JPH11167001A - Optical parts having antifogging function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain transparent optical parts having an antifogging function by providing the surface of a transparent optical substrate with a heating element consisting of an electroless plating film and utilizing the heat generated when electric power is thrown to the heating element. SOLUTION: The surface of an optical glass lens 1 is subjected to ultrasonic cleaning by using a water-soluble degreasing agent, then to strong acid cleaning and strong alkaline cleaning and is further subjected to washing with pure water. A resist film 2 is formed on the optical effective surface of the lens 1 and is again subjected to acid and alkaline cleaning, then to washing with the pure water. The catalyst nucleus impartation of Pd is executed by a sensitizer activator method and a 'Teflon(R)' jig 3 is press bonded to the resin coating part. The electroless Pd-P plating film 4 is formed on the glass substrate subjected to the Pd catalytic nucleus impartation. The resist film 2 is thereafter peeled. A prescribed voltage and current are applied to the Pd-P plating film 4 part and the fogging condensed onto the lens 1 is removed by the thus generated heat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical component such as a lens having an anti-fog function.

[0002]

2. Description of the Related Art Conventionally, as an antifogging method for an optical element, 1) a chemical coating applied to a hygroscopic organic substance, 2) a transparent conductor is formed on the optical element, and heat is generated so that water droplets are hardly formed. And the like exist as known techniques.

[0003] In the chemical coating of 1), an anti-fog lens (Japanese Patent Laid-Open Publication No. Sho 57) in which a hygroscopic resin (composed of triethylene glycol diacrylate or epoxy acrylate) is laminated on the surface of an inorganic glass lens by dipping or spraying.
Japanese Patent Application Laid-Open No. 56-97302 discloses a method for defogging a plastic lens by immersing a plastic lens in an incompletely cured state in a hydrophilic polymer monomer to integrally form a hydrophilic resin layer. Gazette).

In the heat generation method 2), a transparent conductive film is formed on the glass surface, and the conductive film is heated to evaporate water droplets adhering to the glass surface, thereby providing an anti-fogging effect. For example, there is an example in which an ITO film is formed on a side window glass for an automobile by sputtering (Japanese Patent Application Laid-Open No. 60-146719), or an ITO film is formed on the surface of a glass lens and heat is generated by flowing an electric current therethrough. Then, there is a method of evaporating water droplets, which are the cause of fogging attached to the optical element (JP-A-1-191101). Further, a method is provided in which an insulating layer is formed on a transparent conductive layer formed on glass or plastic, a reflective film is formed on the insulating layer, and the conductive layer is energized to remove heat from the surface of a rearview mirror or the like of an automobile due to heat generation (Japanese Patent Laid-Open No. 55-871
No. 01), a method in which a metal film is vacuum-deposited on the back surface of a substrate glass to form electrodes at the center and the periphery of the metal film (Japanese Patent Application Laid-Open No. 60-193739), and a method of forming a metal film on a glass substrate by sputtering. Alternatively, there is also known a method in which a metal oxide is coated as a reflection film and heating is performed by direct current supply (Japanese Patent Laid-Open No. 7-14668).

[0005]

The anti-fogging action of the chemical coat is due to the absorption and desorption of moisture around the lens, and is very effective under conditions of little environmental change.
The effect cannot be expected under the condition of many environmental changes. On the other hand, in the case of a heat-generating anti-fog lens, the adsorbed moisture can be evaporated by heat generation, and an anti-fog effect can be obtained by keeping the optical element surface warm by heat generation. In comparison, adaptation is possible over a particularly wide temperature range.

However, in the case of the conventional heat generation method, it is necessary to form a dense film on a glass substrate, and therefore, as a method of forming a reflective film, vacuum deposition or sputtering has been the main method. Film formation by such a dry process enables high-quality film formation and good adhesion to the substrate, but requires the use of a vacuum chamber, and therefore, the film formation is a batch process and the throughput (mass production) There is a problem that does not increase. When the substrate is glass, a process for increasing the temperature of the substrate may be included in order to increase the adhesion to the glass. In this case, since the temperature of the substrate needs to be increased and decreased, the throughput is further reduced.

In the case of a conventional substrate, for example, an ITO film or the like does not always have good compatibility with solder, and a vapor deposition film or the like sometimes causes aggregation of the film due to heat when it is connected to wiring by solder.

[0008]

According to the present invention, an antifogging film typified by a chemical coat or an ITO film can be formed by a wet plating process instead of a conventional dry process. An object of the present invention is to provide a transparent optical component having an anti-fog function.

The present invention also provides an anti-fogging function which can be formed by a wet plating process.
An optical component having a mirror surface is provided.

In the present invention, a surface other than the optical function surface of a transparent optical component such as a Fresnel lens on the optical element,
For example, an electroless plating film having good adhesion is applied to a surface such as an edge portion.

Furthermore, in the present invention, an electroless plating film having good adhesion is applied on the mirror surface of the optical component made of non-roughened glass or plastic substrate having a mirror surface.

The electroless plating film formed on the surface of the optical component preferably has a resistance value of about 1 × 10 ⁻⁴ Ωcm, and can function as a heating element. When a voltage is applied to such an electroless plating film, an electric current flows and the entire film generates heat, which raises the temperature of the optical component surface and evaporates water droplets adhered to the optical element surface, which causes fogging of the lens. Can be done.

[0013] Furthermore, by generating heat by directly applying a current to the electroless plating film on the surface of the optical element in advance, it is possible to provide the optical element with an anti-fog effect by preventing dew condensation.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a first embodiment of the present invention, an electroless plating film having good adhesion on a mirror-finished glass lens is formed on a glass surface other than the effective surface of the lens (the surface on the lens having an optical function). By forming the lens at the periphery of the lens or at the edge of the lens (the edge of the lens), the glass lens can have an anti-fog effect. Since the optical lens can expose the base material of the optical glass on its effective surface, a post-treatment such as an ordinary antireflection film can be easily performed in a subsequent vapor deposition step.

In the present invention, when electroless plating is formed on an optical component maintaining a mirror surface state, in order to sufficiently maintain the adhesion between the electroless plating film and the optical component, the electroless plating film is required. It is important to provide a nucleus on an optical component serving as a stepping stone for forming a sphere. For example, a sensitizer that replaces Sn adsorbed on the optical substrate surface with Pd.
Activator method, catalyst accelerator method for adsorbing Sn · Pd colloid on glass substrate surface, and alkali catalyst method for adsorbing alkaline Pd complex on optical substrate surface and then reducing to deposit metal Pd And the like.

The optimum thickness range in which the electroless plated film sufficiently maintains the adhesion to the optical component and functions as a heating element film is 0.1 μm to 0.5 μm. By forming the electroless plating film on the optical element with an appropriate film thickness, good adhesion between the optical element and the electroless plating film can be obtained.

In the second embodiment of the present invention, an electroless plating film is formed on a non-roughened glass or plastic substrate which has been mirror-finished in advance, so that the electroless plating film generates heat as a heating element to generate heat. To the substrate. Conventionally, there is a method of forming electroless plating on roughened glass or plastic by an anchor effect, but in order to form electroless plating on mirror-like non-roughened glass that can be a mirror, It becomes possible by defining the formation method, film quality, and film thickness conditions. Then, the electroless plating film formed on the optical substrate is subjected to a resistance value of preferably 1 × 10 ^−4.
A heating element can be obtained by controlling and forming the film thickness so as to have a value of about Ωcm.

When a voltage is applied to the heating element made of the electroless plating film, a current flows, and the entire film generates heat.
It is possible to elevate the surface temperature of the optical substrate and evaporate water droplets adhering to the surface, which cause fogging. Furthermore, an exothermic reaction can be caused by applying a current directly to the electroless plating film in advance, thereby preventing dew condensation and giving the substrate an anti-fog effect.

The electroless plating film is partially formed in a pattern on a glass or plastic optical substrate having a mirror surface to add an anti-fog function to the optical substrate while partially maintaining transparency. You can do it. For example,
On the non-roughened glass optical substrate, a portion other than a portion where a plating film is to be formed is masked with a resist or the like to perform electroless plating. As a result, a partially transparent area can be provided on the optical substrate, and by applying a current to the electroless plating, the optical substrate can have an anti-fog effect.

When an electroless plating film is formed on an optical substrate having a mirror surface, the most suitable film functioning as a heating element while maintaining sufficient adhesion between the electroless plating film and the optical component is palladium-phosphorus. It is a membrane.

[0021] Preferably, the phosphorus content of the electroless palladium-phosphorous plating film is 10% by weight or less. If the phosphorus concentration is too high, when the wiring and the electroless plating film are directly joined by solder or the like, the electroless plating film may be degenerated by heat.

There is no particular limitation on the optimum thickness range of the electroless plating film serving as a heating element. However, in order to obtain good adhesion between the optical component and the electroless plating film, 0.1 μm to 0.5 μm is required.
m is preferred.

In the present invention, in order to smoothly connect the electroless plating film to the wiring used when power is applied to the electroless plating film provided on the optical substrate, the optical substrate of the electroless plating film is used. 2.5kgf / mm2
It is preferable that, even when the electroless plating film and the wiring are directly joined by soldering or the like, film peeling or deterioration of the film does not occur, and mechanically and electrically reliable joining becomes possible. .

[0024]

[Example 1] (PdP film anti-fog glass lens) FIG. 1 shows a process of manufacturing a glass lens having an anti-fog function of the present invention. In FIG. 1, reference numeral 1 denotes a mirror-finished glass lens, 2 denotes a resist film formed on an optically effective diameter surface, 3 denotes a Teflon jig, and 4 denotes an electroless plating film.

First, the surface of the optical lens (glass material: BAL42 made by OHARA) 1 shown in FIG. 1 (a), whose final shape has been previously obtained by polishing, press molding, etc., is prepared using a water-soluble degreasing agent. After performing ultrasonic cleaning, strong acid cleaning (sulfuric acid + chromium oxide solution) and strong alkali cleaning (10 N sodium hydroxide solution) were performed, and further, water washing with pure water was performed.

Next, a resist film was formed on the optically effective surface of the lens 1 (FIG. 1B). In this example, TLCR-P8008 manufactured by Tokyo Ohka Kogyo was used as the resist.
In the plating step, an adhesive tape may be used as long as the peeling or elution of the resist film 2 does not occur.

Subsequently, the acid (OPC-9 manufactured by Okuno Pharmaceutical Co., Ltd.) was again used.
1,3% solution), alkali (Neos CT-10 3)
% Solution), and then washed and pulled up with pure water.

Subsequently, catalytic nuclei of Pd were applied by a general sensitizer activator method (a method in which Sn adsorbed on the surface of the optical substrate was replaced with Pd). Specifically, a PH containing 0.06 g / l of stannous chloride is used.
1. Immerse in an aqueous solution at a bath temperature of 25 ° C for 3 minutes, wash with pure water, then soak in an aqueous solution containing 0.1 g / l of palladium chloride at 25 ° C for 5 minutes, and wash with pure water. This gave Pd catalyst nuclei on the glass substrate. Subsequently, a Teflon jig 3 as shown in the figure was crimped to the resin-coated portion (FIG. (C)).

Next, an electroless Pd-P plating film 4 was formed at a bath temperature of 55 ° C. to form a 0.1 μm electroless Pd-P plating film 4 on the glass substrate provided with the Pd catalyst nucleus (FIG. 1).
(D)). Since the Teflon jig 3 is not provided with a nucleus, an electroless plating film 4 is formed as shown in FIG. 1D. At this time, if the resist film 2 contains a catalyst poison, the Teflon jig 3 does not need to be used. A resist film 2 continuously provided within the optical effective diameter
Was stripped with a stripping solution 104 manufactured by Tokyo Ohka Kogyo Co., Ltd. (FIG. 1).
(E)).

The PdP of the lens obtained as described above
When a voltage and current of 9 V and 0.4 A were applied to the plating film 4 portion, the fogging that had formed on the lens at an ambient temperature of 5 ° C. could be removed. At this time, the resistance value of the electroless PdP plating film 4 was 35 Ω / cm, and the adhesion strength with the glass lens was 2.5 kgf / 2 mm square or more.
When the film thickness of the electroless PdP plating film 4 is 0.6 μm or more, the adhesion strength to the glass lens is 2.0 kgf / 2.
mm square and below, and as the film thickness increases, the adhesion gradually decreases. On the other hand, although the film resistance becomes high when the film thickness is 0.1 μm or less, the stability of the film deteriorates because the density of the film itself decreases. Therefore, the film thickness is 0.1 μm
It is preferably between 0.5 μm and 0.5 μm.

A lens in which the electroless PdP plating film 4 previously formed on the glass lens 1 is energized at 9 V and 0.4 A for 10 minutes has a higher temperature of the atmosphere around the lens than a lens having no anti-fog function. When the temperature was rapidly lowered by 20 ° C., dew was formed on the lens having no anti-fogging function, but the anti-fogging lens of the present invention did not generate fogging.

Example 2 (NiP film anti-fog glass lens) Electroless PdP of Example 1
An electroless NiP plating film was used instead of the plating film. Pd
Up to the nucleus providing step, the same process as in Example 1 is performed.
An electroless NiP plating film was formed on the surface of the glass lens provided with a 0.1 μm Pd nucleus. Then, the resist provided within the optical effective diameter was peeled off by a UV ozone asher.

The NiP of the lens obtained as described above
When a voltage and current of 2 V and 0.5 A were applied to the plating film portion, it was possible to remove the fogging that caused dew condensation on the lens at an ambient temperature of 5 ° C. At this time, the resistance value of the electroless NiP plating film was 5 Ω / cm, and the adhesion strength with the glass lens was 2.5 kgf / 2 mm square or more. Electroless Ni
When the thickness of the P-plated film is 0.6 μm or more, the adhesion strength with the glass lens is 2.0 kgf / 2 mm square or less, as in the case of the electroless PdP plating film of Example 1, and the adhesion force is lower. It gradually goes down. On the other hand, the film thickness is 0.1μ
If it is less than m, the film resistance will increase, but the density of the film itself will decrease, and the stability as a film will deteriorate. For this reason, the film thickness is desirably between 0.1 μm and 0.5 μm.

Also, a lens in which the electroless NiP plating film previously formed on the glass lens is energized at 2 V and 0.5 A for 10 minutes has a 20% lower atmosphere around the lens than a lens having no anti-fog function. Even when the temperature was rapidly lowered, the lens having no anti-fogging function caused dew condensation, but the anti-fogging lens of the present invention did not cause fogging.

Example 3 (PdP Antifogging Plastic Lens) FIG. 2 shows a process for manufacturing a glass lens having an antifogging function according to the present invention. In FIG. 2, reference numeral 5 denotes a mirror-finished plastic lens,
Reference numeral 6 denotes a resist film formed on the optical effective diameter surface, 7 denotes a Teflon jig, and 8 denotes an electroless plating film. The plastic lens used this time was an injection molded product.

First, the surface of the optical lens (polycarbonate) shown in FIG. 2 (a) in which the final shape has been previously obtained by injection molding is subjected to ultrasonic cleaning using a water-soluble degreasing agent. After drying, the optically effective surface of the lens was masked (FIG. 2B). This time, adhesive tape was used for masking.

Subsequently, Pd catalyst nuclei were applied by a general sensitizer activator method (a method of replacing Sn adsorbed on the surface of an optical substrate with Pd). Specifically, PH1 containing 0.06 g / l of stannous chloride,
Immerse in an aqueous solution at a bath temperature of 25 ° C. for 3 minutes, wash with pure water, then immerse in an aqueous solution containing 0.1 g / l of palladium chloride at 25 ° C. for 5 minutes, and wash with pure water. The catalyst nucleus of Pd was provided on the lens 5 by the above method. Subsequently, a Teflon jig 8 as shown is pressure-bonded to the resin coating portion (FIG. 2C).

Next, an electroless Pd-P plating film 6 was coated at a bath temperature of 55.degree. (FIG. 2D). Since the Teflon jig is not provided with a nucleus, an electroless plating film 4 is formed as shown in FIG. 2D. Subsequently, the adhesive tape provided within the effective optical diameter was peeled off, and solvent cleaning was performed (FIG. 2).
(E)).

The PdP of the lens obtained as described above
When a voltage and current of 9 V and 0.4 A were applied to the plating film portion, it was possible to remove the fogging that had formed on the lens at an ambient temperature of 5 ° C. At this time, the resistance value of the electroless PdP plating film was 38 Ω / cm, and the adhesion strength with the lens 5 was 2.5 kgf / 2 mm square or more. Electroless P
When the thickness of the dP plating film 8 is 0.6 μm or more,
The adhesive strength to the lens 5 is 2.0 kgf / 2 mm square or less, and the adhesive strength gradually decreases as the film thickness increases. On the other hand, when the film thickness is 0.1 μm or less, the film resistance is increased, but the density of the film itself is reduced, so that the stability as the film is deteriorated. Therefore, the film thickness is 0.1 μm to 0.5
It is preferably between μm.

Further, 9 V is applied to the electroless PdP plating film 8 in advance.
The lens that had been energized at 0.4 A for 10 minutes generated condensation on the lens without the anti-fog function even when the atmosphere around the lens was suddenly lowered by 20 ° C., compared to the lens without the anti-fog function. However, the anti-fog lens of the present invention did not cause fogging.

Example 4 (NiP anti-fog plastic lens) Electroless P of Example 3
An electroless NiP plating film was formed instead of the dP plating film. The process up to the Pd nucleus providing step was performed in the same process as in Example 3, and an electroless NiP plating film was formed on the surface of the plastic lens to which the 0.3 μm Pd nucleus was provided. Then, the adhesive tape provided within the optical effective diameter was peeled off, and the solvent was washed.

The NiP of the lens obtained as described above
When a voltage and current of 2 V and 0.5 A were applied to the film portion,
At an ambient temperature of 5 ° C., it was possible to remove the fogging that had formed on the lens. At this time, the resistance value of the electroless NiP plating film was 6 Ω / cm, and the adhesion strength with the lens was 2.5.
Kgf / 2 mm square or more. When the film thickness of the electroless NiP plating film is 0.6 μm or more, the adhesion strength to the glass lens is 2.0 kgf / 2 mm square or less, similarly to the case of the electroless PdP plating film of Example 1. As the number increases, the adhesion gradually decreases. On the other hand, although the film resistance becomes high when the film thickness is 0.1 μm or less, the stability of the film deteriorates because the density of the film itself decreases. For this reason, the film thickness is desirably between 0.1 μm and 0.5 μm.

Also, the electroless NiP formed on the lens in advance
The lens that has been energized at 2V 0.5A for 10 minutes to the plating film is compared with the lens without the anti-fog function as compared with the lens without the anti-fog function. Dew condensation occurred, but the anti-fog lens according to the present invention did not fog.

Example 5 (Anti-Fogging Optical Element) FIG. 3 shows a toric lens used in a laser beam printer or the like, and FIG. 4 shows a Fresnel lens. In FIG. 3, a portion indicated by reference numeral 9 is a portion where an electroless plating film is formed, and 10 is an optically effective surface through which laser light passes. Also, in FIG.
Denotes a portion where an electroless plating film is formed, and 12 denotes an optically effective Fresnel lens portion.

As shown in the present embodiment, by forming electroless PdP plating or electroless NiP film plating on optically unnecessary portions of various optical elements, as described in Examples 1-4. In addition, it was possible to form an optical element having an anti-fog function both of glass and plastic.

Example 6 (PdP-roughened glass optical substrate) FIG. 5 is a cross-sectional view of a glass optical substrate having an anti-fog function according to the present invention.
(A)-(f) show the various shapes. FIG. 5A shows a plate-shaped non-roughened glass optical substrate 21 having an electroless Pd-P plating film 22 formed thereon.
5 (c) shows a concave mirror, FIGS. 5 (d) and 5 (e) show convex mirrors, and FIG. 5 (f) shows an electroless Pd-P plating film 22 formed on the entire surface of an optical substrate 21. It is. The arrow in FIG. 5 indicates the observation direction, and FIG.
(D) shows the case where an electroless Pd-P plating film is formed as a direct reflection surface, and FIGS. 5 (c) and 5 (e) show the case where the electroless Pd-P plating film is used as a reflection surface through an optical substrate. Is shown.

The production method will be described below in detail.

First, the surface of a green sheet made of Nippon Sheet Glass, which has been formed into an arbitrary shape or mirror-finished, is subjected to ultrasonic cleaning using a water-soluble degreasing agent, followed by strong acid cleaning (sulfuric acid + chromium oxide solution), After alkali washing (10 N sodium hydroxide solution), washing with pure water was performed. Next, as shown in FIGS. 5D to 5E, when the electroless plating film 22 is formed only on one surface, masking with a resist, a film, or the like is formed on a portion where plating is unnecessary, and then, After washing again with an acid (OPC-91, 3% solution manufactured by Okuno Pharmaceutical Co., Ltd.) and an alkali solution (CT-10 3% solution manufactured by Neos), washing and pulling up were performed with pure water.
This time, TLCR-P made by Tokyo Ohka Kogyo containing plating catalyst poison
8008 was used.

Subsequently, a catalyst nucleus of Pd was applied by a general sensitizer activator method (a method of replacing Sn adsorbed on the surface of an optical substrate with Pd). Specifically, a PH containing 0.06 g / l of stannous chloride is used.
1. Immerse in an aqueous solution at a bath temperature of 25 ° C for 3 minutes, wash with pure water, then soak in an aqueous solution containing 0.1 g / l of palladium chloride at 25 ° C for 5 minutes, and wash with pure water. This gave Pd catalyst nuclei on the glass substrate.

Next, an electroless Pd-P plating solution was formed at a bath temperature of 55 ° C. on the glass substrate to which the Pd catalyst nucleus had been applied, to form a 0.1 μm electroless Pd-P plating film. Subsequently, the resist formed for masking was stripped by immersion in an alkali stripping solution (stripping solution 104 manufactured by Tokyo Ohka Kogyo Co., Ltd.).

The P of the anti-fog mirror obtained as described above
When a voltage and current of 15 V and 0.5 A were applied to the dP plating film portion, fogging formed on the anti-fog mirror at an ambient temperature of 5 ° C. could be removed. Electroless PdP at this time
The resistance value of the plating film was 35 Ω / cm, and the adhesion strength with the glass optical substrate was 2.5 kgf / 2 mm square or more. When the film thickness of the electroless PdP plating film is 0.6 μm or more, the adhesion strength to the glass optical substrate is 2.0 kg.
f / 2 mm square or less, and the adhesive force gradually decreases as the film thickness increases. On the other hand, although the film resistance becomes high when the film thickness is 0.1 μm or less, the stability of the film deteriorates because the density of the film itself decreases. Therefore, the film thickness is 0.1
It is preferably between μm and 0.5 μm.

When the concentration of phosphorus in the electroless Pd-P plating film is 10 wt% or more, the film may be aggregated at the time of soldering. However, when the phosphorus content is 10 wt% or less, stable solderability can be maintained.

The anti-fog mirror in which a current of 15 V and 0.5 A was applied to the electroless PdP plating film formed on the glass optical substrate in advance for 10 minutes was compared with an optical substrate having no anti-fog function. Even if the atmosphere around the mirror was rapidly lowered by 20 ° C., dew condensation occurred on the mirror having no anti-fog function, but the anti-fog mirror of the present invention did not generate fogging.

The flat antifogging mirror as shown in FIG. 5A is effective for use in a mirror stand, a washstand and the like.

Example 7 (NiP film anti-fog glass lens) Electroless PdP of Example 6
An electroless NiP plating film is used instead of the plating film. Pd
Up to the nucleus providing step, the same process as in Example 6 was performed, and an electroless NiP plating film was formed on the surface of the glass optical substrate provided with the 0.1 μm Pd nucleus. Then, the resist film provided in the same manner as in Example 6 was peeled off by alkali immersion.

The N of the anti-fog mirror obtained as described above
When a voltage and current of 4 V and 0.5 A were applied to the iP plating film portion, it was possible to remove the fogging formed on the anti-fog mirror at a peripheral temperature of 5 ° C. Electroless NiP at this time
The resistance value of the plating film was 5 Ω / cm, and the adhesion strength to the glass substrate was 2.5 kgf / 2 mm square or more.
When the film thickness of the electroless NiP plating film is set to 0.6 μm or more, the adhesion strength to the glass optical substrate is 2.0 kgf / 2 mm as in the case of the electroless PdP plating film of Example 6.
The adhesive strength gradually decreases as the film thickness increases. On the other hand, although the film resistance becomes high when the film thickness is 0.1 μm or less, the stability of the film deteriorates because the density of the film itself decreases. Therefore, the film thickness is 0.1 μm or more.
Desirably between 0.5 μm.

Further, when the phosphorus content of the electroless Pd-P plating film is 10 wt% or more, the film may aggregate at the time of soldering, and when it is 10 wt% or less, stable solderability can be maintained.

Further, the anti-fog mirror in which the electroless NiP plating film formed on the glass optical base was previously energized at 4 V and 0.5 A for 10 minutes was compared with a mirror having no anti-fog function, Even when the atmosphere was suddenly lowered by 20 ° C., dew condensation occurred on the mirror having no anti-fogging function, but the anti-fogging mirror of the present invention did not generate fogging.

Example 8 (PdP Antifogging Plastic Mirror) FIG. 6 is a sectional view of a plastic optical substrate having an antifogging function according to the present invention.
6 (a) to 6 (f) show various forms thereof. FIG.
(A) shows a plastic optical substrate 23 in which a flat mirror-like state is maintained and an electroless Pd-P plating film 24 is formed, and FIGS. 6 (b) and 6 (c) show concave mirrors.
FIGS. 6D and 6E show convex mirrors, and FIG. 6F shows an electroless Pd-P plating film formed on the entire surface of the substrate. Each arrow in FIG. 6 indicates an observation direction, and FIGS. 6B and 6D show the case where an electroless Pd-P plating film is formed as a direct reflection surface, as shown in FIGS. FIG. 6 (e) shows an electroless Pd-
This shows an embodiment in which a P plating film is used as a reflection surface.

The production method will be described below in detail.

First, the surface of the plastic material PC (polycarbonate), whose final shape has been previously obtained by injection molding, is subjected to ultrasonic cleaning using a water-soluble degreasing agent, dried, and then dried. Was masked (FIG. 6B). This time, adhesive film tape was used for masking.

Subsequently, Pd catalyst nuclei were applied by a general sensitizer activator method (a method of replacing Sn adsorbed on the surface of an optical substrate with Pd). Specifically, a PH containing 0.06 g / l of stannous chloride is used.
1. Immerse in an aqueous solution at a bath temperature of 25 ° C for 3 minutes, wash with pure water, then soak in an aqueous solution containing 0.1 g / l of palladium chloride at 25 ° C for 5 minutes, and wash with pure water. This gave Pd catalyst nuclei on the glass substrate.

Next, using an electroless Pd-P plating solution,
At a bath temperature of 55 ° C., an electroless Pd—P plating film was formed to a thickness of 0.1 μm on the optical substrate provided with the Pd catalyst nucleus. Subsequently, the adhesive tape provided for masking was peeled off, and alcohol-based solvent washing was performed.

The P of the anti-fog mirror obtained as described above
When a voltage and current of 15 V and 0.5 A were applied to the dP plating film portion, it was possible to remove the fogging formed on the anti-fog mirror at a peripheral temperature of 5 ° C. Electroless PdP at this time
The resistance value of the plating film was 38 Ω / cm, and the adhesion strength to the plastic optical substrate was 2.5 kgf / 2 mm square or more.

The film thickness of the electroless PdP plating film is set to 0.6 μm.
When the thickness is not less than m, the adhesion strength to the plastic substrate is 2.0 kgf / 2 mm square or less, and the adhesion strength gradually decreases as the film thickness increases. On the other hand, although the film resistance becomes high when the film thickness is 0.1 μm or less, the stability of the film deteriorates because the density of the film itself decreases. For this reason, the film thickness is desirably between 0.1 μm and 0.5 μm.

Further, the anti-fog mirror in which the electroless PdP plating film formed on the plastic optical substrate was energized at 15 V and 0.5 A for 10 minutes from the beginning has a lower atmosphere around the mirror than the mirror without the anti-fog function. Even if the temperature was suddenly lowered by 20 ° C., dew condensation occurred on the mirror having no anti-fogging function, but the anti-fogging mirror of the present invention did not generate fogging.

Example 9 (NiP anti-fog plastic lens) Electroless P of Example 8
An electroless NiP plating film was used instead of the dP plating film. The process up to the Pd nucleus providing step was performed in the same process as in Example 6, and an electroless NiP plating film was formed on the surface of the plastic optical substrate provided with the 0.1 μm Pd nucleus. Then, in the same manner as in Example 8, the adhesive tape provided for masking was subsequently peeled off, and an alcohol-based solvent was washed.

The NiP of the lens obtained as described above
When a voltage and current of 4 V and 0.5 A were applied to the plating film portion, it was possible to remove the fogging that caused dew condensation on the lens at an ambient temperature of 5 ° C. At this time, the resistance value of the electroless NiP plating film was 6 Ω / cm, and the adhesion strength to the plastic optical substrate was 2.5 kgf / 2 mm square or more.
When the film thickness of the electroless NiP plating film is 0.6 μm or more, the adhesion strength to the plastic substrate is 2.0 kgf / 2 m, as in the case of the electroless PdP plating film of Example 8.
The adhesion becomes gradually smaller as the film thickness increases. On the other hand, although the film resistance becomes high when the film thickness is 0.1 μm or less, the stability of the film deteriorates because the density of the film itself decreases. Therefore, the film thickness is 0.1 μm or more.
Desirably between 0.5 μm.

The anti-fog mirror, which was previously energized at 4 V and 0.5 A for 10 minutes on the electroless NiP plating film formed on the plastic optical substrate, has a better atmosphere around the mirror than the mirror without the anti-fog function. Even if the temperature was suddenly lowered by 20 ° C., dew condensation occurred on the mirror having no anti-fogging function, but the anti-fogging mirror of the present invention did not generate fogging.

Example 10 (Anti-fogging glass substrate having a transparent portion) FIG. 7 is a schematic view of a step of forming an electroless plating film having good adhesion on a part of a non-roughened glass maintaining a mirror surface state. is there.

First, the surface of a soda lime glass made of Nippon Sheet Glass is subjected to ultrasonic cleaning using a water-soluble degreasing agent, followed by strong acid cleaning (sulfuric acid + chromium oxide solution) and strong alkali cleaning (10N sodium hydroxide solution). , Followed by washing with pure water. Next, a catalyst nucleus of Pd was applied by a general sensitizer activator method (a method of replacing Sn adsorbed on the optical substrate surface with Pd). In particular,
PH1 containing 0.06 g / l stannous chloride, bath temperature 2
After immersion in an aqueous solution of 5 ° C. for 3 minutes, washing with pure water, and 25 ° C. in an aqueous solution containing 0.1 g / l of palladium chloride.
For 5 minutes, and then washed with pure water to apply Pd catalyst nuclei on the glass substrate.

Next, the electroless Pd-P plating solution was applied at a bath temperature of 55 ° C. to the glass optical substrate 27 provided with the Pd catalyst nucleus.
An electroless Pd-P plating film 26 was formed thereon at 0.1 μm (FIG. 7A). Next, after applying a resist film 28 of a positive resist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) (FIG. 7B), a line pattern 29 is provided on the electroless Pd-P plating film formed by photolithography. (FIG. 7C) Unnecessary portions are removed by chemical etching with a mixed acid (a mixed solution of nitric acid, hydrochloric acid, and acetic acid) to form an exposed portion 30 (FIG. 7D). A line pattern as shown in FIG. 7E was formed. The line width at this time was 200 μm.

When a voltage current of 9 V and 0.5 A was applied to the PdP film portion of the anti-fogging glass optical substrate obtained as described above, dew was formed on the anti-fogging glass substrate at an ambient temperature of 5 ° C. Fogging can be removed. At this time, the resistance value of the electroless PdP plating film was 35 Ω / cm, and the adhesion strength to the glass substrate was 2.5 kgf / 2 mm square or more. When the film thickness of the electroless PdP plating film is 0.6 μm or more, the adhesion strength to the glass optical substrate is 2.0K.
gf / 2 mm square and below, and the adhesive force gradually decreases. On the other hand, although the film resistance is increased below 0.1 μm,
Since the density of the film itself decreases, the stability as the film deteriorates. For this reason, the film thickness is desirably between 0.1 μm and 0.5 μm.

Further, when the phosphorus content of the electroless Pd-P plating film is 10 wt% or more, the film may aggregate at the time of soldering, and when it is 10 wt% or less, stable solderability can be maintained.

The antifogging glass substrate in which the electroless PdP plating film formed on the glass optical substrate was previously energized at 9 V and 0.5 A for 10 minutes was compared with the optical substrate having no antifogging function. Even if the atmosphere around the substrate was suddenly lowered by 20 degrees, dew condensation occurred on the optical substrate having no antifogging function, but the antifogging glass substrate of the present invention did not generate fogging.

As shown in Example 7, electroless Pd
The same effect was obtained by changing the -P plating film to an electroless Ni-P plating film.

In the case where the optical substrate is made of plastic, the method shown in Embodiments 8 and 9 can be applied to Embodiment 10.
A similar effect could be obtained by applying the method described above.

Further, in addition to the flat optical substrate shown in this embodiment, it is possible to use various shapes as shown in Embodiments 6 and 7 by performing arbitrary masking.

[Embodiment 11] (Self-supporting curved mirror) By using the convex type anti-fog mirror as shown in Embodiments 6 to 9, a self-supporting curved mirror integrating a solar cell and a storage battery is realized. It becomes possible. 8, reference numeral 31 denotes a convex anti-fog mirror, 32 denotes a solar cell, and 33 denotes a storage battery. In the daytime, by storing the power generated by the solar cell 32 with sunlight in the storage battery 33, 10 V, 0.2 A of power is supplied to the anti-fog mirror 31 using the stored power, and the anti-fog effect is obtained. Was.

FIG. 5 shows an anti-fog mirror as a curved mirror.
5D and FIG. 5E, or FIGS. 6D and 6E are effective.
(D), as shown in FIG. 6 (d), in the case where the electroless plating film which is the anti-fog function surface is in direct contact with the atmosphere, a conventional chemical coating having an anti-fog effect is formed on the electroless plated film. By coating, a further anti-fog effect can be obtained simultaneously with protection of the electroless plating film.

[0081]

As described above, according to the present invention, electroless plating with good adhesion is performed on an optical element made of glass or plastic without impairing the optical performance, and this electroless plated film is heated. As a result, an optical element having an anti-fogging effect could be formed.

As a result, (1) an optical element having an anti-fog effect can be formed over a wide range of temperature conditions as compared with a chemically coated lens, and (2) the original lens surface is exposed within the effective optical diameter. Therefore, it is possible to form a normal anti-reflection film as compared with a chemical coat, (3) has better solderability than conventional vapor-deposited films, has better wiring connectivity, and (4) is manufactured by a wet process by plating. Therefore, as compared with a film forming apparatus for forming a transparent conductor film, a large-capacity continuous line can be manufactured, so that an effect that the throughput (mass productivity) can be improved can be obtained.

[Brief description of the drawings]

FIGS. 1A to 1E are explanatory views showing steps of manufacturing an optical component having an antifogging function according to the present invention.

FIGS. 2A to 2E are explanatory views showing steps of manufacturing another optical component having an antifogging function of the present invention.

FIG. 3 is a perspective view showing a toric lens having an anti-fog function.

FIG. 4 is a plan view showing a Fresnel lens having an anti-fog function.

FIG. 5 is a cross-sectional view showing various forms of an optical component having an anti-fog function according to the present invention.

FIG. 6 is a cross-sectional view showing various forms of a plastic optical component having an anti-fog function according to the present invention.

FIG. 7 is an explanatory view showing a step of manufacturing an optical component having partial transparency according to the present invention.

FIG. 8 is a side view of a self-standing curve mirror using the optical component having an anti-fog function of the present invention.

[Explanation of symbols]

 1 glass lens 2 resist film. REFERENCE SIGNS LIST 3 Teflon jig 4 Electroless plating film 5 Plastic lens 6 Masking 7 Teflon jig 8 Electroless plating film 9 Electroless plating film 10 Optically effective surface 11 Electroless plating film 12 Fresnel lens part 21 Non-roughening Glass optical substrate 22 Electroless plated film 23 Plastic optical substrate 24 Electroless plated film 26 Electroless plated film 27 Non-roughened glass optical substrate 28 Resist film 29 Line pattern 30 Exposed portion 31 Convex anti-fog mirror 32 Solar cell 33 Storage battery

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 3/08 G02B 3/08 5/08 5/08 F

Claims (10)

[Claims] 1. A heating element made of an electroless plating film having good adhesion to the optical base is provided on a transparent optical base made of glass or plastic, and heat generated when power is applied to the heating element is used. An optical component having an anti-fog function, wherein the optical substrate is subjected to anti-fog. 2. The optical component according to claim 1, wherein the transparent substrate is an optical glass lens or an optical plastic lens, and the heating element is provided outside an optically effective surface of the optical glass lens or the optical plastic lens. 3. The electroless plating film constituting the heating element comprises at least one of an electroless palladium-phosphorous plating film and an electroless nickel-phosphorous plating film.
Or the optical component according to 2. 4. The optical component according to claim 1, wherein the thickness of the electroless plating film constituting the heating element is 0.1 μm to 0.5 μm. 5. A heating element made of an electroless plating film having good adhesion to the optical substrate is provided on an optical substrate made of non-roughened glass or plastic having a mirror surface, and generated when power is applied to the heating element. An optical component having an anti-fog function, wherein the optical base is subjected to anti-fog using heat generated. 6. The optical component according to claim 5, wherein the electroless plating film constituting the heating element is formed on a part of a mirror surface of the optical component. 7. The electroless plating film constituting the heating element comprises at least one of an electroless palladium-phosphorous plating film and an electroless nickel-phosphorous plating film.
Or the optical component according to 6. 8. The electroless plating film constituting the heating element comprises at least one of an electroless palladium-phosphorus plating film and an electroless nickel-phosphorus plating film, and the phosphorus content of the electroless plating film is 10 wt. % Or less. 9. The optical component according to claim 5, wherein the thickness of the electroless plating film constituting the heating element is 0.1 μm to 0.5 μm. 10. An electroless plating film constituting the heating element is connected to external wiring by direct soldering.
10. The optical component according to any one of items 9 to 9.