JPH0153972B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a method for producing an allyl carbonate high refractive index resin molded product, which forms a thermosetting film with good adhesion on the surface of the allyl carbonate high refractive index resin molded product, which has excellent impact resistance, moldability, transparency, etc. It is related to. Conventionally, synthetic resins with excellent transparency have been used as organic glass for optical lenses, eyeglass lenses, prisms, glass plates, etc., taking advantage of their characteristics such as high impact resistance, light weight, good moldability, and dyeability compared to inorganic glass. It is widely used as. Recently, in order to further enhance the characteristics of this organic glass, efforts have been made to develop transparent synthetic resins with a higher refractive index than that of conventional synthetic resins, such as polyallyl diglycol carbonate (1.50). ing. The present applicant has already developed an allyl carbonate-based synthetic resin made by copolymerizing bis(oxyalkylene phenyl) diallyl carbonate and a specific polyoxyalkylene polyol polyallyl carbonate as a high refractive index resin with particularly excellent impact resistance. provided. However, similar to conventional transparent synthetic resins, such allyl carbonate-based high refractive index synthetic resins also lack solvent resistance, surface hardness, and scratch resistance, and are attacked by organic solvents, resulting in devitrification of the resin surface. The disadvantage is that transparency is easily impaired by scratches and scratches. Therefore, in order to compensate for the above-mentioned drawbacks of allyl carbonate-based high refractive index resins, the present invention aims to produce good allyl carbonate-based high refractive index resins by forming a hard coating on the surface of the resins with good adhesion, similar to conventional synthetic resins. The purpose is to obtain a refractive index resin molded product. Many proposals have been made for such hard coatings, among which silicon-based,
Melamine-based, epoxy-based, acrylic-based materials have excellent hardness and durability, and some of them are already in practical use. However, even if these hard coatings are simply formed on the surface of a synthetic resin, the film may peel off due to insufficient adhesion to the synthetic resin, and its performance may not be fully exhibited. As will be described later, the allyl carbonate-based high refractive index resin that is the object of the present invention also has the problem of poor adhesion to hard coatings such as silicone-based coatings, resulting in film peeling. Generally, methods for improving the adhesion of coatings include adding a component that improves adhesion to a hard substance, providing an undercoat layer that can adhere to both the synthetic resin and the hard coating, and There is a method in which the surface of a synthetic resin is treated and activated before being coated with a curable substance. However, the method of adding an adhesion-imparting component to a curable substance may lead to a decrease in the performance of the hard coating, and the method of providing an undercoat layer may cause the film to peel after long-term use or in a high-temperature, humid atmosphere, so it is not sufficient. . In addition, in order to achieve good adhesion with the hard coating without impairing the properties of the synthetic resin, the method of pre-treating the surface of the synthetic resin requires a treatment agent or treatment depending on the type of the synthetic resin. The selection of conditions is extremely important. As a result of intensive research into a method for forming a durable hard coating with excellent adhesion on the surface of molded products made of allyl carbonate high refractive index resin, the present inventor discovered that the moldability of the allyl carbonate high refractive index resin molded product could be improved using an alkaline solution. The inventors have discovered that by pre-treating with the above, the adhesion of the formed hard coating to the substrate is significantly superior, and the present invention has been completed. That is, the present invention comprises at least one monomer selected from bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof, and a polyoxoalkylene polyol polyallyl carbonate in which the molecular weight of the polyoxyalkylene polyol is 150 or more. This is a method for producing a high refractive index resin molded product, which comprises contact-treating the surface of a molded product made of a copolymer of the above with an alkaline solution in advance, and then coating it with a curable substance. The allyl carbonate high refractive index resin targeted by the present invention is a new high refractive index resin with high transparency and particularly excellent impact resistance, and is a bis(oxyalkylene phenyl) diallyl represented by the general formula below. A polyoxyalkylene polyol polyallyl carbonate in which at least one monomer selected from carbonates or derivatives thereof and a polyoxyalkylene polyol have a molecular weight of 150 or more;
Alternatively, it is a polymer obtained by copolymerizing these with other monomers that can be copolymerized with bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof, and is used for optical lenses such as microscopes and cameras. It is a transparent polymer that is typified by organic glasses such as prisms, eyeglass lenses, dustproof glass, and windshield glasses. As bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof, (In the above formula, R ₁ is H, CH ₃ , R ₂ is -CH ₂ CH ₂ O-,

【formula】

[Formula] X is Cl, Br Y is -, -O-, -CO-, -SO ₂ -, -CH ₂ -, -CH=CH-,

[Formula] m and n are integers of 1, 2, 3, or 4, a is an integer of 0, 1, 2, 3, or 4, and l is an integer of 1 or 2), which is particularly typically used. Specific examples of bis-(oxyalkylene phenyl) diallyl carbonate or derivatives thereof include: etc., and mixtures thereof. Further, specific examples of polyoxyalkylene polyol polyallyl carbonate include tetraethylene glycol bisallyl carbonate (hereinafter abbreviated as TEG-BAC), polyethylene glycol whose molecular weight is 200, 300, 400, and 600. Bisallyl carbonate (hereinafter referred to as PEG200BAC, PEG300−BAC, respectively)
(abbreviated as PEG40-BAC, PEG600-BAC), similarly the molecular weight of polypropylene glycol is 200,
400, 950, and 1000 polypropylene glycol bisallyl carbonate (hereinafter, respectively)
PPG200−BAC, PPG400−BCA, PPG950−
BAC, abbreviated as PPG1000-BAC), polyoxypropylated glycerin trisallyl carbonate whose molecular weight is 400 and 600 (hereinafter referred to as GP400-TAC, respectively)
GA600-TAC), polyoxypropylated sorbitol with a molecular weight of 750, polyoxypropylated sorbitol polyallyl carbonate (hereinafter abbreviated as SP750-PAC), polyoxyethylated glycerin with a molecular weight of 400 and 600. A polyoxyethylated glycerin trisallyl carbonate (hereinafter referred to as GE400-TAC, respectively)
(abbreviated as GE600-TAC), polyoxyethylated sorbitol polyallyl carbonate (hereinafter abbreviated as SE600-PAC) in which polyoxyethylated sorbitol has a molecular weight of 600, and polyoxytetramethylene glycol in which molecular weight is 1000. Oxytetramethylene glycol bisallyl carbonate (hereinafter abbreviated as PTMG1000-BAC) and the like. The component amount of polyoxyalkylene polyol polyallyl carbonate ranges from 0.5 to 25% by weight based on bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof. Further, for the above-mentioned high refractive index resin, it is possible to select and use other monomers that can be copolymerized with bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof. Other monomers that can be copolymerized with the bis(oxyalkylene phenyl) diallyl carbonate or their derivatives include monomers that can undergo radical polymerization such as vinyl compounds and allyl compounds, and representative examples that are generally preferably used include For example, allyl compounds such as diethylene glycol bis(allyl carbonate), diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl maleate, allyl cinnamate, styrene, chlorostyrene , aromatic vinyl compounds such as methylstyrene, vinylnaphthalene, isopropenyl phthalene, methyl methacrylate, 2-hydroxyethyl methacrylate, phenyl methacrylate,
Pentabrome methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, bisphenol A bisglycidyl methacrylate, 2,2 bis(4-methacryloxyethoxyphenyl)propane, 2,2 Bis(3,5-diprom-4-methacryloxyethoxyphenyl)
These include acrylic and methacrylic ester compounds such as propane, and mixtures thereof. The amount of other monomers that can be copolymerized with bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof as described above should be determined relative to the main component bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof. and generally ranges from 1 to 90% by weight. In addition, when obtaining a high refractive index resin using a mixed composition of bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof and other copolymerizable monomers, the mixed composition may be Oxyalkylene polyol polyallyl carbonate is generally used in a range of 0.5 to 20% by weight. The allyl carbonate-based high refractive index resin can be obtained by subjecting the above-mentioned mixed composition to a known radical polymerization method in the presence of a radical polymerization initiator or under irradiation with ultraviolet rays or radiation without particular limitation. In the present invention, the effects of the present invention are almost equally recognized regardless of the composition of any allyl carbonate high refractive index resin molded from the above mixed composition. In addition, various stabilizers and additives such as mold release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, and fluorescent dyes can be selected and used as necessary during polymerization. This does not impair the processing effect of the present invention. In the present invention, the allyl carbonate-based high refractive index resin described above can be molded into a desired shape and subjected to pretreatment. In the present invention, amines represented by the general formula RnH _3-o N (where R is a C ₁ to C ₆ hydroxides of alkali metals such _as lithium, sodium, potassium, rubidium, _cesium and a solution consisting of a basic compound such as an alcoholate and ammonia alone or in a mixture of two or more thereof. In particular, alkaline solutions containing strongly basic sodium and potassium hydroxides or alcoholates have a particularly high treatment effect, and can be used to create a durable hard coating with excellent adhesion on the surface of allyl carbonate-based high refractive index resin molded products. It is suitably used for pre-treatment of the molded article for forming. The solvent can be used without any particular restriction as long as it dissolves the above basic compound, but water is usually used from the viewpoint of solubility and workability. In addition, organic solvents such as alcohols such as methyl alcohol and ethyl alcohol and cellosolves such as methyl cellosolve dissolve the above basic compounds and have good compatibility with water, so they can be used as mixed solvents with water. It can also be used as a system. The alkali metal alcoholates may therefore be used in alcoholic solutions or in water-alcohol mixed solvent systems with the addition of water. The concentration of the above basic compound in the alkaline solution is
Although it varies depending on the processing time and processing temperature, generally 1
The range of ~50% by weight is preferable; below this range, not only will the treatment take a long time, but the treatment effect will not be sufficient. Further, at a concentration higher than this, the treatment effect is not particularly improved. The treatment of an allyl carbonate high refractive index resin molded article with an alkaline solution is carried out by bringing the molded article into contact with the alkaline solution. Examples of the treatment method include a dipping method, a spray method, and a flow method, but a dipping method in which the molded product is immersed in an alkaline solution is preferred from the viewpoint of workability. The contact time (processing time) is generally 30 seconds to 1 hour at 5 to 70°C. Molded products made of allyl carbonate high refractive index resin treated with an alkaline solution are coated with a curable substance by thoroughly washing with water or an evaporable organic solvent that dissolves the above basic compounds and drying. The previous surface pretreatment of the molded product is completed. In addition,
Prior to the alkaline solution treatment of the present invention, it is preferable that the surface of the molded article be sufficiently degreased and cleaned in advance in order to effectively promote contact with the alkaline solution. In the present invention, the allyl carbonate-based high refractive index resin molded product is surface-modified by pre-treating the surface with the above-mentioned alkaline solution, then coating it with a curable substance and curing it. As the curable substance used in the present invention, so-called crosslinkable substances that react with heat, catalysts, curing agents, light, radiation, etc. to form a three-dimensional network structure to form a cured film can be used without particular restrictions. . For example, melamine-based curable compositions made of melamines and other reactive substances such as formaldehyde, acrylic curable compositions made of acrylic esters, acrylamides, etc.
Epoxy-based curable compositions made of epoxies and other reactive substances such as bisphenol A, silicon-based curable compositions made of organosilicon compounds such as methyltrimethoxysilane, or curable compositions that are a combination of these. is preferably used. As a method for coating the allyl carbonate high refractive index resin molded article of the present invention with a curable substance, any known method can be used without particular limitation. For example, a dipping method, a flow coating method, a brushing method, a rotation method, etc. are generally employed. Further, the thickness of the coating is not particularly limited, but is generally 0.1μ to 50μ. Further, the curing of the curable substance may be carried out as appropriate depending on the type thereof. In this way, according to the method of the present invention, it is possible to form a scratch-resistant hard coating that has extremely excellent adhesion to allyl carbonate-based high refractive index resin molded products and has good durability. EXAMPLES Below, Examples and Comparative Examples will be shown to specifically explain the present invention, but the present invention is not limited to these Examples. The performance of the film formed on the surface of the allyl carbonate synthetic resin molded product was evaluated by the following method. (1) Adhesion test After making 100 squares of 1 mm x 1 mm on the surface of the sample using a cutter knife with a sharp tip, apply commercially available cellophane tape, then quickly peel it off and visually observe the peeling state of the film. The evaluation was made based on the number of squares that remained without peeling out of 100 squares. (2) Scratch resistance test Attach #0000 steel wool to a scratch resistance tester manufactured by Fukuda Machinery Co., Ltd., and visually observe the degree of scratches on the surface after moving the sample surface back and forth 10 times under a load of 1 kg. The evaluation was made on a five-level scale from A to E, with A indicating a state in which there was no damage at all, and E indicating a state in which the allyl carbonate-based high refractive index resin fabric was extremely easily damaged. (3) Hot water resistance test The adhesion test described above was conducted after being left in boiling water for 2 hours, and evaluated using the same criteria. (4) Weather resistance test The above adhesion test was conducted after 300 hours of exposure using a carbon arc sun shine weather meter.
Evaluated using the same criteria. The curing method using the curable substance or curable composition used in Examples and Comparative Examples is shown below. () 20 parts by weight of methyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane 10
10 parts by weight of tetraethoxysilane, 20 parts by weight of 0.05N hydrochloric acid necessary for hydrolysis, 40 parts by weight of isopropyl alcohol, and 1 part by weight of a mixture of sodium acetate/acetic acid (1/10) as a curing catalyst. A specified molded product is dipped in it to coat it, and after thoroughly air-drying it at room temperature,
It was cured by heating at ℃ for 1 hour. () Bis(γ-triethoxysilylpropyl)
20 parts by weight of carbonate, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane, 30 parts by weight of colloidal silica (methanol sol manufactured by Nissan Chemical Co., Ltd.), 30 parts by weight of meticello, 10 parts by weight of 0.05N hydrochloric acid, perchloric acid as a curing catalyst Ammonium 0.25
A predetermined molded article was immersed and coated in a curable material consisting of parts by weight, thoroughly air-dried at room temperature, and then heated at 130° C. for 1 hour to cure. () Trimethylolpropane triacrylate
50 parts by weight of triethylene glycol diacrylate and 1 part by weight of benzophenone dissolved in 50 parts by weight of isopropyl alcohol.
After sufficiently drying with nitrogen air at room temperature, it was cured under ultraviolet irradiation. () 25 parts by weight of hexamethoxymethyl melamine and 25 parts by weight of 2-hydroxyethyl methacrylate were mixed and dissolved in 50 parts by weight of methyl cellosolve, and 0.2 parts by weight of ammonium thiocyanate was added to the mixture. After soaking and coating the product and thoroughly air-drying it at room temperature,
It was heat cured at ℃ for 1 hour. Example 1 85 parts by weight of 2,2-bis[4-(2-allyloxycarbonyloxy)ethoxy-3,5-dibromophenyl]-propane and 15 parts by weight of PEG200-BAC as an allyl carbonate-based high refractive index resin molded product 1.3 parts by weight of diisopropyl peroxydicarbonate (hereinafter abbreviated as IPP) was added as a radical polymerization initiator to the mixed solution, and a plate-shaped body was used which was produced by ordinary cast polymerization. The refractive index of the plate-like body was 1.580 (20°C). First, as a pretreatment,
After washing the plate with acetone and thoroughly air-drying it to a clear state, it was immersed in an alkaline solution under the conditions shown in Table 1, and then washed with water and dried. The plate-like body described above was subjected to a treatment method () using a curable substance to form a hard film. The evaluation results of the coating are also shown in Table 1.

[Table] No. 1 is a comparative example.
Example 2 A film was formed in the same manner as in Example 1 except that NaOH was used as the basic compound. Table 2 shows the evaluation results of the coating.

【table】

[Table] Example 3 The allyl carbonate high refractive index synthetic resin plate of Example 1 was washed with acetone and thoroughly air-dried to a clear state, and then treated with a 10% alkali solution.
It was immersed in a NaOH aqueous solution for 10 minutes, then washed with water and dried. The above-mentioned plate-shaped body was subjected to treatment methods (), (), and () using a curable substance to form a hard film. Table 3 shows the evaluation results of the coating.

[Table] Note that Nos. 1, 3, and 5 are comparative examples.
Example 4 As an allyl carbonate-based high refractive index resin molded product, 2,2-bis[4-(2-allyloxycarbonyloxy)ethoxy-3,5-dibromophenyl]propane and various polyalkylenes shown in Table 4 were used. Mixture of polyol polyallyl carbonate
A plate-shaped body manufactured by cast polymerization with the addition of 1.3 parts by weight of IPP and a mixed solution of various bis(oxyalkylene phenyl) diallyl carbonates and various polyalkylene polyallyl carbonates shown in Table 5 were manufactured in the same manner. After thoroughly washing the plate-like material with acetone and thoroughly air-drying it to make it clear, 10%
It was immersed in NaOH aqueous solution for 10 minutes, then washed with water and dried. A hardened film was formed by dip-coating the plate-shaped body using a pretreatment method () using a curable substance. The scratch resistance of the cured film for all plate-like materials is B, and the initial adhesion, hot water resistance, and weather resistance are all B.
It was 100.

【table】

【table】

Example 5 As allyl carbonate-based high refractive index resin molded products, 2,2-bis[4-(2-allyloxycarbonyloxy)ethoxy-3,5-dibromophenyl]propane, diallylisophthalate, and
PEG200-BAC was mixed at a composition of 55, 30, and 15 weight percent, respectively, and IPP1.3 was added as a polymerization initiator.
Parts by weight were added to produce a plate-like body by cast polymerization. The plate-shaped body was treated in the same manner as in Example 4 to obtain a cured film. The scratch resistance of the cured film was B, and the initial adhesion, hot water resistance, and weather resistance were all 100. Comparative Examples 1-2 Instead of the allyl carbonate-based high refractive index resin plate in No. 2 of Table 3 of Example 3, polycarbonate made of bisphenol A (Comparative Example 1) and poly(diallyl isophthalate) (Comparative) were used. Example 2) was carried out in the same manner as in Example 3 except that Example 2) was used. However, since polycarbonate is attacked by acetone, its surface was cleaned with methanol. The results are in Table 6
It was as shown in.

【table】

Claims (1)

[Claims] 1 From a copolymer of at least one monomer selected from bis(oxyalkylene phenyl) diallyl carbonate or derivatives thereof and a polyoxyalkylene polyol polyallyl carbonate whose molecular weight is 150 or more. A method for producing a high refractive index resin molded product, which comprises contact-treating the surface of the molded product with an alkaline solution in advance and then coating it with a curable substance.