JP4486404B2 - Translucent resin product manufacturing method and translucent resin product - Google Patents

Description

  The present invention relates to a method for producing a resin substrate having translucency and a resin substrate having translucency.

  Resin products have penetrated deeply into our lives, taking advantage of their properties. Although the properties vary depending on the type of resin, translucent resin products are lighter in weight and superior in impact resistance than glass. New products are being developed and their applications are expanding. In automotive parts, translucent resin products are used for covers such as headlights, tail lamps, winkers, etc., and some are beginning to be used for resin windows. Even for eyeglass lenses, plastic lenses are now the mainstream because they are lighter, safer, and rich in color variations than glass lenses. However, since resin products have a drawback of being easily damaged, it is indispensable to apply a hard coat coating film to the resin base material to compensate for this.

In the plastic lens for spectacles, a method of providing a silicone-based hard coat film on a plastic lens substrate is generally performed, but even if the hard coat liquid is applied to the substrate as it is, adhesion is not sufficient, The coating film is often peeled off. Therefore, in order to improve the adhesion between the plastic lens substrate and the hard coat film, for example, it is disclosed in JP-A-5-93803, JP-A-6-171028, JP-A-9-136978, etc. As described above, it is a common practice to provide a liquid-coated primer layer on a plastic lens substrate. Further, as another method for improving the adhesion, it is generally performed that the substrate is pretreated by alkali treatment, plasma treatment, corona treatment or the like immediately before the hard coat liquid coating step. For example, Japanese Patent Application Laid-Open No. 7-96555 discloses a plastic optical having a hard coat layer on a transparent substrate mainly composed of a resin containing sulfur and having a base material surface treated with an alkali solution. An article is disclosed. Japanese Patent Application Laid-Open No. 11-316302 discloses a method for producing a plastic lens, in which a plastic lens substrate is subjected to plasma treatment on or in the vicinity of an electrode and then a hard coat layer is applied. . Japanese Patent Application Laid-Open No. 10-67869 discloses a method of performing corona treatment with a high voltage pulse while blowing a gas onto a plastic surface with poor wettability.
JP-A-5-93803 Japanese Patent Laid-Open No. 6-171028 JP-A-9-136978 Japanese Patent Laid-Open No. 7-96555 JP-A-11-316302 JP-A-10-67869 JP 2002-53982 A JP 2003-238710 A

  However, these conventional treatment methods require labor and cost, and the improvement in adhesion cannot be obtained so much by alkali treatment, plasma treatment, and corona treatment.

  In the method of providing a liquid coating type primer layer, a primer liquid is applied to a plastic lens substrate and cured by heating. However, this process requires a lot of time and energy, which causes an increase in cost. Moreover, when applying by the dipping method which is a general application method of the primer solution, the yield of the primer solution is very poor and a large amount of solution is required. If the primer solution is not sufficiently cured by heating, the primer layer may be eluted when the hard coat solution is immersed in the next step, which may contaminate the hard coat solution. In addition, the provision of a liquid-coated primer layer forms a thickness that affects the visible light, so the refractive index of the primer layer and the nonuniformity of the film thickness in the layer are involved. The interference pattern of the product is affected. Interference fringes are a major drawback for translucent resin products such as optical products. When trying to reduce the influence of the primer layer on the interference fringes, it is difficult to eliminate the non-uniformity of the film thickness, so it is necessary to match the refractive index of the primer layer with the refractive index of the substrate. Cause up.

  Alkali treatment is a method to roughen the lens surface and improve adhesion by treating the plastic lens substrate with strong alkali, but the hard coat used in the subsequent coating process because the alkali cannot be removed in the washing tank. Since the liquid is weak against alkali, it has adverse effects such as inclusion and hard coat liquid contamination. In plasma processing and corona processing, although a large-scale apparatus is required, a small batch processing takes time, and production efficiency is low. In particular, plasma processing requires that the substrate to be processed be placed in a vacuum chamber and can be easily performed on relatively small substrates such as plastic lenses, but relatively large substrates such as automotive resin windows. The material becomes large and expensive.

  The problem to be solved by the present invention is to improve the adhesion of the hard coat film to the translucent resin base material and obtain a translucent resin product having excellent scratch resistance. Another problem is to obtain a translucent resin product with less interference fringes by eliminating the influence on the interference fringes due to the treatment for improving the adhesion.

  Japanese Patent Application Laid-Open No. 2002-53982 discloses a method of modifying the surface of a solid substrate by modifying the surface of the solid substrate of glass, ceramic, metal, or plastic product by oxidation flame treatment and silicic acid flame treatment. A method for printing a solid substrate surface by applying an ink or paint to a modified solid substrate surface is disclosed. Japanese Patent Application Laid-Open No. 2003-238710 discloses a modifier compound containing silane, titanium, or aluminum as an improvement of problems such as incomplete combustion in the method for modifying the solid substrate surface. A method for surface modification of a solid material, characterized in that a flame of a fuel gas containing a modifier compound having a boiling point of 10 to 100 ° C. is sprayed entirely or partially on the surface of the solid material. It is disclosed. Using these methods, the present inventors sprayed a flame with a fuel gas containing an organosilicon compound modifier on the translucent resin base material to modify the surface of the base material. It has been found that providing a hard coat film on the surface modified layer results in an excellent translucent resin product, leading to the present invention. That is, the present invention has the following configuration.

  According to the first aspect of the present invention, a flame of a fuel gas containing an organosilicon compound modifier is sprayed entirely or partially on the surface of a translucent resin substrate, and silicon oxide is formed on the translucent resin substrate. A method for producing a translucent resin product, comprising: forming a modified film and then forming a hard coat film on the silicon oxide film.

  The translucent resin substrate used in the present invention includes, but is not limited to, polycarbonate resin, acrylic resin, polyurethane resin, polyolefin resin, epoxy resin, polyepisulfide resin, polyimide resin, polyamide resin, styrene resin and the like. . Of these, those having translucency are used.

  An organosilicon compound modifier is a modifier by a silane compound, and examples thereof include an alkylsilane compound and an alkoxysilane compound. Of these compounds, alkylsilane compounds are more preferred modifier compounds. Preferred examples of such alkylsilane compounds include tetramethylsilane, tetraethylsilane, 1,2-dichlorotetramethylsilane, 1,2-diphenyltetramethylsilane, 1,2-dichlorotetraethylsilane, 1,2-diphenyl. Examples thereof include tetraethylsilane, 1,2,3-trichlorotetramethylsilane, 1,2,3-triphenyltetramethylsilane, dimethyldiethyltetrasilane and the like. In the present invention, these organosilicon compound modifiers are mixed with oxygen or a flammable gas to form a fuel gas, and the treatment substrate is sprayed with a flame of the fuel gas. It is preferable to treat the flame temperature within a range of 500 to 1500 ° C. When the temperature is less than 500 ° C, it becomes difficult to prevent incomplete combustion of the organosilicon compound modifier. Will be thermally deformed or deteriorated. The spray treatment depends on the temperature of the flame, but the treatment is performed at a treatment speed or treatment time at which the treated substrate does not undergo thermal deformation or thermal deterioration. The silicon oxide film formed by this treatment has excellent adhesion to the hard coat film that improves the scratch resistance.

  The invention according to claim 2 is the manufacturing method according to claim 1, wherein the hard coat film is formed by a silicone resin hard coat liquid containing a metal oxide sol.

  The metal oxide sol is obtained by dispersing metal oxide fine particles in a colloidal form using water or an organic solvent such as alcohol as a dispersion. The metal oxide fine particles are fine particles made of an oxide of a metal selected from the group consisting of Si, Al, Ti, Zr, Sn, Sb, W, In, Ce, Zn, Fe, La, and Ta. It is preferable that the metal oxide fine particles having a particle diameter of 1 to 100 nm include one or more kinds. More preferably, the metal oxide fine particles are composite fine particles made of an oxide of at least two kinds of metals selected from the group consisting of the above element group. An example of composite fine particles is to suppress the photocatalytic action of organic matter decomposition, which is a characteristic of titanium oxide, by using a composite with other metal oxides such as antimony oxide while utilizing the high refractive characteristics of titanium oxide. There is. Interference fringes resulting from non-uniformity of the thickness of the hard coat layer by using one or more of these composite fine particles to match or approximate the refractive indexes of the hard coat layer and the translucent resin substrate. And a hard coat film having excellent weather resistance can be formed. Particularly in an optical product such as a plastic lens, since a high refractive index resin is used for the base material, the effect of the metal oxide sol is great. Further, by using a hard coat of a silicone resin type, compatibility with the silicon oxide film layer is good and adhesion is improved.

  The invention according to claim 3 is the manufacturing method according to claim 1 or 2, wherein the resin base material is a plastic lens base material.

  In a plastic lens in which a high refractive index is particularly required, the influence of interference fringes due to the difference in refractive index and the nonuniformity of the film thickness is large, and those with conspicuous interference fringes are defective. Therefore, using the present invention for a plastic lens leads to a decrease in the defective product occurrence rate and is very effective.

  The invention according to claim 4 is the manufacturing method according to any one of claims 1 to 3, wherein the silicon oxide film is formed to have a thickness of 1 to 60 nm.

  By forming the silicon oxide film with a thickness of 1 to 60 nm, which is much smaller than the wavelength of visible light, the behavior of visible light is not affected, and interference fringes caused by the silicon oxide film are not generated. .

  The invention which concerns on Claim 5 is a translucent resin product which has a hard-coat coating film manufactured by the manufacturing method of any one of Claims 1-4.

The translucent resin product thus produced is excellent in interference fringes, scratch resistance, and hard coat film adhesion. After the hard coat film is formed, a single-layer or multi-layer antireflection film may be selectively provided. Thereby, the improvement of the transmittance | permeability by reduction of reflection and the improvement of a weather resistance can be aimed at. Antireflection film by inorganic _{materials, SiO, SiO 2, SiN 4} , TiO 2, ZrO 2, Al 2 O 3, MgF 2, Ta 2 O 5, Sb 2 O 3, Sb 2 O vacuum evaporation method or the like ₅ A thin film is formed by sputtering, ion beam assist, or the like.

  According to the surface modification method of the present invention, the adhesion of the hard coat film can be increased by an easy treatment in a very short time, and the hard coat solution is not contaminated. In addition, a translucent resin product with no inclusion and less interference fringes can be obtained. In addition, a light-transmitting resin product having good adhesion of the hard coat film and excellent scratch resistance can be obtained.

  Embodiments of the present invention will be described below using examples, but the present invention is not limited to these examples.

  A plastic lens substrate made of urethane resin (trade name MR-7, a lens substrate obtained by thermal polymerization of a monomer manufactured by Mitsui Chemicals Co., Ltd.) was prepared, and a surface reformer manufactured by Ishimat Japan Co., Ltd. was used. The flame by the fuel gas which vaporized and contained the silane compound was sprayed to each side of the lens substrate for 2 to 3 seconds. Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the sprayed lens substrate by a dipping method at 120 ° C. A plastic lens having been hardened by drying and curing for 2 hours was obtained.

  A plastic lens substrate made of urethane resin (trade name PU-170, a lens substrate formed by thermal polymerization of a monomer manufactured by Mitsui Chemicals Co., Ltd.) is prepared, and a surface modification device manufactured by Ishimat Japan Co., Ltd. is used. The flame by the fuel gas which vaporized and contained the silane compound was sprayed to each side of the lens substrate for 2 to 3 seconds. Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the sprayed lens substrate by a dipping method at 120 ° C. A plastic lens having been hardened by drying and curing for 2 hours was obtained.

  A plastic lens substrate made of episulfide resin (trade name MR-174, a lens substrate obtained by thermal polymerization of a monomer manufactured by Mitsui Chemicals Co., Ltd.) was prepared, and a surface modification device manufactured by Ishimat Japan Co., Ltd. was used. The flame by the fuel gas which vaporized and contained the silane compound was sprayed to each side of the lens substrate for 2 to 3 seconds. Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the sprayed lens substrate by a dipping method at 120 ° C. A plastic lens having been hardened by drying and curing for 2 hours was obtained.

  Fuel gas containing a plastic lens substrate made of polycarbonate resin (trade name Panlite, manufactured by Teijin Chemicals Ltd.) and vaporized and containing a silane compound using a surface reformer manufactured by Ishimat Japan Co., Ltd. The flame by was applied to both surfaces of the lens substrate and sprayed on each side for 2-3 seconds. Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the sprayed lens base material by an immersion method at 125 ° C. A plastic lens having been hardened by drying and curing for 2 hours was obtained.

A fuel gas containing a plastic transparent plate substrate made of polycarbonate resin (trade name: Polycaace, manufactured by Chuchu Plastic Co., Ltd.) and vaporized silane compound using a surface reformer manufactured by Ishimat Japan Co., Ltd. The flame by was sprayed on each side of the transparent base material for 2-3 seconds. Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the spray-treated transparent plate substrate by a dipping method, and a temperature of 125 ° C. And dried for 2 hours to obtain a plastic transparent plate with a hard coat.
[Comparative Example 1]

A plastic lens substrate made of urethane resin (product name MR-7, a lens formed by thermal polymerization of a monomer manufactured by Mitsui Chemicals, Inc.) is produced, and the lens substrate is immersed in potassium hydroxide, which is a strong alkali, for about 3 minutes. And washed with water and dried. Thereafter, a hard coat liquid composition mainly comprising a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol as a main component was applied to an alkali-treated lens substrate by an immersion method at 120 ° C. A plastic lens having been hardened by drying and curing for 2 hours was obtained.
[Comparative Example 2]

A plastic lens substrate made of urethane resin (trade name MR-7, a lens obtained by thermal polymerization of a monomer manufactured by Mitsui Chemicals Co., Ltd.) is manufactured, and a plasma processing apparatus PCR1008-SR type (manufactured by Daido Steel Co., Ltd.) A lens base material was installed in the chamber (having electrodes in the chamber), RF output was 100 W, oxygen gas was flowed at a flow rate of 20 cc / min, and the treatment was performed for 5 minutes in an atmosphere having a degree of vacuum of 2.3 to 2.5 mmbar. . Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the plasma-treated lens base material by an immersion method at 120 ° C. A plastic lens having been hardened by drying and curing for 2 hours was obtained.
[Comparative Example 3]

A plastic lens substrate made of urethane resin (product name MR-7, a lens formed by thermal polymerization of a monomer manufactured by Mitsui Chemicals Co., Ltd.) is prepared, and the corona discharge device PS-801C manufactured by Kasuga Electric Co., Ltd. is used. The electrode was installed at a distance of 35 mm, and was treated for 2 minutes on both surfaces of the lens substrate with a discharge voltage of 12 KV. Thereafter, a hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol was applied to the lens substrate subjected to corona treatment by a dipping method. And dried and cured for 2 hours to obtain a hard coated plastic lens.
[Comparative Example 4]

  Primer liquid composition comprising a plastic lens substrate made of urethane resin (trade name MR-7, a lens formed by thermal polymerization of a monomer manufactured by Mitsui Chemicals Co., Ltd.) and containing a polyisocyanate, a polyol and a composite metal oxide sol Was applied to the lens substrate by a dipping method. The applied plastic lens was heat-cured at 90 ° C. for 35 minutes to form a primer layer. A hard coat liquid composition mainly composed of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and a composite metal oxide sol is applied to the plastic lens on which the primer layer is formed by a dipping method. The plastic lens which hardened by time drying and gave the hard coat was obtained.

In order to evaluate the performance of the translucent resin products obtained in each Example and each Comparative Example, the following evaluation tests were performed.
(1) An adhesion cross hatch test was performed. Use a cutter to form 100 1 mm grids on a resin product, and then strongly press cellophane adhesive tape (trade name Cello Tape, manufactured by Nichiban Co., Ltd.) on it, then peel it off in a 90-degree direction and peel it off. The number m of grids remaining without counting was counted. The result was expressed as “m / 100”. “100/100” indicates that the film was not peeled off at all.
(2) A scratch-resistant steel wool test was conducted. The resin product was rubbed with # 0000 steel wool and the degree of damage was evaluated.
A ... No scratches can be confirmed.
B: Some scratches can be confirmed.
C: A conspicuous scratch can be confirmed.
D: Many conspicuous scratches can be confirmed.
E: Scratches can be confirmed in a band shape.

The results of the above test are shown in Table 1. Table 1 also shows whether or not interference fringes are generated due to the process for providing adhesion in each of the examples and comparative examples. When an interference fringe is generated due to each process, it is indicated as “present”, and when it does not occur, “not present” is indicated.

  In the Example of this invention, it became a translucent resin product with good adhesiveness without minding the influence on an interference fringe. In the present invention, it can be seen that interference fringes can be eliminated or reduced by adjusting the refractive index of the hard coat film to or close to the refractive index of the translucent resin substrate. The present invention can be preferably used for translucent resin products typified by automobile parts such as headlights, tail lamps, winkers, and resin windows, in addition to optical products such as plastic lenses.

Claims (5)

After the surface of the translucent resin base material is completely or partially sprayed with a flame of a fuel gas containing an organosilicon compound modifier to form a silicon oxide modified film on the translucent resin base material A method for producing a translucent resin product, comprising forming a hard coat film on the silicon oxide film. The manufacturing method according to claim 1, wherein the hard coat film is formed by a silicone resin hard coat liquid containing a metal oxide sol. The manufacturing method according to claim 1, wherein the translucent resin base material is a plastic lens base material. The manufacturing method according to claim 1, wherein the silicon oxide modified film is formed to have a thickness of 1 to 60 nm. The translucent resin product which has a hard-coat coating film manufactured by the manufacturing method of any one of Claims 1-4.