおいて、本発明は、かかる事情を背景にして為されたものであって、その解決すべき課題とするところは、インクジェット印刷に供した際に、インクジェット印刷装置のヘッドから安定的に吐出されると共に、インク組成物の乾燥によるヘッドの目詰まりの発生が効果的に抑制され、また、レンズの目的とする部位を効果的に着色することが可能であり、更には、着色対象である含水性コンタクトレンズ内に効果的に浸透可能な含水性コンタクトレンズ用インク組成物を提供することにある。
Here, the present invention has been made in the background of such circumstances, and the problem to be solved is that the ink is stably discharged from the head of the ink jet printing apparatus when subjected to ink jet printing. In addition, the occurrence of clogging of the head due to drying of the ink composition is effectively suppressed, and the target portion of the lens can be effectively colored. It is an object of the present invention to provide an ink composition for a hydrous contact lens that can effectively penetrate into a conductive contact lens.
そして、本発明は、かかる課題を解決すべく、ａ）２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上である水溶性有機溶媒と、ｂ）分子量が１０００以下であり、且つ、沸点が１００℃以上である水溶性有機増粘剤とを含み、６０℃で８５時間の加熱処理を実施した際の重量減少率：ＬＯＤが３０％以下であることを特徴とする含水性コンタクトレンズ用インク組成物を、その要旨とするものである。
In order to solve this problem, the present invention provides: a) a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more; b) a molecular weight of 1000 or less; And a water-soluble organic thickening agent having a boiling point of 100 ° C. or higher, and a weight reduction rate when heat treatment is performed at 60 ° C. for 85 hours: LOD is 30% or less. The gist of the composition is an ink composition for lenses.
ここで、本発明に従う含水性コンタクトレンズ用インク組成物の、好ましい第一の態様においては、水分含有量が０～１０重量％である。
Here, in a first preferred embodiment of the ink composition for a hydrous contact lens according to the present invention, the water content is 0 to 10% by weight.
また、本発明の含水性コンタクトレンズ用インク組成物における、好ましい第二の態様においては、炭素－炭素二重結合を有するラジカル重合性基を有さない化合物より構成されている。
In a preferred second embodiment of the ink composition for a hydrous contact lens of the present invention, it is composed of a compound having no radically polymerizable group having a carbon-carbon double bond.
さらに、本発明の含水性コンタクトレンズ用インク組成物における、好ましい第三の態様においては、前記水溶性有機溶媒が、Ｎ－メチル－２－ピロリドン、炭酸プロピレン、ジメチルスルホキシド、１，３－ジメチル－イミダゾリジノン、リン酸トリエチルの中より選択される一種又は二種以上である。
Furthermore, in the third preferred embodiment of the ink composition for water-containing contact lenses of the present invention, the water-soluble organic solvent is N-methyl-2-pyrrolidone, propylene carbonate, dimethyl sulfoxide, 1,3-dimethyl- It is one or more selected from imidazolidinone and triethyl phosphate.
さらにまた、本発明の含水性コンタクトレンズ用インク組成物における、好ましい第四の態様においては、前記水溶性有機増粘剤が、２－ピロリドン、ε－カプロラクタム、プロピレングリコール、グリセロール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオールの中より選択される一種又は二種以上である。
Furthermore, in a preferred fourth aspect of the water-containing contact lens ink composition of the present invention, the water-soluble organic thickener is 2-pyrrolidone, ε-caprolactam, propylene glycol, glycerol, ethylene glycol, diethylene glycol. , One or more selected from triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 2-methyl-2,4-pentanediol.
加えて、本発明の含水性コンタクトレンズ用インク組成物は、１）前記水溶性有機溶媒がＮ－メチル－２－ピロリドンであり、前記水溶性有機増粘剤が２－ピロリドンであること、２）前記水溶性有機溶媒が炭酸プロピレンであり、前記水溶性有機増粘剤がジエチレングリコールであること、及び、３）前記水溶性有機溶媒が炭酸プロピレンであり、前記水溶性有機増粘剤がプロピレングリコールであることをも、その望ましい態様とするものである。
In addition, the water-containing contact lens ink composition of the present invention has the following advantages: 1) The water-soluble organic solvent is N-methyl-2-pyrrolidone, and the water-soluble organic thickener is 2-pyrrolidone. ) The water-soluble organic solvent is propylene carbonate, the water-soluble organic thickener is diethylene glycol, and 3) the water-soluble organic solvent is propylene carbonate, and the water-soluble organic thickener is propylene glycol. This is also a desirable mode.
また、本発明の含水性コンタクトレンズ用インク組成物にあっては、好ましくは、着色対象である含水性コンタクトレンズに対する接触角が７０～９０°である。
In the ink composition for a hydrous contact lens of the present invention, preferably, the contact angle with respect to the hydrous contact lens to be colored is 70 to 90 °.
このように、本発明に従う含水性コンタクトレンズ用インク組成物は、所定の水溶性有機溶媒と、所定の水溶性有機増粘剤とを含み、更に、６０℃で８５時間の加熱処理を実施した際の重量減少率：ＬＯＤが３０％以下となるように調製されてなるものである。かかる構成を採用したことにより、本発明の含水性コンタクトレンズ用インク組成物にあっては、インクジェット印刷にて含水性コンタクトレンズを着色すると、印刷の際にインクジェット印刷装置のヘッドから安定的に吐出され得ると共に、インク組成物の乾燥によるヘッドの目詰まりの発生も効果的に抑制される。加えて、本発明のインク組成物は、着色対象である含水性コンタクトレンズ内に効果的に浸透可能なものであるところから、レンズの目的とする部位を有利に着色可能であり、また、着色処理後のレンズ表面にインク組成物が残留する恐れも少ないものである。従って、本発明のインク組成物を用いて着色された含水性コンタクトレンズにあっては、インク組成物に起因する眼障害の発生が効果的に抑制され得るのである。
As described above, the ink composition for a hydrous contact lens according to the present invention includes a predetermined water-soluble organic solvent and a predetermined water-soluble organic thickener, and is further subjected to a heat treatment at 60 ° C. for 85 hours. Weight reduction ratio at the time: It is prepared so that LOD is 30% or less. By adopting such a configuration, in the water-containing contact lens ink composition of the present invention, when the water-containing contact lens is colored by ink jet printing, it is stably ejected from the head of the ink jet printing apparatus during printing. In addition, the occurrence of clogging of the head due to drying of the ink composition is effectively suppressed. In addition, since the ink composition of the present invention is capable of effectively penetrating into the water-containing contact lens to be colored, the target portion of the lens can be advantageously colored. There is also little risk of the ink composition remaining on the lens surface after processing. Therefore, in the hydrous contact lens colored using the ink composition of the present invention, the occurrence of eye damage caused by the ink composition can be effectively suppressed.
ところで、本発明に従う含水性コンタクトレンズ用インク組成物（以下、単にインク組成物とも言う）は、ａ）２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上である水溶性有機溶媒と、ｂ）分子量が１０００以下であり、且つ、沸点が１００℃以上である水溶性有機増粘剤とを必須の構成成分として、含有するものである。
By the way, the ink composition for a hydrous contact lens according to the present invention (hereinafter also simply referred to as an ink composition) is a) a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more. And b) a water-soluble organic thickener having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more as an essential component.
先ず、本発明のインク組成物を構成する溶媒は、２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上、好ましくは１５０℃以上である水溶性有機溶媒である。かかる水溶性有機溶媒は、従来のインク組成物にて用いられる各種溶媒と同様に、着色剤を溶解乃至は分散せしめるために用いられるものである。
First, the solvent constituting the ink composition of the present invention is a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more, preferably 150 ° C. or more. Such a water-soluble organic solvent is used to dissolve or disperse the colorant in the same manner as various solvents used in conventional ink compositions.
含水性コンタクトレンズに対する着色処理は、通常、乾燥状態（非膨潤状態）にある含水性コンタクトレンズ（以下、レンズ前駆体ともいう）に対して実施される。乾燥状態（非膨潤状態）にある含水性コンタクトレンズ（レンズ前駆体）表面にインク組成物を付着させ、かかるインク組成物をレンズ前駆体内に浸透せしめ、組成物中の着色剤をレンズ前駆体に内包させることによって着色する場合、有機溶媒も、着色剤と共にレンズ前駆体内に浸透する。角膜上に装着するというコンタクトレンズの性質上、レンズ内に有機溶媒が残留すると、様々な眼障害を引き起こす恐れがあることから、上述の着色処理が施されたレンズ前駆体に対しては、その内部に残留する有機溶媒の除去処理が必要となる。一方、着色処理が施されたレンズ前駆体に対しては、水和処理が施され、膨潤させることによって、目的とする含水性コンタクトレンズとされる。従って、インク組成物を構成する溶媒として水溶性有機溶媒を用いると、水和処理の際に、レンズ前駆体内の有機溶媒が効果的に溶出し、レンズ外へ効果的に除去されることとなるのであり、別途の有機溶媒の除去処理が不要になるという利点がある。
The coloring treatment for the water-containing contact lens is usually performed on the water-containing contact lens (hereinafter also referred to as a lens precursor) in a dry state (non-swelled state). An ink composition is attached to the surface of a hydrous contact lens (lens precursor) in a dry state (non-swelled state), the ink composition is allowed to penetrate into the lens precursor, and the colorant in the composition is used as the lens precursor. When coloring by encapsulating, the organic solvent also penetrates into the lens precursor together with the colorant. Due to the nature of contact lenses that are mounted on the cornea, if an organic solvent remains in the lens, it may cause various eye damages. It is necessary to remove the organic solvent remaining inside. On the other hand, the lens precursor that has been subjected to the coloring treatment is subjected to a hydration treatment and swollen to obtain the intended hydrous contact lens. Therefore, when a water-soluble organic solvent is used as a solvent constituting the ink composition, the organic solvent in the lens precursor is effectively eluted during the hydration treatment, and is effectively removed outside the lens. Thus, there is an advantage that a separate organic solvent removal process is not required.
また、水溶性有機溶媒の中でも、特に、２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上であるものを用いることにより、インクジェット印刷の際の、インク組成物の乾燥によるヘッドの目詰まりの発生が効果的に抑制され、更には、後述する着色処理における加熱時に、インク組成物の乾燥（溶媒の蒸発）が有利に抑制されることとなり、インク組成物に含まれる着色剤をレンズ前駆体内に安定的に浸透せしめることが可能となる。加えて、このような特定の水溶性有機溶媒を用いることにより、後述する、インク組成物の重量減少率（ＬＯＤ：乾燥減量）を３０％以下とすることが、可能となる。
In addition, among water-soluble organic solvents, particularly those having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more can be used for the head by drying the ink composition during ink jet printing. Occurrence of clogging is effectively suppressed, and furthermore, drying of the ink composition (evaporation of the solvent) is advantageously suppressed during heating in the coloring process described later, and the colorant contained in the ink composition is reduced. It is possible to stably penetrate the lens precursor. In addition, by using such a specific water-soluble organic solvent, the weight reduction rate (LOD: loss on drying) of the ink composition described later can be reduced to 30% or less.
本発明のインク組成物において、水溶性有機溶媒としては、上述の如き、２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上であるものであれば、如何なるものであっても使用することが可能である。本発明においては、水溶性有機溶媒として、Ｎ－メチル－２－ピロリドン、炭酸プロピレン、ジメチルスルホキシド、１，３－ジメチル－イミダゾリジノン、リン酸トリエチルの中より選択される一種又は二種以上のものを用いることが好ましく、特に好ましくは、Ｎ－メチル－２－ピロリドン及び／又は炭酸プロピレンが使用される。
In the ink composition of the present invention, any water-soluble organic solvent may be used as long as it has a viscosity of 10 cp or less at 25 ° C. and a boiling point of 100 ° C. or more as described above. Is possible. In the present invention, as the water-soluble organic solvent, one or two or more kinds selected from N-methyl-2-pyrrolidone, propylene carbonate, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, and triethyl phosphate are used. N-methyl-2-pyrrolidone and / or propylene carbonate are preferably used.
一方、本発明のインク組成物において使用される水溶性有機増粘剤は、分子量が１０００以下であり、且つ、沸点が１００℃以上のものである。より具体的には、分子量が１０００以下であり、且つ、沸点が１００℃以上である、１）２５℃における粘度が１０～１０００ｃｐである液体状の、又は、２）２５℃で固体状の、水に可溶な有機増粘剤であって、上記した水溶性有機溶媒と混合することによって、インク組成物の粘度を増加させる機能を有するものである。
On the other hand, the water-soluble organic thickener used in the ink composition of the present invention has a molecular weight of 1000 or less and a boiling point of 100 ° C. or more. More specifically, the molecular weight is 1000 or less and the boiling point is 100 ° C. or higher, 1) a liquid having a viscosity of 10 to 1000 cp at 25 ° C., or 2) a solid at 25 ° C. An organic thickener that is soluble in water and has a function of increasing the viscosity of the ink composition when mixed with the above-described water-soluble organic solvent.
インクジェット印刷に使用されるインク組成物には、インクジェットヘッドより安定的にインク組成物が吐出されるように、従来より、増粘剤が添加されているところ、かかる増粘剤としては、ポリエチレングリコール（ＰＥＧ）やポリビニルピロリドン（ＰＶＰ）、アクリル系モノマーの共重合体等、高分子量のものが一般的である。しかしながら、このような高分子量の増粘剤をインク組成物に配合し、かかるインク組成物を用いて、乾燥状態（非膨潤状態）にある含水性コンタクトレンズ（レンズ前駆体）に着色処理を施すと、高分子量の増粘剤がレンズ前駆体内に効果的に浸透せず、レンズ前駆体の表面にインク組成物が残留することとなり、レンズ前駆体の所望とする部位が着色されていないことに起因して、着色により得られる文字や模様等が乱れたものとなる恐れがある。また、レンズ前駆体表面に残留したインク組成物が角膜と接触することによって、眼障害を引き起こす恐れがある。その一方、曲率を有するコンタクトレンズの表面に、インクジェット印刷にてインク組成物を付着せしめる場合、インク組成物の液滴がレンズ表面に着弾した後においても、インク組成物の粘性が必要とされる。即ち、インク組成物の粘性が低すぎると、かかるインク組成物の液滴がレンズ表面に着弾後、時間の経過と共に液ダレを生じ、その結果、レンズの目的とする部位にインク組成物からなる液滴を着弾させたにもかかわらず、着色によって得られる文字や模様等が、所望とするものではなく、乱れたものとなる等の問題を生ずる恐れがある。更に、水溶性の有機増粘剤を使用することにより、水和処理の際に効果的にレンズ前駆体より溶出され得ることとなり、特に、沸点が１００℃以上の水溶性有機増粘剤を使用することにより、インク組成物の乾燥を有利に抑制することが可能となる。以上の点を総合的に勘案して、本発明においては、分子量が１０００以下であり、且つ、沸点が１００℃以上である水溶性有機増粘剤が、使用されるのである。
Conventionally, a thickener has been added to the ink composition used for inkjet printing so that the ink composition can be stably ejected from the inkjet head. High molecular weights such as (PEG), polyvinylpyrrolidone (PVP), and copolymers of acrylic monomers are common. However, such a high-molecular-weight thickener is blended in the ink composition, and the water-containing contact lens (lens precursor) in a dry state (non-swelled state) is colored using the ink composition. The high molecular weight thickener does not effectively penetrate into the lens precursor, and the ink composition remains on the surface of the lens precursor, and the desired portion of the lens precursor is not colored. As a result, there is a risk that characters or patterns obtained by coloring may be disturbed. In addition, the ink composition remaining on the surface of the lens precursor may come into contact with the cornea to cause eye damage. On the other hand, when the ink composition is adhered to the surface of a contact lens having a curvature by ink jet printing, the viscosity of the ink composition is required even after the ink composition droplets land on the lens surface. . That is, if the viscosity of the ink composition is too low, the droplet of the ink composition lands on the lens surface and then sags with time. As a result, the ink composition is formed at the target portion of the lens. In spite of the landing of the liquid droplets, there is a possibility that characters, patterns and the like obtained by coloring become undesired and disturbed. Furthermore, by using a water-soluble organic thickener, it can be effectively eluted from the lens precursor during the hydration treatment, and in particular, a water-soluble organic thickener having a boiling point of 100 ° C. or higher is used. By doing so, drying of the ink composition can be advantageously suppressed. Considering the above points comprehensively, in the present invention, a water-soluble organic thickener having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more is used.
本発明のインク組成物において、水溶性有機増粘剤としては、上述の如き、分子量が１０００以下であり、且つ、沸点が１００℃以上であるものであれば、如何なるものであっても使用することが可能である。本発明においては、水溶性有機増粘剤として、２－ピロリドン、ε－カプロラクタム、プロピレングリコール、グリセロール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオールの中より選択される一種又は二種以上のものを使用することが好ましく、特に好ましくは、２－ピロリドン、ε－カプロラクタム、プロピレングリコール、グリセロール、エチレングリコール、ジエチレングリコールの中より選択される一種又は二種以上のものが使用される。
In the ink composition of the present invention, any water-soluble organic thickener may be used as long as it has a molecular weight of 1000 or less and a boiling point of 100 ° C. or more as described above. It is possible. In the present invention, as the water-soluble organic thickener, 2-pyrrolidone, ε-caprolactam, propylene glycol, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5- One or more selected from pentanediol and 2-methyl-2,4-pentanediol are preferably used, and particularly preferably 2-pyrrolidone, ε-caprolactam, propylene glycol, glycerol, One or two or more selected from ethylene glycol and diethylene glycol are used.
本発明に係るインク組成物において、上述した水溶性有機溶媒及び水溶性有機増粘剤の配合割合（使用割合）は、使用される水溶性有機溶媒及び水溶性有機増粘剤の種類に応じて、適宜に決定されることとなるが、通常は、水溶性有機溶媒：水溶性有機増粘剤＝１：９～９：１（重量比）となるような割合において、各々、使用される。好ましい範囲としては、以下の組合せについて例示することが出来る。水溶性有機溶媒としてＮ－メチル－２－ピロリドンを使用し、水溶性有機増粘剤として２－ピロリドンを使用する場合、水溶性有機溶媒（Ｎ－メチル－２－ピロリドン）及び水溶性有機増粘剤（２－ピロリドン）の合計量の１００重量部に対して、Ｎ－メチル－２－ピロリドンを１０～３０重量部の割合において、２－ピロリドンを７０～９０重量部の割合において、各々、使用することが好ましい。また、水溶性有機溶媒として炭酸プロピレンを使用し、水溶性有機増粘剤としてジエチレングリコールを使用する場合、水溶性有機溶媒（炭酸プロピレン）及び水溶性有機増粘剤（ジエチレングリコール）の合計量の１００重量部に対して、炭酸プロピレンを２０～９０重量部の割合において、ジエチレングリコールを１０～８０重量部の割合において、各々、使用することが好ましい。更に、水溶性有機溶媒として炭酸プロピレンを使用し、水溶性有機増粘剤としてプロピレングリコールを使用する場合、水溶性有機溶媒（炭酸プロピレン）及び水溶性有機増粘剤（プロピレングリコール）の合計量の１００重量部に対して、炭酸プロピレンを６０～９０重量部の割合において、プロピレングリコールを１０～４０重量部の割合において、各々、使用することが好ましい。
In the ink composition according to the present invention, the blending ratio (use ratio) of the water-soluble organic solvent and the water-soluble organic thickener described above depends on the type of the water-soluble organic solvent and the water-soluble organic thickener used. Usually, the water-soluble organic solvent: water-soluble organic thickener = 1: 9 to 9: 1 (weight ratio) is usually used, respectively. As preferable ranges, the following combinations can be exemplified. When N-methyl-2-pyrrolidone is used as the water-soluble organic solvent and 2-pyrrolidone is used as the water-soluble organic thickener, the water-soluble organic solvent (N-methyl-2-pyrrolidone) and the water-soluble organic thickener are used. N-methyl-2-pyrrolidone in a proportion of 10 to 30 parts by weight and 2-pyrrolidone in a proportion of 70 to 90 parts by weight with respect to 100 parts by weight of the total amount of the agent (2-pyrrolidone) It is preferable to do. When propylene carbonate is used as the water-soluble organic solvent and diethylene glycol is used as the water-soluble organic thickener, 100 weight of the total amount of the water-soluble organic solvent (propylene carbonate) and the water-soluble organic thickener (diethylene glycol) It is preferable to use propylene carbonate in a proportion of 20 to 90 parts by weight and diethylene glycol in a proportion of 10 to 80 parts by weight, respectively. Further, when propylene carbonate is used as the water-soluble organic solvent and propylene glycol is used as the water-soluble organic thickener, the total amount of the water-soluble organic solvent (propylene carbonate) and the water-soluble organic thickener (propylene glycol) It is preferable to use propylene carbonate in a proportion of 60 to 90 parts by weight and propylene glycol in a proportion of 10 to 40 parts by weight with respect to 100 parts by weight, respectively.
本発明のインク組成物には、従来のインク組成物と同様に、着色剤が、上述した水溶性有機溶媒及び水溶性有機増粘剤と共に使用される。本発明においては、従来よりインク組成物に使用されている各種の着色剤が、本発明の目的を阻害しないものである限りにおいて使用可能であるが、特に、有機溶媒に不溶な顔料ではなく、染料と称されているものが有利に使用される。染料の中でも、特に、炭素－炭素二重結合を有するラジカル重合性基を分子内に有さない、所謂、非重合性の染料（非重合性色素）が有利に使用される。非重合性色素としては、カラーインデックス（Ｃ．Ｉ．）で示される以下の化合物、具体的には、Ｃ．Ｉ．２６１００、Ｃ．Ｉ．４７００５、Ｃ．Ｉ．６１５２０、Ｃ．Ｉ．６１５６５、Ｃ．Ｉ．４７０２０、Ｃ．Ｉ．６０５０５、Ｃ．Ｉ．１２７４０、Ｃ．Ｉ．１８９５０、Ｃ．Ｉ．６０７２５、Ｃ．Ｉ．４７０００、Ｃ．Ｉ．１２７７０等を、例示することが出来る。
In the ink composition of the present invention, a colorant is used together with the above-described water-soluble organic solvent and water-soluble organic thickener as in the case of conventional ink compositions. In the present invention, various colorants conventionally used in ink compositions can be used as long as they do not impair the object of the present invention, but are not particularly pigments insoluble in organic solvents, What are referred to as dyes are advantageously used. Among the dyes, so-called non-polymerizable dyes (non-polymerizable dyes) that do not have a radically polymerizable group having a carbon-carbon double bond in the molecule are particularly preferably used. Non-polymerizable dyes include the following compounds represented by the color index (C.I.), specifically, C.I. I. 26100, C.I. I. 47005, C.I. I. 61520, C.I. I. 61565, C.I. I. 47020, C.I. I. 60505, C.I. I. 12740, C.I. I. 18950, C.I. I. 60725, C.I. I. 47000, C.I. I. 12770 etc. can be illustrated.
なお、上述した着色剤の、本発明のインク組成物における配合割合は、印刷方法や、被印刷物である含水性コンタクトレンズの種類等に応じて適宜に決定されることとなるが、一般には、上述した水溶性有機溶媒及び水溶性有機増粘剤の合計量：１００重量部に対して、０．０２～１０重量部、好ましくは０．０２～５重量部、より好ましくは０．０２～２重量部の量的割合において、配合されることとなる。
The blending ratio of the above-described colorant in the ink composition of the present invention is appropriately determined according to the printing method, the type of the hydrous contact lens that is the printing object, etc. Total amount of the above-mentioned water-soluble organic solvent and water-soluble organic thickener: 0.02 to 10 parts by weight, preferably 0.02 to 5 parts by weight, more preferably 0.02 to 2 parts per 100 parts by weight. It will mix | blend in the quantitative ratio of a weight part.
本発明に係る含水性コンタクトレンズ用インク組成物においては、従来のコンタクトレンズ用インク組成物を調製する際に用いられる他の成分であっても、本発明の効果を阻害しない限りにおいて、使用することが可能ではあるが、かかる他の成分は、炭素－炭素二重結合を有するラジカル重合性基を有しない化合物であることが好ましい。また、上述した水溶性有機溶媒、水溶性有機増粘剤及び着色剤についても、炭素－炭素二重結合を有するラジカル重合性基を有しない化合物であることが好ましい。けだし、炭素－炭素二重結合を有するラジカル重合性基を有する化合物を含むインク組成物は、その物性が経時変化や周辺環境の変化によって変化し易く、例えば、インクジェット印刷装置のヘッド内において重合が開始し、その結果、ノズルの目詰まりが生じて、ノズルよりインク組成物が効果的に吐出されない恐れがあるからである。
In the water-containing contact lens ink composition according to the present invention, other components used in preparing the conventional contact lens ink composition are used as long as the effects of the present invention are not impaired. Although it is possible, such other component is preferably a compound having no radically polymerizable group having a carbon-carbon double bond. In addition, the above-described water-soluble organic solvent, water-soluble organic thickener and colorant are also preferably compounds having no radically polymerizable group having a carbon-carbon double bond. However, an ink composition containing a compound having a radically polymerizable group having a carbon-carbon double bond tends to change its physical properties due to changes with time or changes in the surrounding environment. For example, polymerization can occur within the head of an ink jet printing apparatus. As a result, nozzle clogging occurs, and the ink composition may not be effectively discharged from the nozzle.
本発明に従う含水性コンタクトレンズ用インク組成物の調製は、従来のコンタクトレンズ用インク組成物と同様に、上述した水溶性有機溶媒、水溶性有機増粘剤及び着色剤、更には、必要に応じて他の成分を、従来より公知の手法に従って混合せしめることにより、行なわれることとなる。
The water-containing contact lens ink composition according to the present invention is prepared in the same manner as in the conventional contact lens ink composition. The water-soluble organic solvent, the water-soluble organic thickener and the colorant described above are used as necessary. The other components are mixed by a conventionally known method.
そして、本発明のインク組成物にあっては、６０℃で８５時間の加熱処理を実施した際の重量減少率：ＬＯＤが３０％以下となるように、各成分の配合割合が決定され、調製されているところに、大きな技術的特徴が存するのである。前述のＬＯＤが３０％以下であることから、本発明のインク組成物は、インクジェット印刷に使用した際に、インク組成物の乾燥によるヘッドの目詰まりの発生が効果的に抑制され得ると共に、後述する着色処理における加熱時に、インク組成物の乾燥（溶媒の蒸発）が有利に抑制され、インク組成物がレンズ前駆体内へ効果的に浸透することとなるのである。
And, in the ink composition of the present invention, the blending ratio of each component is determined so that the weight reduction ratio: LOD when the heat treatment is performed at 60 ° C. for 85 hours: LOD is 30% or less. There is a great technical feature. Since the aforementioned LOD is 30% or less, the ink composition of the present invention can effectively prevent clogging of the head due to drying of the ink composition when used in ink jet printing, and will be described later. During heating in the coloring process, drying of the ink composition (evaporation of the solvent) is advantageously suppressed, and the ink composition effectively penetrates into the lens precursor.
ここで、インク組成物の重量減少率：ＬＯＤ（乾燥減量）［％］とは、６０℃で８５時間の加熱処理を実施し、以下の式より算出されるものである。
Here, the weight reduction rate of the ink composition: LOD (loss on drying) [%] is calculated by the following equation after heat treatment at 60 ° C. for 85 hours.
なお、本発明のインク組成物は、水分含有量が０～１０重量％となるように、調製することが好ましい。けだし、水分含有量が１０重量％を超えると、上記した重量減少率：ＬＯＤ（乾燥減量）を３０％以下とすることが困難となり、また、インクジェット印刷において、レンズ前駆体に着弾したインク組成物からなる液滴が、時間の経過と共に液ダレを生じ、その結果、得られる着色部（文字や模様等）が滲んだものとなる恐れがあるからである。
The ink composition of the present invention is preferably prepared so that the water content is 0 to 10% by weight. However, if the water content exceeds 10% by weight, it is difficult to make the above-mentioned weight reduction rate: LOD (loss on drying) 30% or less, and an ink composition that has landed on the lens precursor in ink jet printing. This is because there is a risk that the liquid droplets formed from the liquid will sag with time, and as a result, the resulting colored portion (characters, patterns, etc.) may be blurred.
また、本発明のインク組成物は、着色対象含水性コンタクトレンズ（レンズ前駆体）に対する接触角が７０～９０°となるように、調製されることが好ましい。含水性コンタクトレンズに対して、インクジェット印刷によって印刷処理（着色処理）を実施する場合、着色対象である含水性コンタクトレンズに対する接触角が７０°未満であるインク組成物を用いると、レンズ前駆体に着弾したインク組成物からなる液滴が液だれを生じ、その結果、高い解像度を有する印刷部（着色部）が得られない恐れがある。その一方、含水性コンタクトレンズに対する接触角が９０°を超えるインク組成物を用いると、レンズ前駆体に着弾した液滴の形状に起因して、液滴を構成するインク組成物がレンズ前駆体内に完全に浸透するまでの移動距離が長くなるため、インク組成物の浸透を促進させるべく加熱処理時間の長期化や高い加熱処理温度が必要となり、その結果、レンズの変形や変質を引き起こす恐れがある。尚、本明細書及び請求の範囲において、含水性コンタクトレンズに対する接触角とは、着色対象である乾燥状態（非膨潤状態）の含水性コンタクトレンズ（レンズ前駆体）におけるレンズ面の頂点にインク組成物の液滴を形成し、かかる液滴について測定されるもの、即ち、液滴法に従って測定されるものを意味する。
Further, the ink composition of the present invention is preferably prepared so that the contact angle with respect to the water-containing contact lens (lens precursor) to be colored is 70 to 90 °. When a printing process (coloring process) is performed on a water-containing contact lens by ink jet printing, when an ink composition having a contact angle with respect to the water-containing contact lens that is a coloring target is less than 70 ° is used as a lens precursor. There is a possibility that the liquid droplets made of the landed ink composition cause liquid dripping, and as a result, a printed portion (colored portion) having high resolution cannot be obtained. On the other hand, when an ink composition having a contact angle of more than 90 ° with respect to the hydrous contact lens is used, the ink composition constituting the droplet is contained in the lens precursor due to the shape of the droplet landed on the lens precursor. Since the movement distance until complete penetration becomes longer, a longer heat treatment time and a higher heat treatment temperature are required to promote the penetration of the ink composition, and as a result, the lens may be deformed or deteriorated. . In the present specification and claims, the contact angle with respect to the water-containing contact lens means the ink composition at the apex of the lens surface of the dry (non-swelled) water-containing contact lens (lens precursor) to be colored. It means what forms a droplet of an object and is measured on such a droplet, i.e. measured according to the droplet method.
さらに、本発明の含水性コンタクトレンズ用インク組成物は、含水性コンタクトレンズであれば、従来より公知の各種レンズに対して使用可能であり、特に、シリコーンハイドロゲルレンズに対して有利に用いることが可能である。
Further, the water-containing contact lens ink composition of the present invention can be used for various conventionally known lenses as long as it is a water-containing contact lens, and particularly preferably used for silicone hydrogel lenses. Is possible.
ところで、本発明に従う含水性コンタクトレンズ用インク組成物を用いた、含水性コンタクトレンズに対する印刷処理（着色処理）は、有利には、以下の手順に従って実施される。
Incidentally, the printing process (coloring process) for the water-containing contact lens using the water-containing contact lens ink composition according to the present invention is advantageously performed according to the following procedure.
先ず、本発明に従う含水性コンタクトレンズ用インク組成物を、乾燥状態（非膨潤状態）にある含水性コンタクトレンズの前駆体（レンズ前駆体）の表面に付着させる。インク組成物をレンズ前駆体の表面に付着させる方法としては、液状のインク組成物をレンズ前駆体表面に塗布する方法等、従来より公知の方法を使用することが可能である。特に、インク組成物をレンズ前駆体表面に塗布する方法としては、例えば、パッド印刷方法、スクリーン印刷方法、インクジェット式印刷装置を用いる方法等を、挙げることが出来る。これらの中で、所望の文字や数字、虹彩模様等の図形のパターン（以下、本段落において文字等と総称する。）を簡便に印刷できる観点から、インクジェット式印刷装置を用いることが特に好ましい。インクジェット式印刷装置は、液状のインク組成物を、非常に微細な液滴としてレンズ表面に噴霧するものであり、表面に着弾した液滴は一つのドットを形成し、このドットの集まりによって、所望とする文字等が形成される。一般に、小さなドットが高密度で集合してなる文字等は、鮮鋭なコントラストを与え、優れた視認性を発揮する。インクジェット式印刷装置にて印字、描画する際、液滴の大きさ、液滴が着弾する地点などは、コンピューター等によって正確に制御することが可能であり、コンピューターのプログラムを変更することによって、文字等の形や大きさを容易に変更することが可能である。このように、インクジェット式印刷装置を用いた塗布方法は、非常に生産性が高く、また一定した高品質の印刷ができるという優れた利点を有する。更に、インクジェット式印刷装置によれば、塗布される液滴が微細であり、レンズへ着弾した際の界面面積に比して液滴量が少ないので、より迅速に、レンズ前駆体に浸透し易くなる。従って、インクジェット式印刷装置は、上記した利点以外に、レンズ表面への着色剤の析出や残渣の発生をより低減させて、着色剤をレンズ内部へ浸透させることが可能ならしめられ、この点においても、非常に有利な方法である。
First, the ink composition for a hydrous contact lens according to the present invention is attached to the surface of a precursor (lens precursor) of a hydrous contact lens in a dry state (non-swelled state). As a method of attaching the ink composition to the surface of the lens precursor, a conventionally known method such as a method of applying a liquid ink composition to the surface of the lens precursor can be used. In particular, examples of the method for applying the ink composition to the surface of the lens precursor include a pad printing method, a screen printing method, and a method using an ink jet printing apparatus. Among these, it is particularly preferable to use an ink jet printing apparatus from the viewpoint of easily printing a desired pattern of characters, numbers, iris patterns and the like (hereinafter collectively referred to as characters in this paragraph). The ink jet printing apparatus sprays a liquid ink composition on the lens surface as very fine droplets, and the droplets that have landed on the surface form one dot, and a desired collection of dots is formed. Are formed. In general, characters or the like in which small dots are gathered at high density give a sharp contrast and exhibit excellent visibility. When printing and drawing with an ink jet printer, the size of droplets, the point where droplets land, etc. can be accurately controlled by a computer, etc., and characters can be changed by changing the computer program. It is possible to easily change the shape and size of the like. As described above, the coating method using the ink jet printing apparatus has an excellent advantage that the productivity is very high and a constant high quality printing can be performed. Furthermore, according to the ink jet printing apparatus, the applied droplets are fine, and the amount of droplets is small compared to the interface area when landed on the lens, so that it can easily penetrate into the lens precursor more quickly. Become. Therefore, in addition to the above-described advantages, the ink jet printing apparatus can further reduce the deposition of colorant on the lens surface and the generation of residues, and allow the colorant to penetrate into the lens. Is also a very advantageous method.
なお、本発明においては、従来より公知の各種インクジェット式印刷装置の何れであっても、使用することが可能である。代表的なインクジェット式印刷装置は、インク組成物供給系とピエゾ素子等の圧電素子を備えたノズルから構成された吐出装置とからなり、圧電素子に電圧を負荷することによって生じる振動で、インク組成物を微細な液滴として、ノズルから吐出する機構を有している。所望の液滴を吐出できるものである限り、何れのインクジェット式印刷装置であっても好適に用いることができる。なお、ノズルは、単一であっても、複数であっても構わない。
In the present invention, any of various conventionally known ink jet printing apparatuses can be used. A typical ink jet printing apparatus is composed of an ink composition supply system and an ejection device composed of a nozzle equipped with a piezoelectric element such as a piezoelectric element. The ink composition is generated by vibration generated by applying a voltage to the piezoelectric element. It has a mechanism for discharging an object as fine droplets from a nozzle. Any ink jet printing apparatus can be suitably used as long as it can eject desired droplets. The nozzles may be single or plural.
本発明のインク組成物をレンズ前駆体の表面に付着するために要する時間は、インク組成物を接触させる方法や、印刷面積やその形状等によって変化することとなるが、例えば、インクジェット式印刷装置を用いる場合、通常、数秒～１０分程度である。
The time required for adhering the ink composition of the present invention to the surface of the lens precursor will vary depending on the method of contacting the ink composition, the printing area, its shape, etc., for example, an ink jet printing apparatus Usually, it is about several seconds to 10 minutes.
次いで、本発明のインク組成物が付着せしめられたレンズ前駆体に対して、加熱処理が施される。この加熱処理によって、インク組成物を構成する水溶性有機溶媒、水溶性有機増粘剤及び着色剤が、効果的にレンズ前駆体内に浸透することとなる。
Next, the lens precursor to which the ink composition of the present invention is adhered is subjected to a heat treatment. By this heat treatment, the water-soluble organic solvent, the water-soluble organic thickener and the colorant constituting the ink composition effectively penetrate into the lens precursor.
ここで、上記加熱処理は、９０～１３０℃の加熱温度にて、一般には数秒～１分程度、好ましくは５～３０秒程度の加熱時間で実施することが好ましい。加熱温度が低すぎたり、加熱時間が短すぎると、加熱処理の効果を享受し得ない恐れがあり、その一方、加熱温度が高すぎたり、加熱時間が長すぎると、レンズ前駆体が変形、変質等する恐れがあるからである。なお、本発明における加熱処理は、コンタクトレンズの加熱方法として従来より公知の方法の何れかに従って、実施することが可能である。
Here, the heat treatment is preferably carried out at a heating temperature of 90 to 130 ° C., generally for a few seconds to 1 minute, preferably for a heating time of about 5 to 30 seconds. If the heating temperature is too low or the heating time is too short, the effect of the heat treatment may not be enjoyed, while if the heating temperature is too high or the heating time is too long, the lens precursor will be deformed, This is because there is a risk of deterioration. Note that the heat treatment in the present invention can be performed according to any conventionally known method for heating a contact lens.
そして、以上の処理が施されたレンズ前駆体に対して、従来と同様の手法に従って水和処理を施すと、レンズ前駆体が吸水（膨潤）する一方で、レンズ前駆体内の水溶性有機溶媒及び水溶性有機増粘剤は、レンズ前駆体の外部へ効果的に溶出するのであり、以て、所望とする部位が着色された含水性コンタクトレンズが得られることとなるのである。
Then, when the lens precursor subjected to the above treatment is subjected to a hydration treatment according to a conventional method, the lens precursor absorbs water (swells), while the water-soluble organic solvent in the lens precursor and The water-soluble organic thickener is effectively eluted to the outside of the lens precursor, so that a water-containing contact lens in which a desired portion is colored is obtained.
以下に、本発明の実施例を幾つか示し、本発明を更に具体的に明らかにすることとするが、本発明が、そのような実施例の記載によって、何等の制約をも受けるものでないことは、言うまでもないところである。また、本発明には、以下の実施例の他にも、更には上記した具体的記述以外にも、本発明の趣旨を逸脱しない限りにおいて、当業者の知識に基づいて、種々なる変更、修正、改良等が加え得るものであることが、理解されるべきである。
Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements and the like can be added.
なお、以下の表１～表３において、「（＊）」が付された化合物は、本発明における「２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上である水溶性有機溶媒」であり、「（＊＊）」が付された化合物は、本発明における「分子量が１０００以下であり、且つ、沸点が１００℃以上である水溶性有機増粘剤」である。
In the following Tables 1 to 3, the compounds marked with “(*)” are water-soluble organic solvents having a viscosity of 10 cp or less at 25 ° C. and a boiling point of 100 ° C. or more in the present invention. The compound to which “(**)” is attached is a “water-soluble organic thickener having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more” in the present invention.
－実施例１～実施例１９－
下記表１及び表２に示す配合組成に従い、１９種類の含水性コンタクトレンズ用インク組成物を調製した（実施例１～実施例１９）。各インク組成物について、以下の手法に従い、重量減少率（ＬＯＤ）及び接触角を測定乃至は算出した。得られた重量減少率（ＬＯＤ）及び接触角を、下記表１及び表２に併せて示す。 -Example 1 to Example 19-
According to the composition shown in Table 1 and Table 2 below, 19 types of ink compositions for hydrous contact lenses were prepared (Examples 1 to 19). For each ink composition, the weight loss rate (LOD) and the contact angle were measured or calculated according to the following method. The obtained weight loss rate (LOD) and contact angle are shown in Table 1 and Table 2 below.
下記表１及び表２に示す配合組成に従い、１９種類の含水性コンタクトレンズ用インク組成物を調製した（実施例１～実施例１９）。各インク組成物について、以下の手法に従い、重量減少率（ＬＯＤ）及び接触角を測定乃至は算出した。得られた重量減少率（ＬＯＤ）及び接触角を、下記表１及び表２に併せて示す。 -Example 1 to Example 19-
According to the composition shown in Table 1 and Table 2 below, 19 types of ink compositions for hydrous contact lenses were prepared (Examples 1 to 19). For each ink composition, the weight loss rate (LOD) and the contact angle were measured or calculated according to the following method. The obtained weight loss rate (LOD) and contact angle are shown in Table 1 and Table 2 below.
－重量減少率（ＬＯＤ）－
５ｍＬのバイアル瓶（φ１８ｍｍ×４０ｍｍ）に０．５ｇのインク組成物を投入し、バイアル瓶全体の重量を測定した。次いで、バイアル瓶を、その蓋を閉めない状態で（開放状態で）、６０℃に保たれている乾燥機内に載置した。乾燥機内で８５時間、載置した後に、再度、バイアル瓶の重量を測定し、上記した式より、インク組成物の重量減少率（ＬＯＤ）を算出した。 -Weight loss rate (LOD)-
0.5 g of the ink composition was put into a 5 mL vial (φ18 mm × 40 mm), and the weight of the whole vial was measured. The vial was then placed in a dryer maintained at 60 ° C. with its lid not closed (in an open state). After placing in the dryer for 85 hours, the weight of the vial was measured again, and the weight reduction rate (LOD) of the ink composition was calculated from the above formula.
５ｍＬのバイアル瓶（φ１８ｍｍ×４０ｍｍ）に０．５ｇのインク組成物を投入し、バイアル瓶全体の重量を測定した。次いで、バイアル瓶を、その蓋を閉めない状態で（開放状態で）、６０℃に保たれている乾燥機内に載置した。乾燥機内で８５時間、載置した後に、再度、バイアル瓶の重量を測定し、上記した式より、インク組成物の重量減少率（ＬＯＤ）を算出した。 -Weight loss rate (LOD)-
0.5 g of the ink composition was put into a 5 mL vial (φ18 mm × 40 mm), and the weight of the whole vial was measured. The vial was then placed in a dryer maintained at 60 ° C. with its lid not closed (in an open state). After placing in the dryer for 85 hours, the weight of the vial was measured again, and the weight reduction rate (LOD) of the ink composition was calculated from the above formula.
－接触角－
乾燥状態（非膨潤状態）のシリコーンハイドロゲルレンズ（Ａｓｍｏｆｉｌｃｏｎ Ａ）のレンズ頂点に、約２μＬのインク組成物からなる液滴を接触させ、液適法に従い、液滴の接触角を測定した。 -Contact angle-
A droplet made of about 2 μL of the ink composition was brought into contact with the apex of a silicone hydrogel lens (Asmofilcon A) in a dry state (non-swelled state), and the contact angle of the droplet was measured according to a liquid suitable method.
乾燥状態（非膨潤状態）のシリコーンハイドロゲルレンズ（Ａｓｍｏｆｉｌｃｏｎ Ａ）のレンズ頂点に、約２μＬのインク組成物からなる液滴を接触させ、液適法に従い、液滴の接触角を測定した。 -Contact angle-
A droplet made of about 2 μL of the ink composition was brought into contact with the apex of a silicone hydrogel lens (Asmofilcon A) in a dry state (non-swelled state), and the contact angle of the droplet was measured according to a liquid suitable method.
実施例１～実施例１９に係る各インク組成物を、ピエゾ式インクジェット印刷装置を用いて、乾燥状態（非膨潤状態）のシリコーンハイドロゲルレンズ（Ａｓｍｏｆｉｌｃｏｎ Ａ）表面の所定部位に付着させた。その後、直ちに、レンズに対して、遠赤外線ヒーター（株式会社ノリタケカンパニーリミテド製、商品名：ＳＣＨ－１１０、入力電圧：１００Ｖ、電力容量：４００Ｗ）にて、遠赤外線を２０秒間、照射した。照射終了直後のレンズ表面の温度を、非接触式温度計（安立計器株式会社製、商品名：デュアルサーモＡＲ－１５００）にて測定したところ、約１００℃であった。レンズ温度が常温に至るまで放置し、その後、レンズ表面を目視で観察したところ、実施例１～実施例１９に係るインク組成物の全てにおいて、レンズ内に着色剤が浸透し、滲みを生ずることなくレンズを着色していることが確認された。
Each ink composition according to Examples 1 to 19 was attached to a predetermined portion of the surface of a dry (non-swelled) silicone hydrogel lens (Asmofilcon A) using a piezo ink jet printing apparatus. Immediately thereafter, the lens was irradiated with far-infrared rays for 20 seconds with a far-infrared heater (manufactured by Noritake Company Limited, trade name: SCH-110, input voltage: 100 V, power capacity: 400 W). The temperature of the lens surface immediately after the end of irradiation was measured with a non-contact thermometer (manufactured by Anritsu Keiki Co., Ltd., trade name: Dual Thermo AR-1500), and was about 100 ° C. When the lens temperature is allowed to reach room temperature and then the surface of the lens is visually observed, in all of the ink compositions according to Examples 1 to 19, the colorant penetrates into the lens and causes bleeding. It was confirmed that the lens was colored.
－比較例１～比較例７－
下記表３に示す配合組成に従い、７種類のインク組成物を調製した（比較例１～比較例７）。なお、下記表３に示す配合組成は、重量部を単位とするものである。また、比較例３に係るインク組成物の調製に使用した「monomer mixture A 」とは、以下に示す配合組成からなる混合物である。
・ＨＥＭＡ［ヒドロキシエチルメタクリレート］：５５重量部
・２－ＭＴＡ［２－メトキシエチルアクリレート］：０．５重量部
・２－（ジメチルアミノ）エチルメタクリレート：１．２重量部
・メタクリル酸：１．０重量部
・２－プロパノール：４２重量部
・２，２’－アゾビス－（２，４－ジメチルバレロニトリル）：０．３重量部 -Comparative Example 1 to Comparative Example 7-
Seven types of ink compositions were prepared according to the composition shown in Table 3 below (Comparative Examples 1 to 7). In addition, the compounding composition shown in following Table 3 makes a unit a weight part. The “monomer mixture A” used for the preparation of the ink composition according to Comparative Example 3 is a mixture having the following composition.
-HEMA [hydroxyethyl methacrylate]: 55 parts by weight-2-MTA [2-methoxyethyl acrylate]: 0.5 parts by weight-2- (dimethylamino) ethyl methacrylate: 1.2 parts by weight-Methacrylic acid: 1.0 Part by weight ・ 2-propanol: 42 parts by weight ・ 2,2′-azobis- (2,4-dimethylvaleronitrile): 0.3 part by weight
下記表３に示す配合組成に従い、７種類のインク組成物を調製した（比較例１～比較例７）。なお、下記表３に示す配合組成は、重量部を単位とするものである。また、比較例３に係るインク組成物の調製に使用した「monomer mixture A 」とは、以下に示す配合組成からなる混合物である。
・ＨＥＭＡ［ヒドロキシエチルメタクリレート］：５５重量部
・２－ＭＴＡ［２－メトキシエチルアクリレート］：０．５重量部
・２－（ジメチルアミノ）エチルメタクリレート：１．２重量部
・メタクリル酸：１．０重量部
・２－プロパノール：４２重量部
・２，２’－アゾビス－（２，４－ジメチルバレロニトリル）：０．３重量部 -Comparative Example 1 to Comparative Example 7-
Seven types of ink compositions were prepared according to the composition shown in Table 3 below (Comparative Examples 1 to 7). In addition, the compounding composition shown in following Table 3 makes a unit a weight part. The “monomer mixture A” used for the preparation of the ink composition according to Comparative Example 3 is a mixture having the following composition.
-HEMA [hydroxyethyl methacrylate]: 55 parts by weight-2-MTA [2-methoxyethyl acrylate]: 0.5 parts by weight-2- (dimethylamino) ethyl methacrylate: 1.2 parts by weight-Methacrylic acid: 1.0 Part by weight ・ 2-propanol: 42 parts by weight ・ 2,2′-azobis- (2,4-dimethylvaleronitrile): 0.3 part by weight
得られた各インク組成物について、上述した実施例１～実施例１９と同様の手法に従い、重量減少率（ＬＯＤ）及び接触角を測定乃至は算出した。但し、比較例５に係るインク組成物にあっては、乾燥中に硬化してしまったため、重量減少率（ＬＯＤ）を算出することは出来なかった。比較例１、比較例２、比較例４～比較例７に係る各インク組成物の重量減少率（ＬＯＤ）及び接触角を、下記表３に併せて示す。
For each ink composition obtained, the weight loss rate (LOD) and the contact angle were measured or calculated according to the same method as in Examples 1 to 19 described above. However, in the ink composition according to Comparative Example 5, the weight loss rate (LOD) could not be calculated because the ink composition was cured during drying. Table 3 below shows the weight loss rate (LOD) and contact angle of each ink composition according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7.
比較例１、比較例２、比較例４～比較例７に係る各インク組成物を用いて、実施例１～実施例１９と同様の手法に従い、乾燥状態（非膨潤状態）のシリコーンハイドロゲルレンズ（Ａｓｍｏｆｉｌｃｏｎ Ａ）に対して着色処理を実施した。かかる処理後のレンズ表面を目視で観察したところ、比較例１、比較例２、比較例４～比較例７に係るインク組成物の全てにおいて、着色部分に滲みが生じていることが、認められたのである。
Silicone hydrogel lenses in a dry state (non-swelled state) using the ink compositions according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7 according to the same method as in Examples 1 to 19 The coloring process was implemented with respect to (Asmofilcon A). When the surface of the lens after such treatment was visually observed, it was observed that in all of the ink compositions according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7, bleeding occurred in the colored portion. It was.
Silicone hydrogel lenses in a dry state (non-swelled state) using the ink compositions according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7 according to the same method as in Examples 1 to 19 The coloring process was implemented with respect to (Asmofilcon A). When the surface of the lens after such treatment was visually observed, it was observed that in all of the ink compositions according to Comparative Example 1, Comparative Example 2, and Comparative Examples 4 to 7, bleeding occurred in the colored portion. It was.
Claims (9)
- ａ）２５℃における粘度が１０ｃｐ以下であり、且つ、沸点が１００℃以上である水溶性有機溶媒と、ｂ）分子量が１０００以下であり、且つ、沸点が１００℃以上である水溶性有機増粘剤とを含み、６０℃で８５時間の加熱処理を実施した際の重量減少率：ＬＯＤが３０％以下であることを特徴とする含水性コンタクトレンズ用インク組成物。 a) a water-soluble organic solvent having a viscosity at 25 ° C. of 10 cp or less and a boiling point of 100 ° C. or more; b) a water-soluble organic thickening having a molecular weight of 1000 or less and a boiling point of 100 ° C. or more. An ink composition for a hydrous contact lens, comprising: an agent, and having a weight reduction rate of LOD of 30% or less when heat treatment is performed at 60 ° C. for 85 hours.
- 水分含有量が０～１０重量％である請求項１に記載の含水性コンタクトレンズ用インク組成物。 The water-containing contact lens ink composition according to claim 1, wherein the water content is 0 to 10% by weight.
- 炭素－炭素二重結合を有するラジカル重合性基を有さない化合物より構成されている請求項１又は請求項２に記載の含水性コンタクトレンズ用インク組成物。 The ink composition for a hydrous contact lens according to claim 1 or 2, comprising a compound having no radically polymerizable group having a carbon-carbon double bond.
- 前記水溶性有機溶媒が、Ｎ－メチル－２－ピロリドン、炭酸プロピレン、ジメチルスルホキシド、１，３－ジメチル－イミダゾリジノン、リン酸トリエチルの中より選択される一種又は二種以上である請求項１乃至請求項３の何れか１項に記載の含水性コンタクトレンズ用インク組成物。 2. The water-soluble organic solvent is one or more selected from N-methyl-2-pyrrolidone, propylene carbonate, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, and triethyl phosphate. The ink composition for a hydrous contact lens according to any one of claims 3 to 4.
- 前記水溶性有機増粘剤が、２－ピロリドン、ε－カプロラクタム、プロピレングリコール、グリセロール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオールの中より選択される一種又は二種以上である請求項１乃至請求項４の何れか１項に記載の含水性コンタクトレンズ用インク組成物。 The water-soluble organic thickener is 2-pyrrolidone, ε-caprolactam, propylene glycol, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2 The water-containing contact lens ink composition according to any one of claims 1 to 4, wherein the ink composition is one or more selected from methyl-2,4-pentanediol.
- 前記水溶性有機溶媒がＮ－メチル－２－ピロリドンであり、前記水溶性有機増粘剤が２－ピロリドンである請求項１乃至請求項３の何れか１項に記載の含水性コンタクトレンズ用インク組成物。 4. The water-containing contact lens ink according to claim 1, wherein the water-soluble organic solvent is N-methyl-2-pyrrolidone, and the water-soluble organic thickener is 2-pyrrolidone. Composition.
- 前記水溶性有機溶媒が炭酸プロピレンであり、前記水溶性有機増粘剤がジエチレングリコールである請求項１乃至請求項３の何れか１項に記載の含水性コンタクトレンズ用インク組成物。 The water-containing contact lens ink composition according to any one of claims 1 to 3, wherein the water-soluble organic solvent is propylene carbonate and the water-soluble organic thickener is diethylene glycol.
- 前記水溶性有機溶媒が炭酸プロピレンであり、前記水溶性有機増粘剤がプロピレングリコールである請求項１乃至請求項３の何れか１項に記載の含水性コンタクトレンズ用インク組成物。 The water-containing contact lens ink composition according to any one of claims 1 to 3, wherein the water-soluble organic solvent is propylene carbonate and the water-soluble organic thickener is propylene glycol.
- 着色対象である含水性コンタクトレンズに対する接触角が７０～９０°である請求項１乃至請求項８の何れか１項に記載の含水性コンタクトレンズ用インク組成物。
The water-containing contact lens ink composition according to any one of claims 1 to 8, wherein a contact angle with a water-containing contact lens to be colored is 70 to 90 °.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016508403A JP6002351B2 (en) | 2014-03-19 | 2014-03-19 | Ink composition for hydrous contact lenses |
| PCT/JP2014/057596 WO2015140968A1 (en) | 2014-03-19 | 2014-03-19 | Ink composition for hydrous contact lenses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2014/057596 WO2015140968A1 (en) | 2014-03-19 | 2014-03-19 | Ink composition for hydrous contact lenses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015140968A1 true WO2015140968A1 (en) | 2015-09-24 |
Family
ID=54143974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2014/057596 WO2015140968A1 (en) | 2014-03-19 | 2014-03-19 | Ink composition for hydrous contact lenses |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6002351B2 (en) |
| WO (1) | WO2015140968A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521545A (en) * | 2020-12-29 | 2021-03-19 | 甘肃康视达科技集团有限公司 | Ink intermediate for colored contact lenses and preparation method thereof |
| CN112552741A (en) * | 2020-12-29 | 2021-03-26 | 甘肃康视达科技集团有限公司 | Ink for color contact lenses and ink drying agent |
| CN114578582A (en) * | 2022-03-17 | 2022-06-03 | 江苏海伦隐形眼镜有限公司 | Shining 5D colorful beautiful pupil and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61211382A (en) * | 1985-03-18 | 1986-09-19 | Toyo Contact Lens Co Ltd | Ink for marking of soft contact lens |
| JPH03197570A (en) * | 1989-01-30 | 1991-08-28 | Lab Pfortner Cornealent Sa Cif | Manufacture of pigmented lacquer or varnish for coloring contact lens, pigmented or colorless lacquer thus obtained, and contact lens colored with the lacquer |
| JPH05125309A (en) * | 1991-05-16 | 1993-05-21 | Xerox Corp | Ink for ink jet printing process |
| JPH1077427A (en) * | 1996-07-10 | 1998-03-24 | Sony Corp | Water-base ink composition and colored composite material |
| JPH111645A (en) * | 1997-06-13 | 1999-01-06 | Mitsubishi Chem Corp | Recording fluid and recording process |
| JP2004525413A (en) * | 2001-03-16 | 2004-08-19 | ノバルティス アクチエンゲゼルシャフト | Colored printing inks for contact lenses |
| JP2007507758A (en) * | 2003-10-06 | 2007-03-29 | ドーシ，プレイフール | Colored lens and manufacturing method |
| JP2008506031A (en) * | 2004-07-16 | 2008-02-28 | トランジションズ オプティカル， インコーポレイテッド | Method for making photosensitive microparticles, its aqueous composition and articles prepared using it |
| JP2011106064A (en) * | 2009-11-18 | 2011-06-02 | Menicon Co Ltd | Dye composition for ophthalmic lens, method for producing colored ophthalmic lens using the same, and colored ophthalmic lens |
| JP2011164431A (en) * | 2010-02-10 | 2011-08-25 | Menicon Co Ltd | Method for producing colored ophthalmic lens using the same, and colored ophthalmic lens obtained by the same |
| JP2013097384A (en) * | 2011-11-02 | 2013-05-20 | Johnson & Johnson Vision Care Inc | Contact lens oriented to have brightly stained sclera |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001040846A2 (en) * | 1999-11-01 | 2001-06-07 | Praful Doshi | Tinted lenses and methods of manufacture |
| EP2330161B1 (en) * | 2009-11-18 | 2017-01-25 | Menicon Co., Ltd. | Dye composition for ophthalmic lens, method for producing colored ophthalmic lens using the same and colored ophthalmic lens |
-
2014
- 2014-03-19 WO PCT/JP2014/057596 patent/WO2015140968A1/en active Application Filing
- 2014-03-19 JP JP2016508403A patent/JP6002351B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61211382A (en) * | 1985-03-18 | 1986-09-19 | Toyo Contact Lens Co Ltd | Ink for marking of soft contact lens |
| JPH03197570A (en) * | 1989-01-30 | 1991-08-28 | Lab Pfortner Cornealent Sa Cif | Manufacture of pigmented lacquer or varnish for coloring contact lens, pigmented or colorless lacquer thus obtained, and contact lens colored with the lacquer |
| JPH05125309A (en) * | 1991-05-16 | 1993-05-21 | Xerox Corp | Ink for ink jet printing process |
| JPH1077427A (en) * | 1996-07-10 | 1998-03-24 | Sony Corp | Water-base ink composition and colored composite material |
| JPH111645A (en) * | 1997-06-13 | 1999-01-06 | Mitsubishi Chem Corp | Recording fluid and recording process |
| JP2004525413A (en) * | 2001-03-16 | 2004-08-19 | ノバルティス アクチエンゲゼルシャフト | Colored printing inks for contact lenses |
| JP2007507758A (en) * | 2003-10-06 | 2007-03-29 | ドーシ，プレイフール | Colored lens and manufacturing method |
| JP2011076105A (en) * | 2003-10-06 | 2011-04-14 | Praful Doshi | Tinted lens and method for manufacturing the same |
| JP2008506031A (en) * | 2004-07-16 | 2008-02-28 | トランジションズ オプティカル， インコーポレイテッド | Method for making photosensitive microparticles, its aqueous composition and articles prepared using it |
| JP2011106064A (en) * | 2009-11-18 | 2011-06-02 | Menicon Co Ltd | Dye composition for ophthalmic lens, method for producing colored ophthalmic lens using the same, and colored ophthalmic lens |
| JP2011164431A (en) * | 2010-02-10 | 2011-08-25 | Menicon Co Ltd | Method for producing colored ophthalmic lens using the same, and colored ophthalmic lens obtained by the same |
| JP2013097384A (en) * | 2011-11-02 | 2013-05-20 | Johnson & Johnson Vision Care Inc | Contact lens oriented to have brightly stained sclera |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521545A (en) * | 2020-12-29 | 2021-03-19 | 甘肃康视达科技集团有限公司 | Ink intermediate for colored contact lenses and preparation method thereof |
| CN112552741A (en) * | 2020-12-29 | 2021-03-26 | 甘肃康视达科技集团有限公司 | Ink for color contact lenses and ink drying agent |
| CN114578582A (en) * | 2022-03-17 | 2022-06-03 | 江苏海伦隐形眼镜有限公司 | Shining 5D colorful beautiful pupil and preparation method thereof |
| CN114578582B (en) * | 2022-03-17 | 2024-03-22 | 江苏海伦隐形眼镜有限公司 | Blazed 5D colorful beauty pupil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015140968A1 (en) | 2017-04-06 |
| JP6002351B2 (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102194356B1 (en) | Water-based ink for inkjet recording | |
| JP6348279B2 (en) | Inkjet recording method | |
| JP2005508432A (en) | Ink formulations and uses thereof | |
| US10076909B2 (en) | Printing ink | |
| EP1878774B1 (en) | Ink composition, recording method using the same, and recorded matter | |
| JP7208580B2 (en) | Inkjet textile composition set and inkjet textile printing method | |
| JP6002351B2 (en) | Ink composition for hydrous contact lenses | |
| ES2753448T3 (en) | Procedure for direct ink jet printing or ink printing with liquid ink receiving layers or films | |
| CN112384577B (en) | Ink composition for printing on non-permeable substrate and image recording method | |
| JP6233166B2 (en) | Water-based ink | |
| WO2017103603A1 (en) | Printing ink | |
| JP6156534B1 (en) | Inkjet ink | |
| US11104821B2 (en) | Receptive solution, ink set containing said receptive solution and method for producing printed material using ink set | |
| CN112585013A (en) | Method for producing inkjet printed material | |
| JP6471026B2 (en) | Inkjet recording method | |
| EP3101069B1 (en) | Inkjet ink and inkjet recording method | |
| JP6658668B2 (en) | Inkjet ink | |
| JP2009256447A (en) | Photocurable ink composition, inkjet recording method, recorded matter, ink set, ink cartridge, and recording device | |
| JP5343366B2 (en) | Water-based inkjet recording ink | |
| EP3532551B1 (en) | Ink jet inks having ir-absorbing dye | |
| ES2972352T3 (en) | Aqueous ink for inkjet printing | |
| WO2020202773A1 (en) | Inkjet ink for forming infrared absorbing image, method for forming infrared absorbing image, and method for forming image | |
| ES2974976T3 (en) | Water-based ink for inkjet printing | |
| JP2019177560A (en) | Acceptor solution, ink set comprising that acceptor solution, and method of producing print using ink set | |
| JP2015178571A (en) | Ink composition for hydrous contact lens |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14886010 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2016508403 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 14886010 Country of ref document: EP Kind code of ref document: A1 |