JPH0451802B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Fields] The present invention has excellent scratch resistance, abrasion resistance, impact resistance, chemical resistance, flexibility, heat resistance, hot water resistance, light resistance, weather resistance, dyeability, etc. The present invention relates to a transparent molded body suitable for optical applications such as lenses for cameras and lenses for cameras, and a method for manufacturing the same. [Prior art] Transparent molded bodies, especially plastic molded bodies represented by plastic lenses, have been in great demand in recent years because they have extremely excellent impact resistance and transparency, are lightweight, and can be easily dyed. is increasing. However, plastic lenses have a disadvantage in that their surface hardness is lower than that of inorganic glass and they are easily scratched. Many attempts have already been made to improve this drawback. Japanese Patent Publication No. 57-2735 and Japanese Patent Publication No. 52-39691 disclose coating compositions containing fine silica particles on the surface of a plastic substrate. [Problems to be Solved by the Invention] The technology disclosed in Japanese Patent Publication No. 57-2735 has the characteristics of having high surface hardness and further being dyeable. However, increasing the amount of silica added has the disadvantage that cracks occur in the film or cracks in the base material after heat curing in negative altitude number lenses. On the other hand, the technique disclosed in Japanese Patent Publication No. 52-39691 has the drawbacks that although the film has a fairly high hardness, it cannot be dyed, has poor flexibility, and has low heat resistance and hot water resistance. [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention described below. That is, the first aspect of the present invention has the following configuration. The present invention relates to a transparent molded article characterized in that a coating made of the following components A and B is provided on the surface of a transparent base material. A: Fine silica particles that are at least partially agglomerated and have an average particle diameter of 5 to 300 mμ. B Organic substance-containing polymer Furthermore, the second invention provides the above-mentioned A polymer on the surface of the transparent base material.
The present invention relates to a method for producing a transparent molded body, which comprises applying a liquid coating composition containing component B and forming a cured film by heating. In the present invention, the transparent substrate includes inorganic glass,
Various plastics, such as acrylic resins, polycarbonates, diethylene glycol bisallyl carbonate polymers, screw (meth)acrylate polymers of (halogenated) bisphenol A and copolymers thereof, urethane-modified (meth)acrylate polymers of (halogenated) bisphenol A , and copolymers thereof are preferably used. Furthermore, a base material having dyeability is particularly preferably used. In the present invention, component A, silica fine particles at least partially aggregated and having an average particle diameter of 5 to 300 mμ, is a colloidal dispersion of high molecular weight silicic anhydride in an organic solvent such as water and/or alcohol. Supplied. Such colloidal dispersions of silica are available in various
Although it can be supplied as a substance that can exist stably at any pH, an acidic one is preferable from the viewpoint of paint stability, coating hardness, etc., and those having a pH value of 3 to 6.9 are particularly preferably used. In addition, as for the average particle diameter of the silica fine particles, 5 to 300 mμ can be used, but from the viewpoint of sol stability, coating film transparency, cracking of the film due to heat curing, or cracking of the base material, etc. A material having a diameter of 100 mμ is preferably used. Furthermore, in the present invention, the silica fine particles in which at least a portion of the particles are aggregated are those in which several spherical silica fine particles are aggregated to form one fine particle. Here, the spherical silica fine particles are produced by a known method and are not particularly limited. In addition, the proportion of aggregated silica particles in the total silica particles should be determined depending on the coating thickness, intended performance, applied substrate, etc., but in the case of negative altitude number lenses such as corrective lenses, From the viewpoint of edge cracking, it is used in an amount of 10% by weight or more, preferably 20% by weight or more. In addition, it is possible to produce partially aggregated silica fine particles by aging, concentrating, and adjusting the pH of spherical silica.
Furthermore, it is fully possible to agglomerate the spherical silica at the same time as the preparation, and the method for producing the same is not particularly limited in the present invention. These silica sol are preferably contained in the coating in an amount of 40 to 75% by weight, but from the viewpoint of flexibility, dyeability, hot water resistance, heat resistance, etc. of the coating, 50 to 65% by weight is more preferably used. be done. That is, if the amount is less than 40% by weight, the hardness after dyeing and hot water treatment will decrease significantly, making it difficult to obtain a product with high surface hardness. 75 again
If the amount exceeds % by weight, there will be problems such as whitening of the coating film, cracking of the coating film due to heat curing, cracking of the substrate, poor adhesion to the substrate, and decreased dyeability. The organic substance-containing polymer serving as component B in the present invention may be any polymer as long as it does not impair the transparency of the film. Examples of usable polymers include polyvinyl butyral, polyvinyl alcohol, celluloses, melamine resins, epoxy resins, polysiloxane resins, acrylic resins, and the like. Among them, thermosetting resins are preferably used from the viewpoint of surface hardness, heat resistance, hot water resistance, chemical resistance, etc., and polysiloxane resins are particularly preferably used from the viewpoint of improving surface hardness. Typical examples of compositions for forming organopolysiloxanes include organosilicon compounds represented by the following general formula () and/or hydrolyzates thereof. RR ¹ _a SiX _3-a () (where, R is an organic group having 1 to 10 carbon atoms, R ¹ is a hydrocarbon group or halogenated hydrocarbon group having 1 to 6 carbon atoms, and X is a hydrolyzable group. (a is 0 or 1.) Specific representative examples of these organosilicon compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, and methyltripropoxysilane. , methyltributoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,
Vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3 , 3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane Methoxyethoxysilane, γ-mercaptopropyltriethoxysilane, N-β-(aminoethyl)-γ
-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane,
Chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane Silane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxy Ethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyl Triethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxy cyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-
(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,
4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4
-Epoxycyclohexyl)ethyltrimethoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-
(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-
Trialkoxysilanes such as (3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, triacyloxysilanes, or triphenoxysilanes or their hydrolysates, and dimethyldimethoxysilane Silane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane , γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, Methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethyl Methyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycid Xypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ
-Glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropyl Ethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-
glycidoxypropylvinyldiethoxysilane,
Examples include dialkoxysilanes such as γ-glycidoxypropylphenyldimethoxysilane and γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilanes, diacyloxysilanes, and hydrolysates thereof. It is also possible to add one type or two or more types of these organosilicon compounds. Particularly for the purpose of imparting dyeability, it is suitable to use organosilicon compounds containing epoxy groups and glycidoxy groups. In addition, from the point of view of curing speed, ease of hydrolysis, etc.,
C1 _{- C4} alkoxy or alkoxyalkoxy is preferably used. These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and further promote curing. Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. During hydrolysis, it is particularly preferable to add pure water or acidic aqueous solution in an amount equal to or more than 3 times the mole of the X group in the general formula (), from the viewpoint of accelerating curing. During hydrolysis, alcohol and other substances are produced, so it is possible to hydrolyze without a solvent, but in order to make the hydrolysis more uniform, hydrolysis is performed after mixing the organosilicon compound and a solvent. It is also possible. Depending on the purpose, it is also possible to remove an appropriate amount of alcohol etc. after hydrolysis by heating and/or under reduced pressure.
It is also possible to add a suitable solvent afterwards. These solvents include alcohols, esters,
Examples include solvents such as ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene. Moreover, these solvents can also be used as a mixed solvent of two or more types as required. Furthermore, depending on the purpose, it is possible to accelerate the hydrolysis reaction and further advance reactions such as precondensation by heating above room temperature, or to suppress precondensation, the hydrolysis temperature can be lowered to below room temperature. Needless to say, it is possible to do so. The present invention is made by applying a coating composition consisting of silica fine particles, at least a part of which is aggregated, and an organic substance-containing polymer to the surface of a transparent substrate, and heating and curing the coating composition. It is possible to perform various pretreatments on the base material for the purpose of improving properties, water resistance, etc. Particularly effective means for the present invention include activated gas treatment and chemical treatment. When curing the coating composition of the present invention, various curing agents can be used in combination for the purpose of accelerating curing and enabling low-temperature curing. As the curing agent, various epoxy resin curing agents or various organosilicon resin curing agents are used. Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds or metal alkoxides, and organic carboxylates of alkali metals.
Examples include various salts such as carbonates. It is also possible to use a mixture of two or more of these curing agents. Among these curing agents, the aluminum chelate compounds shown below are particularly useful for the purpose of the present invention from the viewpoint of paint stability, coloring of the film after coating, etc. The aluminum chelate compound mentioned here is
For example, it is an aluminum chelate compound represented by the general formula AIY _o Z _3-o . However, in the formula, Y is OL (L is a lower alkyl group),
Z is a ligand derived from a compound represented by the general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are both lower alkyl groups) and a ligand derived from the general formula M ³ COCH ₂ COOM ⁴ (M ³ and M ⁴ are both lower alkyl groups). is at least one ligand derived from a compound represented by a lower alkyl group), and n is 0, 1 or 2. As the aluminum chelate compound represented by the general formula AIY _o Z _3-o , which is particularly useful as a curing agent in the present invention, various compounds can be mentioned. Particularly preferred from the viewpoint of be. It is also possible to use a mixture of two or more of these. As a method for applying the coating composition to be applied to the transparent substrate of the present invention, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, spin coating, and flow coating can be easily used. be. The coating of the present invention is obtained by coating and curing using the coating means described above, and curing is mainly performed by heat treatment. It should be noted that the heating temperature can be used over a much wider range than in the case of conventional coating compositions, and sufficiently good results are obtained between 50 and 250°C. The thickness of the coating in the present invention is not particularly limited. However, from the viewpoint of maintaining adhesive strength and hardness, it is preferably used in a range of 0.1 to 20 microns. More preferably, it is 0.4 to 10 microns. In addition, when applying the film, it is diluted with various solvents for workability, film thickness adjustment, etc. Dilution solvents include water, alcohol,
Examples include esters, ethers, halogenated hydrocarbons, and the like. A preferred embodiment of the present invention is particularly excellent in surface hardness and dyeability, and is therefore useful for optical lenses such as lenses for sunglasses and lenses for prescription glasses. It is particularly useful for negative altitude number lenses such as optical lenses such as CR-39. EXAMPLES In order to clarify the characteristics of the present invention, Examples are given below, but the present invention is not limited to these Examples. Note that the number of parts in the formula is based on weight. Example 1 (1) Preparation of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane cohydrolyzate γ-glycidoxypropyltrimethoxysilane was prepared in a reactor equipped with a rotor. 42.2 parts of γ-glycidoxypropylmethyldiethoxysilane and 99.7 parts of γ-glycidoxypropylmethyldiethoxysilane were added, and while stirring using a magnetic stirrer, 24.2 parts of a 0.05N hydrochloric acid aqueous solution was heated to 10°C.
After the dropwise addition was completed, stirring was continued for an additional 30 minutes to obtain a hydrolyzate. (2) Preparation of coating composition 199.6 parts of isopropyl alcohol, 11.9 parts of acetylacetone, and 1.6 parts of silicone surfactant were added and mixed to the cohydrolyzate of (1) above, and further, 40% by weight of the silica was agglomerated silica sol ( Average particle size 1
383.3 parts of isopropyl alcohol-dispersed silica sol (~15 mμ) and 6.45 parts of aluminum acetylacetonate were added, and after thorough stirring, a coating composition was obtained. (3) Preparation of coated product Using a CR-39 (diethylene glycol bisallyl carbonate polymer) -6.00 diopter lens as a transparent base material, the coating composition prepared in (2) above was pulled up at a rate of 10 cm/min. The coating was applied by dip coating, then precured at 82°C for 12 minutes, and further heated at 100°C for 4 hours to obtain a coated product. (4) Dyeing of the coated product A disperse dye bath consisting of three colors of red, blue, and yellow was prepared for the coated product of (3) above, and the dye bath was kept at 93° C. and dyed for 10 minutes. (5) Performance evaluation The performance of the obtained transparent molded body was tested according to the following method. The results are shown in Table 1. (a) Steel wool with a hardness of #0000 is rubbed against the painted surface 50 times under a load of 1.5 kg to determine the degree of damage. ○...There are almost no scratches and the rubbed surface does not turn white. △...The rubbed surface has fine scratches and turns white. ×...The surface of the rubbed surface is turned over. (B) Adhesion: Insert 100 goblets reaching the base material at 1 mm intervals on the coating surface using a steel knife, and firmly adhere cellophane adhesive tape (trade name: "Cello Tape" manufactured by Nichiban Co., Ltd.) at 90 degrees. The film was peeled off rapidly in the direction of the paint to check for peeling. Good ones were marked as ○. (c) Appearance The obtained transparent molded product was visually inspected for cracks at the edges. (d) Stainability The dyed lens obtained in (4) above was rotated under a fluorescent lamp to examine the uniformity of the dyeing. ○...Uniformly dyed. ×... Not uniformly dyed. Comparative Example 1 The same procedure as in Example 1 was carried out except that the silica fine particles were changed to non-agglomerated silica sol (average particle size 10 to 15 mμ). The test results are shown in Table 1.

[Table] [Effects of the Invention] The transparent molded article obtained by the present invention has the following effects. A highly hard coating film that can withstand repeated abrasion from steel wool, etc. can be obtained. Excellent dyeing properties. Excellent heat resistance and hot water resistance. Excellent flexibility. It can be applied to negative altitude number lenses in corrective lenses, and high-quality lenses can be obtained without cracking at the edges.

Claims (1)

[Scope of Claims] 1. A transparent molded article, characterized in that a coating consisting of the following components A and B is provided on the surface of a transparent base material. A: Silica fine particles at least partially agglomerated and having an average particle diameter of 5 to 300 mμ B: Organic matter-containing polymer 2: The silica fine particles are present in an amount of 40 to 75% by weight. Transparent molded body. 3. The transparent molded article according to claim 1, wherein the organic substance-containing polymer is a thermosetting resin. 4. The transparent molded article according to claim 3, wherein the thermosetting resin is a polymer obtained from an organosilicon compound represented by the following general formula () and/or a hydrolyzate thereof. _RR ¹ _a ^S _i (a is 0 or 1) 5 The transparent molded article according to claim 4, wherein the organic group represented by R is an organosilicon compound having an epoxy group or a glycidoxy group. . 6. A method for producing a transparent molded article, which comprises applying a liquid coating composition containing the following components A and B to the surface of a transparent substrate, and further forming a cured film by heating. A: Fine silica particles that are at least partially agglomerated and have an average particle diameter of 5 to 300 mμ. B Organic substance-containing polymer 7 The method for producing a transparent molded body according to claim 6, wherein the organic substance-containing polymer is an organosilicon compound represented by the following general formula () and/or a hydrolyzate thereof. _RR ¹ _a ^S _i (a is 0 or 1.) 8 The transparent molded article according to claim 7, wherein the organic group represented by R is an organosilicon compound having an epoxy group or a glycidoxy group. manufacturing method.