JPH0436554B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to the surface hardness, scratch resistance, antireflection, etc. of a molded product made of a polymer of a compound having three or more allyl carbonate groups in one molecule, coated with an antireflection agent. Concerning synthetic resin molded products with excellent properties. [Conventional technology and its problems] In general, synthetic resins are lightweight, easy to process, and have good impact resistance, so they are used in a wide range of fields, and colorless and transparent synthetic resins are used in lenses such as eyeglass lenses, various windows, and cover glasses. , etc., are often used. However, such synthetic resins have the disadvantage of poor surface hardness, especially poor scratch resistance, compared to glass, and even if they have good transparency, they still reflect a few percent of light; It has various drawbacks due to Conventionally, in order to solve these drawbacks, a method has been used to form a coating of inorganic hard materials such as metal oxides and fluorides on the surface of synthetic resin substrates by vacuum deposition. For this purpose, it is common to form a single layer or multiple layers of inorganic compounds having different refractive indexes to an optical thickness. However, although the anti-reflection effect can be sufficiently satisfied with the coating of such an inorganic hardened substance, the resulting synthetic resin molded product has poor surface hardness and scratch resistance, and its transparency may deteriorate due to devitrification and scratches. There was a problem that could easily be damaged. [Means for Solving the Problems] Therefore, in view of the above, the present inventors have determined the surface hardness,
As a result of developing synthetic resin molded products with excellent scratch resistance, antireflection, and transparency, we have applied an antireflection agent to the surface of molded products made from polymers of compounds that have three or more allyl carbonate groups in one molecule. By forming a film, it is possible to obtain a molded product with particularly superior surface hardness and scratch resistance compared to molded products formed with a conventional anti-reflective coating, thereby achieving the intended purpose. This discovery led to the completion of the present invention. That is, the present invention is a transparent synthetic resin molded product in which the surface of a molded product made of a polymer of a compound having three or more allyl carbonate groups in one molecule is coated with an antireflection agent. According to the present invention, a synthetic resin group made of a polymer of the above specified allyl carbonate compound having three or more allyl carbonate groups in one molecule (hereinafter also simply referred to as an allyl carbonate polymer) having good scratch resistance. By coating the surface of the material with an antireflection agent, a transparent synthetic resin molded product with excellent surface hardness, scratch resistance, and antireflection can be obtained. That is, the transparent synthetic resin molded product of the present invention uses a carbonate polymer synthetic resin with excellent scratch resistance as a base material, but the scratch resistance of the synthetic resin base material is improved by the synthetic resin molded product coated with an antireflection coating. It also appears on the surface of
Because it exhibits extremely high scratch resistance, transparency is not impaired by scratches. In the present invention, the carbonate compound that is the raw material for the synthetic resin base material has three or more carbonate compounds in one molecule.

There are no particular restrictions as long as it has an allyl carbonate group represented by the formula. Specifically, the following compounds may be mentioned. (1) General formula [However, R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
It is a halogen atom, nitro group or alkoxy group, and R′ is (-CH ₂ ) _-n or (-OCHR″CHR) _-l
(However, R'' and R are the same or different hydrogen atoms or alkyl groups, m is an integer of 0 or more, and l is an integer of 1 or more.), and n is 3 or 4.] Here, there is no limit to the number of carbon atoms in the alkyl group and alkoxy group, but if the surface hardness of the resin obtained by polymerization is taken into consideration, the number of carbon atoms is The range is preferably from 1 to 10.Also, examples of the aryl group include phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, benzyl group, etc.These alkyl groups and aryl groups As substituents, halogen atoms,
Examples include hydroxyl group, alkoxy group, and epoxy group. Further, in the general formula [], m may be an integer of 0 or more, but from the viewpoint of the hardness of the resulting resin, m is preferably an integer of 0 to 30. Also, l may be an integer greater than or equal to 1, but
It is preferably an integer from 1 to 20. (2) General formula [However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a halogen atom, a hydroxyl group or an allyl carbonate group, and three or more of these are allyl carbonate groups, and k is It is an integer greater than or equal to 1. ] An allyl carbonate compound represented by In the above general formula [], the halogen atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include fluorine,
Chlorine, bromine, and iodine atoms are employed. Further, k may be an integer of 1 or more, but in order to easily handle the viscosity of the allyl carbonate compound represented by the above general formula [] at an appropriate value, k is an integer of 1 to 3. It is preferable. (3) General formula [] [However, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are
Each is a hydrogen atom or an allyl carbonate methyl group, and three or more of these are allyl carbonate methyl groups, and l is an integer of 2 to 4. ] An allyl carbonate compound represented by (4) Allyl carbonate compounds in which three or more hydroxyl groups of carbohydrates are substituted with allyl carbonate groups. The above carbohydrates include glycerin, glucose, fructose, mannose, galactose, glucopyranose, xylopyranose, arabinose, fructopyranose, xylulose,
These include xylulose 5-phosphate, sorbitol, maltose, cellobiose, isomaltose, lactose, sucrose, amylose, and the like. As the allyl carbonate compound used in the present invention, from the viewpoint of the transparency and scratch resistance of the polymer, allyl carbonate compounds represented by the above general formulas [] and [] are suitable, and especially the allyl carbonate compounds shown by the above general formula [] The allyl carbonate compound represented by is the most preferred. Specific examples of such allyl carbonate compounds suitably used in the present invention include, for example:

【formula】

etc. can be mentioned. Further, in the present invention, a copolymerizable compound can be added together with the allyl carbonate compound as described above to the extent that the scratch resistance as a synthetic resin base material is not impaired. Examples of such copolymerizable compounds include ethylene glycol bisallyl carbonate (EG-BAC) and diethylene glycol bisallyl carbonate (DEG-BAC) to improve the impact resistance of synthetic resin base materials.
BAC), the molecular weight of polyethylene glycol is 200,
300, 400, 600 polyethylene glycol bisallyl carbonate (PEG-200-
BAC, PEG-300-BAC, PEG-400-BAC,
(abbreviated as PEG-600-BAC), etc. Also, to improve the refractive index of the synthetic resin base material, styrene, divinylbenzene, chloromethylstyrene, diallyl terephthalate, benzyl methacrylate, bisphenol A dimethacrylate, etc.
A copolymerizable compound of 1.5 or more is used. A polymer of the above-mentioned compound or a copolymer of the compound and another compound to be used as the synthetic resin base material of the present invention can be produced by a known radical polymerization method in the presence of a radical polymerization initiator or under irradiation with ultraviolet rays or radiation. can be obtained by using without any particular restriction. Further, during polymerization, various stabilizers and additives such as a mold release agent, ultraviolet absorber, antioxidant, anti-coloring agent, antistatic agent, and fluorescent dye can be selected and used as necessary. Furthermore, in the present invention, a known curable substance can be coated to improve the scratch resistance of the synthetic resin base material. At that time, the type of curable substance,
The coating method is not particularly limited and may be selected and used as required. 3 allyl carbonate groups in one molecule of the present invention
As a method for forming a coating of an inorganic hard substance, which is an antireflection agent, on the surface of a molded article made of a polymer of a compound having 1 or more compounds, any known method can be used without particular limitation. For example, dry plating methods such as vacuum evaporation method, ion plating method, and sputtering method are common. The thickness of the inorganic hard material coating is
Although it is not particularly limited as it varies depending on the purpose, it generally ranges from 0.1μ to 10μ. The inorganic hard material forming the coating of the present invention includes:
In general, any inorganic substance that can be deposited on the surface of a synthetic resin base material by the dry plating method described above can be used without any restriction, and it may be selected as appropriate depending on the purpose. For example, silicon oxide (SiOx, x=1-2), aluminum oxide, etc. are generally used to impart scratch resistance. Further, in order to impart antireflection properties, a single layer of a low refractive index material or a layer of a low refractive index material and a high refractive index material may be alternately laminated to an optical thickness. Examples of the inorganic hard substances constituting the specific antireflection film used in the present invention include silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, cerium oxide, iredium oxide, tantalum oxide, and tantalum oxide. Metal oxides such as hafnium; magnesium fluoride, cerium fluoride, lithium fluoride, lanthanum fluoride,
Examples include metal fluorides such as sodium fluoride and neodymium fluoride. In addition, aluminum
Good films can also be formed using metals such as gold, silver, and chromium, and inorganic compounds other than those mentioned above, such as zinc sulfide. Furthermore, since scratch resistance is imparted at the same time, antireflection can be achieved even if amorphous carbon is coated with a diamond-like carbon film in which diamond microcrystals are interspersed. [Effects of the Invention] As described above, according to the present invention, a molded article of a base material having excellent scratch resistance made of a polymer of a compound having three or more allyl carbonate groups in one molecule is made of a durable inorganic material. It is possible to provide a synthetic resin molded product coated with a hard material film, which has excellent scratch resistance and improved antireflection. [Example] In order to specifically explain the present invention, Examples and Comparative Examples are shown below, but the present invention is not limited to these Examples. In addition, the surface characteristics of a synthetic resin molded product made of a polymer of a compound having three or more allyl carbonate groups in one molecule and coated with an antireflection agent were evaluated using the following method. . (1) Scratch resistance Attach #0000 steel wool to a scratch resistance tester manufactured by Fukuda Machinery Co., Ltd., and after moving the sample surface back and forth 10 times under a 1 kg load, visually observe the degree of scratches on the surface. , A is the completely undamaged state, and E is the very brittle state of the diethylene glycol bisallyl carbonate resin fabric.
The grades A to E were divided into B, C, and D and evaluated in five stages. (2) Visible light transmittance The wavelength of a 2 mm thick test piece was measured using a spectrophotometer.
The transmittance was measured from 400 to 700 nm. (3) Adhesion test Use a cutter knife with a sharp tip to test the surface of the sample.
After attaching 100 squares of mm x 1 mm, commercially available cellophane tape was applied and then quickly peeled off, and the state of peeling of the film was visually observed. Evaluation was based on the number of squares. (4) Weather resistance test The changes in the film after 500 hours of irradiation were evaluated using a xenon lamp fade meter manufactured by Suga Test Instruments Co., Ltd. Those with no change were marked with ○, and those with cracks were marked with ×. did. The antireflective agents used in Examples and Comparative Examples and their coating methods are shown below. () 10 ^-6 on the surface of the specified molded product using a vacuum evaporation device (EBS-10A manufactured by Japan Vacuum Technology Co., Ltd.)
Al ₂ O ₃ was vacuum-deposited as a first layer to a thickness of 280 nm using Thor, and MgF ₂ was vacuum-deposited as a second layer to a thickness of 140 nm. () An antireflection layer made of SiO ₂ ZrO ₂ with a thickness of 300 nm was applied to the surface of a predetermined molded product using a vacuum evaporation device. () The surface of the specified molded product is coated with 1 μm of silicon using an ion plating device using an electric shock type ion source under the conditions of vacuum attainment of 4.5 × 10 ^-6 Torr, ionization rate of 3%, and electrode gap voltage of 8 kV, and then cleaned. Thereafter, tungsten was coated to a thickness of 0.5 μm under the same conditions. () Hydrolyze a mixture of γ-glycidoxymethylethoxysilane and phenyltrimethoxysilane to form an epoxy resin (“Epicron 750” product of Dainippon Ink Chemical Co., Ltd.), benzyl alcohol, diacet alcohol, and a silicone-based interface. Added activator. Further, methanol-dispersed colloidal silica ("Methanol Silica Sol" manufactured by Nissan Chemical Co., Ltd.), aluminum acetylacetonate, and methanol were added in this order. These were sufficiently stirred and mixed to form a paint, which was applied to the surface of a predetermined molded product by a dipping method. After heating the coated molded product for 4 hours in a hot air dryer at 90℃,
Type low temperature ashing equipment Output 50W Oxygen flow rate 50c.c./
The treatment was carried out for 210 seconds. Example 1 As a molded product made of a polymer of a compound having three or more allyl carbonate groups in one molecule, diisopropyl peroxydicarbonate (hereinafter abbreviated as IPP) was added to trimethylolpropane triallyl carbonate as a radical polymerization initiator. )of
A plate-shaped body with excellent abrasion resistance manufactured by ordinary cast polymerization with the addition of 2.2 parts by weight was used. First, the plate-shaped body was washed with acetone and thoroughly air-dried to a clear state, and then subjected to the treatment method (), (), (), () using an inorganic hard material to form an antireflection coating. Table 1 shows the evaluation results of the coated synthetic resin molded products.

[Table] Example 2 As a molded product made of a polymer of a compound having three or more allyl carbonate groups in one molecule, trimethylolpropane-triallyl carbonate and various polyalkylene glycol bisallyl carbonates shown in Table 2, and A plate-shaped body was produced by cast polymerization by adding 2.2 parts by weight of IPP to each mixture of copolymerizable compounds with a refractive index of 1.5 or more shown in Table 3, and thoroughly washed with acetone. After thorough air drying and clarification, an antireflection coating was formed which was subjected to a treatment method (2) using an inorganic hard material. For all synthetic resin molded products, the scratch resistance is B, the visible light transmittance is 96.5%, and the adhesion is all
100, and weather resistance was also all ○.

【table】

[Table] Example 3 A plate-shaped plate produced by ordinary cast polymerization by adding 2.2 parts by weight of IPP to various compounds having three or more allyl carbonate groups in one molecule shown in Table 4 as a synthetic resin base material. I used my body. First, the plate-shaped body was washed with acetone and thoroughly air-dried to a clear state, and then subjected to a treatment method (2) using an inorganic hard material to form an antireflection coating. Table 4 shows the evaluation results of the coated synthetic resin molded products.

[Table] Example 4 The synthetic resin plate of Example 1 made of a polymer of trimethylolpropane triallyl carbonate, which has excellent scratch resistance, was washed with acetone and thoroughly air-dried to a clear state. To coat the material, it was first immersed in a 10% NaOH aqueous solution for 10 minutes as a pretreatment, then washed with water and dried. Then, 20 parts by weight of bis(γ-trimethoxysilylpropyl) carbonate, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane, 30 parts by weight of colloidal silica (methanol sol manufactured by Nissan Chemical Co., Ltd.),
A prescribed molded product was dipped and coated in a curable substance consisting of 30 parts by weight of meticello, 10 parts by weight of 0.05N hydrochloric acid, and 0.25 parts by weight of ammonium perchlorate as a curing catalyst, and after thoroughly air-dried at room temperature, It was cured by heating at ℃ for 1 hour. Furthermore, this molded article was subjected to the inorganic hard material treatment method () to form an antireflection coating. The results are shown in Table-5.

【table】

Claims (1)

[Claims] 1. A transparent synthetic resin molded product made of a polymer of a compound having 3 or more allyl carbonate groups, and the surface of which is coated with an antireflection agent.