JP4396232B2 - Method for producing antifouling optical article - Google Patents

Description

  The present invention relates to a method for producing an antifouling optical article, and more particularly to a method for producing an antifouling optical article having an improved appearance after the formation of an antifouling layer.

  Optical articles such as lenses usually have an anti-reflective coating on the surface to suppress light reflection and increase light transmission. There is a problem that dirt due to the adhesion of the toner is conspicuous and it is difficult to remove the dirt. Therefore, an antifouling layer is further provided on the surface of the antireflection film in order to make it difficult to get dirt or to easily wipe off dirt.

  A surface treatment agent for providing an antifouling layer on an optical article is described in Patent Document 1.

  An optical article formed with a surface treatment with a fluorine-containing silane compound described in Patent Document 1 to form an antifouling layer has good antifouling properties, maintains its effect, and easily removes dirt.

Japanese Patent Laid-Open No. 9-258003

  However, since the fluorine-containing silane compound described in Patent Document 1 is inferior in reactivity with the surface of the optical article, it is necessary to promote the reaction by annealing after applying the water repellent treatment liquid to the substrate surface. Here, the annealing is performed by putting it in a bath set at high temperature and high humidity or leaving it in a room.

  When the step of forming the antifouling layer on the substrate surface is performed by using the fluorine-containing silane compound described in Patent Document 1, generally an organic solvent is used as a solvent so that the fluorine-containing silane compound has a predetermined concentration. The water-repellent treatment liquid prepared in this manner is applied to the substrate surface by dipping, spin coating, brushing, or the like. After application, the organic solvent gradually evaporates, and the fluorine-containing silane compound that is a water repellent component remains on the substrate.

  In the above process, a water repellent and a solvent are present in a mixed state on the substrate surface immediately after application of the water repellent treatment liquid. In this state, when the substrate is put into high temperature and high humidity for annealing, water droplets adhere to the lens surface. This is because the substrate surface moves below the dew point due to the substrate moving from room temperature to a high temperature and high humidity environment, and moisture is condensed. Furthermore, the evaporation of the solvent causes the substrate to be cooled by the heat of vaporization, which promotes the condensation of moisture. At this time, since the fluorine-containing silane compound and the solvent are mixed on the substrate surface, the fluorine-containing silane compound molecules are relatively easy to flow. For this reason, the distribution of fluorine-containing silane compound molecules is locally biased by water droplets generated by condensation of moisture on the substrate surface. When annealing is continued in this state, the deviation of the fluorine-containing silane compound molecules is fixed by chemical bonds, and remains on the substrate as an appearance defect. That is, due to the uneven distribution of the fluorine-containing silane compound molecules, fine irregularities and density intensities are generated on the substrate surface, which are visually recognized as defects. Many of these defects have a fine mottled or speckled pattern and are difficult to remove even by washing with an organic solvent.

  As a measure to improve this, it is conceivable that after applying the water repellent treatment liquid to the substrate, it is allowed to stand for a certain period of time to completely evaporate the solvent and then anneal, but in the case of a solvent having a high boiling point, it is completely evaporated. It takes a long time to do so, leading to a decrease in cycle time, and as described below, if the atmosphere to be left is at high temperature and high humidity, it may cause the same appearance defects, which is inappropriate. is there.

  If annealing is performed in a room, if the environment is left under high temperature and high humidity in the summer, for example, the solvent evaporates and the substrate is cooled by heat of vaporization, which causes the substrate temperature to fall below the dew point. If this happens, moisture in the atmosphere will condense. In this case, since the size of water droplets generated by condensation on the substrate is very small, the appearance defect often becomes cloudy cloudy. That is, since the unevenness and the density of the density due to the uneven distribution of the fluorine-containing silane compound molecules on the substrate surface are very fine, it is recognized as white turbidity due to irregular reflection of light. Since this defect is also fixed by annealing as described above, it is difficult to remove it by washing with an organic solvent.

As described above, when a substrate is processed by a wet process using a water-repellent treatment liquid containing a fluorine-containing silane compound, an appearance defect may occur on the lens surface due to annealing after application of the water-repellent treatment liquid. is there. These defects can sometimes be fatal in expressing the function of optical articles, particularly lenses.
The present invention has been made in view of the above circumstances, and when forming an antifouling layer with a fluorine-containing silane compound having an excellent antifouling effect, an optical article having excellent optical performance by preventing defects in appearance. The purpose is to provide a method that enables production of

  As a result of intensive investigations to achieve the above object, the present inventors have forcibly applied a solvent on the substrate surface after applying a water repellent treatment liquid when forming an antifouling layer mainly composed of a fluorine-containing silane compound. The present inventors have found that the appearance of defects can be prevented by providing a step for removing them.

  That is, by removing the solvent, the movement of the water repellent molecules is limited, so that even if moisture is condensed in the next step, the distribution of the water repellent molecules is a defect in appearance. Bias can be prevented.

Therefore, the first invention is a process for forming an antifouling layer by applying a water-repellent fluorine-containing silane compound to the surface of an optical article, and a process of diluting the fluorine-containing silane compound in an organic solvent. A treatment liquid coating process for coating the liquid on the surface of the optical article, a solvent removal process for forcibly removing the solvent of the treatment liquid coated on the surface of the optical article after the coating process, and the solvent removal. after the step, the temperature is 40 ° C. to 60 ° C., relative humidity and placed for 1 to 2 hours to 60% to 90%, having a annealing step of fixing the fluorine-containing silane compound to the optical article surface A method for producing an antifouling optical article is provided.

  According to the first invention, since the solvent is forcibly removed after the treatment liquid coating step, even if water droplets adhere to the surface of the optical article in the subsequent annealing step, the movement of the fluorine-containing silane compound is limited. Therefore, there is no bias in the distribution of the fluorine-containing silane compound, which makes it possible to form an antifouling layer free from defects in appearance, and to produce an optical article having excellent optical performance. .

  2nd invention is a solvent removal process of 1st invention. WHEREIN: A solvent is hold | maintained by hold | maintaining an optical article for 5 to 15 minutes in the heating furnace whose temperature is 50 to 70 degreeC, and humidity is 20% or less. A method for producing an antifouling optical article according to claim 1 is provided.

  According to the second invention, the solvent can be effectively evaporated and removed in a short time in the solvent removal step after the treatment liquid coating step, and even if water droplets adhere to the surface of the optical article in the subsequent annealing step. Since the movement of the fluorinated silane compound is limited, the distribution of the fluorinated silane compound is not biased, thereby forming an antifouling layer free from defects in appearance and having excellent optical performance. Optical articles can be produced.

In a third aspect of the present invention, in the solvent removal step of the first aspect, the optical article is placed in a vacuum dryer having a pressure of 1 × 10 ⁻² to 4 × 10 ⁴ Pa and a temperature of room temperature to 70 ° C. The method for producing an antifouling optical article according to claim 1, wherein the solvent is removed by holding for 5 to 15 minutes.

  According to the third invention, the solvent can be effectively evaporated and removed in a short time in the solvent removal step after the treatment liquid coating step, and even if water drops adhere to the surface of the optical article in the subsequent annealing step. Since the movement of the fluorinated silane compound is limited, the distribution of the fluorinated silane compound is not biased, thereby forming an antifouling layer free from defects in appearance and having excellent optical performance. Optical articles can be produced.

  According to a fourth invention, in the method for producing an antifouling optical article of the first to third inventions, the fluorine-containing silane compound is represented by the following general formula (1): A method for manufacturing an article is provided.

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is iodine or hydrogen, Y is hydrogen or a lower alkyl group, Z is fluorine or a trifluoromethyl group, R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b, c, d are integers of 0-200, e is 0 or 1, m and n are 0-2 An integer, p represents an integer of 1 to 10.)

  According to the fourth invention, it is possible to produce an antifouling optical article having significantly improved antifouling properties than before.

  According to a fifth invention, in the method for producing an antifouling optical article according to any one of the first to fourth inventions, a hard coat layer is formed under the antifouling layer. A method for producing a dirty optical article is provided.

  According to the fifth invention, in the antifouling optical article in which a hard coat layer is formed on the surface of the base material in order to impart scratch resistance when the base material is mainly plastic, there are no defects in appearance. An antifouling layer can be formed, and an optical article having excellent optical performance can be produced.

  According to a sixth invention, in the method for producing an antifouling optical article according to any one of the first to fourth inventions, an antireflection film is formed in a lower layer of the antifouling layer. A method for producing a dirty optical article is provided.

  According to the sixth invention, when the base material is mainly glass, in the antifouling optical article in which the antireflection film is directly formed on the surface of the base material, an antifouling layer free from defects in appearance can be formed, which is excellent It is possible to produce an optical article having optical performance.

  A seventh invention is characterized in that, in the method for producing an antifouling optical article according to the sixth invention, a hard coat layer is formed on the surface of the substrate, and an antireflection film is formed on the surface of the hard coat layer. A method for producing an antifouling optical article is provided.

  According to the seventh invention, when the base material is mainly a plastic, a hard coat layer is formed on the surface of the base material in order to impart scratch resistance and improve the adhesion of the antireflection film. In an antifouling optical article having an antireflection film formed on the surface of the coat layer, an antifouling layer free from defects in appearance can be formed, and an optical article having excellent optical performance can be produced.

  The eighth invention provides the method for producing an antifouling optical article according to any one of the fifth to seventh aspects, wherein the base material is plastic.

  According to the eighth invention, in the antifouling optical article whose base material is plastic, an antifouling layer having no defects in appearance can be formed, and an optical article having excellent optical performance can be produced. Become.

  According to the method for producing an antifouling optical article of the present invention, an optical article having excellent optical performance and having no appearance defect is formed by forming an antifouling layer with a fluorine-containing silane compound having an excellent antifouling effect. Can be produced.

  Hereinafter, although embodiment of the manufacturing method of the antifouling optical article by this invention is described, this invention is not limited to the following embodiment.

  An example of the process of the present invention is shown in FIG.

  As described above, the method for producing an antifouling optical article of the present invention is applied to the surface of an optical article using a treatment liquid prepared by diluting a fluorine-containing silane compound to a predetermined concentration using an organic solvent as a solvent. And an antifouling treatment step for forming an antifouling layer.

  As the substrate, either inorganic glass or plastic can be used. Examples of the plastic include diethylene glycol bisallyl carbonate (CR-39) resin, polyurethane resin, thiourethane resin, polycarbonate resin, and acrylic resin.

  In the case of a glass substrate, the antifouling layer can be provided directly on the glass substrate, but usually, in the case of a glass substrate, an antireflection film is provided, and in the case of plastic, a hard coat layer is provided. It is preferable to provide the antifouling layer after or after the hard coat layer and the antireflection film are provided.

  The hard coat layer imparts scratch resistance to the plastic substrate, and generally the adhesion of the antireflection film to the plastic substrate is not good. Therefore, the hard coat layer is interposed between the plastic substrate and the antireflection film so that the antireflection film adheres. It has a function of improving the property and preventing peeling.

As a method for forming the hard coat layer, a method of applying a curable composition capable of forming a hard coat layer to the surface of a plastic substrate and curing the coating film is common. When the plastic substrate is a thermoplastic resin, those that are cured by electromagnetic waves such as ultraviolet rays or ionizing radiation such as electron beams are preferably used rather than thermosetting types. For example, a photocurable silicone composition mainly composed of a silicone compound that generates a silanol group by ultraviolet irradiation and an organopolysiloxane having a reactive group such as a halogen atom or an amino group that undergoes a condensation reaction with the silanol group, an acrylic ultraviolet ray A curable monomer composition (for example, UK-6074 manufactured by Mitsubishi Rayon Co., Ltd.), inorganic fine particles having a particle diameter of 1 to 100 nm such as SiO ₂ and TiO _2, such as vinyl group, allyl group, acrylic group or methacryl group. Examples thereof include a silane compound having a polymerizable group and a hydrolyzable group such as a methoxy group, a thermosetting composition containing inorganic fine particles dispersed in a silane coupling agent, and the like.

  As a method for forming the coating film, a dipping method, a spin coating method, a spray method, a flow method, a doctor blade method, or the like can be employed.

  In addition, in order to improve adhesiveness before forming a coating film, it is preferable to surface-treat the plastic substrate surface by high voltage discharges, such as corona discharge and a microwave.

  The formed coating film can be cured by heat, ultraviolet light, electron beam or the like to obtain a hard coat layer.

  The thickness of the hard coat layer is preferably in the range of about 0.05 to 30 μm. If it is too thin, basic performance may not be exhibited, while if it is too thick, optical distortion may occur.

The antireflection film is composed of a single layer or multiple layers of an inorganic coating or an organic coating. The material of the inorganic _{film, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O 3, Examples thereof include inorganic substances such as SnO ₂ , MgF ₂ , and WO ₃ , and these can be used alone or in combination of two or more. In the case of a plastic substrate, SiO ₂ , ZrO ₂ , TiO ₂ , and Ta ₂ O ₅ that can be vacuum-deposited at a low temperature are preferable. When it is a multilayer film structure, the outermost layer is preferably a SiO _2.

As the multilayer film of the inorganic coating, the total optical film thickness of the ZrO ₂ layer and the SiO ₂ layer from the substrate side is λ / 4, the optical film thickness of the ZrO ₂ layer is λ / 4, and the optical film of the uppermost SiO ₂ layer A four-layer structure with a film thickness of λ / 4 can be exemplified. Here, λ is a design wavelength, and usually 520 nm is used.

  As a method for forming the inorganic film, for example, a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a method of depositing by a chemical reaction in a saturated solution, or the like can be employed.

  The material of the organic film is selected in consideration of the refractive index of the plastic substrate and the hard coat layer, and it can be formed by a coating method excellent in mass productivity such as a spin coating method and a dip coating method in addition to the vacuum evaporation method. it can.

  The antifouling layer is preferably formed using a fluorine-containing silane compound represented by the following general formula (1).

R _f in the general formula (1) is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably CF ₃ —, C ₂ F ₅ —, C ₃ F ₇ —. R ¹ is a hydrolyzable group, for example, halogen, —OR ³ , —OCOR ³ , —OC (R ³ ) = C (R ⁴ ) ₂ , —ON = C (R ³ ) ₂ , —ON = CR ⁵ is preferred. More preferably, chlorine, -OCH _3, is -OC ₂ H _5. Here, R ³ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ⁴ is hydrogen or a lower aliphatic hydrocarbon group, and R ⁵ is a C 3-6 divalent aliphatic hydrocarbon group. R ² is hydrogen or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. a, b, c and d are integers of 0 to 200, preferably 1 to 50, and e is 0 or 1. m and n are integers of 0 to 2, but preferably 0. p is an integer greater than or equal to 1, Preferably it is an integer of 1-10. Moreover, although molecular weight is 5 * 10 < ² > -1 * 10 < ⁵ >, Preferably it is 5 * 10 < ² > -1 * 10 < ⁴ >.

  Moreover, what is shown by following General formula (2) is mentioned as a thing of the preferable structure of the fluorine-containing silane compound shown by the said General formula (1).

In the above formula, Y represents hydrogen or a lower alkyl group, R ¹ represents a hydrolyzable group, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and r represents an integer of 1 to 10.

In order to form an antifouling layer on a substrate using the above-mentioned fluorine-containing silane compound, a method in which the fluorine-containing silane compound is dissolved in an organic solvent, adjusted to a predetermined concentration, and applied to the surface of an optical article. Can be adopted. As the organic solvent, an organic compound having a perfluoro group excellent in solubility of the fluorine-containing silane compound and having 4 or more carbon atoms is preferable. For example, perfluorohexane, perfluorocyclobutane, perfluorooctane, perfluorodecane. Perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoro-4-methoxybutane, perfluoro-4-ethoxybutane, and metaxylene hexafluoride. Moreover, perfluoroether oil and chlorotrifluoroethylene oligomer oil can be used. In addition, CFC 225 (a mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF) can be exemplified. One of these organic solvents can be used alone or in admixture of two or more.

  The concentration when diluted with an organic solvent is preferably in the range of 0.03 to 1 wt%. If the concentration is too low, it may be difficult to form a sufficiently thick antifouling layer and a sufficient antifouling effect may not be obtained. On the other hand, if the concentration is too high, the antifouling layer may become too thick. There is a risk of increasing the burden of rinsing work to eliminate post-coating unevenness.

  As a coating method, a dipping method, a spin coat method, a spray method, a flow method, a doctor blade method, roll coat coating, gravure coat coating, curtain flow coating, brush coating, and the like are used.

  Although the film thickness of an antifouling layer is not specifically limited, 0.001-0.5 micrometer is preferable. In addition, Preferably it is 0.001-0.03 micrometer. If the film thickness of the antifouling layer is too thin, the antifouling effect is poor, and if it is too thick, the surface becomes sticky, which is not preferable. Further, when the antifouling layer is provided on the antireflection film surface, it is not preferable that the antifouling layer has a thickness of more than 0.03 μm because the antireflection effect is lowered.

In the case of the dipping method, the substrate is immersed in a water repellent treatment liquid adjusted to a predetermined concentration using the above organic solvent, and after a certain period of time, the substrate is pulled up at a constant speed. At this time, the immersion time is preferably about 0.5 to 3 minutes. If it is 0.5 minutes or less, the water repellent is not sufficiently adsorbed on the surface of the substrate, so that a predetermined water repellent performance cannot be obtained. In the case of 3 minutes or more, the cycle time is increased, which is not preferable.
The pulling speed is preferably 100 mm / min to 300 mm / min. This is determined in consideration of the concentration of the water-repellent treatment solution, but at 100 mm / min or less, the antifouling layer becomes too thin to obtain a predetermined antifouling performance, and at 300 mm / min or more, the antifouling property is obtained. The layer becomes too thick, and there is a risk that the burden of rinsing work for eliminating coating unevenness after application will increase.

In the present invention, the step of applying the water-repellent treatment liquid includes the step of forcibly removing the solvent after applying the antifouling film on the substrate of the optical article.
In order to forcibly remove the solvent, there are methods of heating and vacuum drying. These methods will be described sequentially.

  When the solvent is removed by heating, it is effective to put the substrate into a heating furnace maintained at a constant temperature. The temperature is determined by the boiling point of the solvent. The higher the temperature, the shorter the time required for the treatment. However, it is necessary to set the temperature appropriately in consideration of the heat resistant temperature of the substrate.

  The inventors have found that the solvent can be completely removed by heating in a heating furnace at a temperature of 50 ° C. to 70 ° C., a humidity of 20% or less, and a holding time of 5 to 15 minutes. Here, if it is less than 50 ° C., it may take time to remove the solvent and increase the cycle time. If it exceeds 70 ° C., the substrate may be adversely affected. Since it is necessary to do, it is not preferable.

  When the solvent is removed by vacuum drying, it is effective to put the substrate into a vacuum dryer. The pressure and temperature settings are determined by the vapor pressure and boiling point of the solvent. The lower the pressure and the higher the temperature, the shorter the time required for processing.

The inventors have found that the solvent can be completely removed if the pressure is 1 × 10 ⁻² to 4 × 10 ⁴ Pa, the temperature is room temperature to 70 ° C., and the holding time is 0.5 to 15 minutes. . Here, when the pressure exceeds 4 × 10 ⁴ Pa, it takes time to remove the solvent, which may increase cycle time, which is not preferable. Although the pressure can be set to less than 1 × 10 ^-2 Pa, the time required for decompression and the physical properties of the organic solvent used in the present invention can be sufficiently evaporated in a short time without lowering the pressure. Therefore, the pressure value was set as the lower limit.
If the temperature setting exceeds 70 ° C., the substrate may be adversely affected as described above, and it is necessary to take measures against burns during handling, which is not preferable.

  After the solvent removal step, an annealing step for fixing the fluorine-containing silane compound as a water repellent to the surface of the optical article is included. This is intended to increase durability by promoting chemical bonding between the fluorine-containing silane compound and the surface of the optical article.

  An annealing process is performed by leaving the optical article after solvent removal to stand indoors for 8 hours or more. More preferably, it is carried out by putting in a constant temperature and humidity chamber in which the temperature is set to 40 ° C. to 60 ° C. and the relative humidity is set to 60% to 90% for 1 hour to 2 hours. As an example, when R1 of the fluorine-containing silane compound represented by the chemical formula (2) is a methoxy group and the substrate is an inorganic glass, the methoxy group becomes a hydroxyl group by hydrolysis in the presence of moisture in the air, and this is a glass substrate. Silanol groups on the surface and hydroxyl groups generated by hydrolysis of other fluorine-containing silane compounds are bonded by dehydration condensation. These reactions are more accelerated under high temperature and high humidity.

  It has been confirmed that the antifouling optical article produced by the method as described above has excellent optical performance without appearance defects.

A 0.2% solution was prepared by diluting a fluorine-containing silane compound (trade name “KY-130”, manufactured by Shin-Etsu Chemical Co., Ltd.) in perfluorohexane, and used as a dipping treatment liquid for forming an antifouling layer. To prepare a plastic lens for eyeglasses (“Seiko Super Sovereign” manufactured by Seiko Epson Corporation) having a hard coat layer and an antireflection film (the outermost layer being SiO ₂ film) as a processing substrate, and cleaning the substrate surface The plasma treatment was performed. The plasma treatment conditions were as follows: treatment pressure: 0.1 Torr, introduced gas: dry air, distance between electrodes: 24 cm, power output: DC 1 KV, treatment time: 15 sec.

  The plasma-treated lens was immersed in a dipping treatment solution and held for 1 minute, and then pulled up at 150 mm / min to apply a water repellent treatment solution.

  Thereafter, as a solvent removal step, the lens was put into a heating furnace having a temperature of 60 ° C. and a relative humidity of 20%, and held for 10 minutes. Subsequently, as an annealing process, an antifouling layer was formed by placing in a constant temperature and humidity chamber set to 60 ° C. and 60% RH and holding for 2 hours.

A water repellent treatment liquid was applied to the lens in the same manner as in Example 1.
Thereafter, as a solvent removal step, the lens was put into a heating furnace having a temperature of 60 ° C. and a relative humidity of 20% and held for 10 minutes. Subsequently, as an annealing step, an antifouling layer was formed by leaving in an indoor atmosphere at 25 ° C. and 80% RH for 12 hours.

A water repellent treatment liquid was applied to the lens in the same manner as in Example 1.
Thereafter, as a solvent removal step, the lens was put into a vacuum dryer, and the solvent was removed by maintaining the vacuum degree at 1 × 10 ³ Pa and 50 ° C. for 5 minutes. Subsequently, as an annealing process, an antifouling layer was formed by placing in a constant temperature and humidity chamber set to 60 ° C. and 60% RH and holding for 2 hours.

A water repellent treatment liquid was applied to the lens in the same manner as in Example 1.
Thereafter, as a solvent removal step, the lens was put into a vacuum dryer, and the solvent was removed by maintaining the vacuum degree at 1 × 10 ³ Pa and 50 ° C. for 5 minutes. Subsequently, as an annealing process, an antifouling layer was formed by leaving it in an atmosphere of 25 ° C. and 80% RH for 12 hours.

[Comparative Example 1]
Applying a water repellent treatment liquid to the lens in the same manner as in Example 1, without providing a solvent removal step, immediately after application, as an annealing step, put into a constant temperature and humidity chamber set at 60 ° C. and 60% RH, The antifouling layer was formed by holding for 2 hours.

[Comparative Example 2]
A water repellent treatment solution was applied to the lens in the same manner as in Example 1, and then the solvent removal step was not provided, and the lens was left in an atmosphere of 25 ° C. and 80% RH for 12 hours as an annealing step.

(1) Appearance evaluation of lens Appearance evaluation was conducted in four types: a) transmission inspection in a dark box, b) reflection inspection in a dark box, c) transmission inspection in a ceiling light, and d) reflection inspection in a ceiling light. .

The dark box inspection conditions are a black plate with little reflection on the background and the desk, the illuminance in the inspection room is 200 to 250 lux, the illuminance at the test position is 350 to 500 lux, and inspection is performed in a clear vision state.
As the fluorescent lamp in the dark box, a three-wavelength light emitting daylight <FL (R) -20S (S) / EX-N> was used. A commercially available fluorescent lamp was used as the ceiling lamp.

  Next, each inspection method is described. Here, in contrast to c) and d), a) and b) are strict inspection methods, and defects are easily visible.

a) Transmission inspection in dark box In the dark box, the inspection object is held at a position about 30 cm from the eye on the straight line connecting the fluorescent lamp and the eye, and the inspection object is moved up and down for evaluation. Rotate 45-90 °, raise and lower and evaluate again.

b) Reflection inspection in dark box In the dark box, the object to be inspected is held in the vicinity of a desk about 30 cm from the eyes, and the evaluation is performed by changing the inclination angle with the fluorescent light reflected on the surface of the object to be inspected. Rotate 45-90 °, change the tilt angle and evaluate again.

c) Permeation inspection with ceiling lamps At a position where the ceiling fluorescent lamp is viewed obliquely upward, the inspection object is held at a position about 30 cm from the eyes on a straight line connecting the fluorescent lamp and the eyes, and the inspection object is moved up and down for evaluation. To do. Rotate 45-90 °, raise and lower and evaluate again.

d) Reflection inspection with a ceiling lamp At a position where the ceiling fluorescent lamp is viewed obliquely upward, the inspection object is held at a position around 30 cm from the eye, and the inclination angle is changed while the fluorescent lamp is reflected on the surface of the inspection object. To evaluate. Rotate 45-90 °, change the tilt angle and evaluate again.

With the above four evaluation methods, the appearance defect appearance state was determined in the following three stages.
○: No defect.
Δ: There is a thin defect.
It is not visible in the transmission / reflection inspection with the ceiling light, but it is visible in either the transmission / reflection inspection in the dark box.
X: There is a strong defect.
Visible in either transmission / reflection inspection with ceiling lights.

(2) Wiping durability test with cotton cloth Test method: Using cotton cloth, the convex surface of the lens was reciprocated 5000 times while applying a load of 100 g. The antifouling performance before and after the wiping durability test was evaluated by the contact angle and the wiping property of the oil-based ink.

Evaluation 1: Contact angle measurement A contact angle meter ("CA-D type" manufactured by Kyowa Scientific Co., Ltd.) was used to measure the contact angle, and the water contact angle was measured by a droplet method.

Evaluation 2: Wipeability of oil-based ink On the convex surface of the lens, a straight line of about 4 cm was drawn with a black oil-based marker (manufactured by “HIMACKY CARE” Zebra Co., Ltd.) and left for 5 min. After leaving, the mark portion was wiped off with a wipe paper (manufactured by Crecia Co., Ltd.), and the ease of wiping was determined according to the following criteria.
○: Completely removed by wiping 10 times or less.
Δ: Completely removed by wiping 11 to 20 times.
X: The part which is not removed remains after wiping off 20 times.

(3) Alkali resistance test Test method: The test piece is immersed in an aqueous sodium hydroxide solution adjusted to 0.05 N for 3 hours, and the immersed test piece is washed well with water. The antifouling performance before and after the alkali immersion test was evaluated by the contact angle and the wipeability of the oil-based ink.
The evaluation method was the same as (1) the wiping durability test with cotton cloth.

From the results shown in Table 1, it is clear that the antifouling lens produced by providing the step of removing the solvent after applying the water repellent treatment solution has greatly improved the appearance quality.
Moreover, from the results of Table 2, it was confirmed that the antifouling durability performance was not changed as compared with the conventional method by incorporating such a process.

  It is effective for improving the appearance quality of various antifouling optical articles. In addition to those shown in the examples, covers for various displays such as display panels for mobile phones, glass lenses for optical equipment, plastic lenses, etc. It can be used for optical lenses such as hybrid lenses, optical discs such as CD, DVD and MO, and optical fibers.

The process flowchart which showed the example of the process by this invention.

Claims (8)

In the antifouling layer forming method of forming an antifouling layer by applying a water-repellent fluorine-containing silane compound to the surface of an optical article,
A treatment liquid application step of applying a treatment liquid obtained by diluting the fluorine-containing silane compound in an organic solvent to the surface of the optical article;
A solvent removal step of forcibly removing the solvent of the treatment liquid applied to the surface of the optical article after the application step;
After the solvent removal step, an annealing step of fixing the fluorine-containing silane compound to the surface of the optical article by introducing the temperature to 40 ° C. to 60 ° C. and the relative humidity to 60% to 90% for 1 to 2 hours ;
A method for producing an antifouling optical article, comprising: The solvent removing step removes the solvent by holding the optical article coated with the solvent in a heating furnace having a temperature of 50 ° C. to 70 ° C. and a humidity of 20% or less for 5 to 15 minutes. The method for producing an antifouling optical article according to claim 1. The solvent removing step holds the optical article coated with the solvent in a vacuum dryer having a pressure of 1 × 10 ⁻² to 4 × 10 ⁴ Pa and a temperature of room temperature to 70 ° C. for 0.5 to 15 minutes. The method for producing an antifouling optical article according to claim 1, wherein the solvent is removed. The method for producing an antifouling optical article according to any one of claims 1 to 3, wherein the fluorine-containing silane compound is represented by the following general formula (1). .

The method for producing an antifouling optical article according to any one of claims 1 to 4, wherein a hard coat layer is formed in a lower layer of the antifouling layer. 5. The method for producing an antifouling optical article according to claim 1, wherein an antireflection film is formed in a lower layer of the antifouling layer. 6. The method for producing an antifouling optical article according to claim 5, wherein a hard coat layer is formed on the surface of a substrate, and the antireflection film is formed on the surface of the hard coat layer. Article manufacturing method. 8. The method for producing an antifouling optical article according to claim 5, wherein the base material is plastic.

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