JPH0153973B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field of the Invention) The present invention is an allyl carbonate high refractive index resin that forms a curable film with good adhesion on the surface of an allyl carbonate high refractive index resin molded product that has excellent impact resistance, moldability, transparency, etc. This invention relates to a method for manufacturing molded products. (Background Art of the Invention) Synthetic resins with excellent transparency are used in optical lenses, eyeglass lenses, prisms, and glass plates by taking advantage of their characteristics such as high impact resistance, light weight, and good moldability and dyeability compared to inorganic glass. It is widely used as an organic glass. 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 also uses allyl carbonate, which is produced by copolymerizing bis(oxyalkylene phenyl) diallyl carbonate, diallyl ester having an aromatic ring, and monoallyl carbonate having an aromatic ring, as a high refractive index resin with particularly excellent impact resistance. system of synthetic resins. However, like 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, causing devitrification of the resin surface. It has the disadvantage that transparency is easily impaired by scratches. (Problems to be Solved by the Invention) In order to compensate for the above-described drawbacks of the allyl carbonate-based high refractive index resin, the present invention forms a hard coating on the surface of the resin with good adhesion, similar to conventional synthetic resins. The purpose is to obtain a good allyl carbonate-based high refractive index resin molded product. Many proposals have been made for such hard coatings, among which silicone-based, melamine-based,
Epoxy-based, acrylic-based, etc. 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 a film include adding an adhesion-improving component to a curable substance, providing an undercoat layer that can adhere to both the synthetic resin and the hard film, and There is a method of treating and activating the surface of a synthetic resin before coating it 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. (Means for Solving the Problem) As a result of intensive research into a method for forming a durable hard coating with excellent adhesion on the surface of an allyl carbonate-based high refractive index resin molded product, the present inventor found that the allyl carbonate-based high refractive index resin molded product The present inventors have discovered that by pre-treating a high refractive index resin molded product with an alkaline solution, the adhesion of the formed hard coating to the base material is significantly superior, leading to the completion of the present invention. That is, the present invention includes at least three components: (i) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, (ii) diallyl ester having an aromatic ring, and (iii) monoallyl carbonate having an aromatic ring. This is a method for producing a high refractive index resin molded article, which is characterized in that the surface of a molded article made of a copolymer is previously contacted with an alkaline solution and then coated with a curable substance. The allyl carbonate high refractive index resin that is the object of the present invention is a new high refractive index resin that has high transparency and particularly excellent impact resistance. A copolymer obtained by copolymerizing a monomer mixture containing at least three components: enyl) diallyl carbonate or a derivative thereof, (ii) diallyl ester having an aromatic ring, and (iii) monoallyl carbonate having an aromatic ring. It is a transparent polymer typified by optical lenses and prisms for microscopes and cameras, eyeglass lenses, and organic glasses such as dustproof glass and windshield glass. The bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof is represented by the following general formula. (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, l is an integer of 1 or 2) Specific examples of (oxyalkylene phenyl) diallyl carbonate or derivatives thereof include: etc., and mixtures thereof. In addition, as the diallyl ester having an aromatic ring, for example, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, triallyl isocyanurate, etc. are suitable, and the It is used in a range of 1 to 99% by weight, particularly 5 to 80% by weight. Furthermore, as the monoallyl carbonate having an aromatic ring, for example, benzyl allyl carbonate, phenoxyethyl allyl carbonate, metabromopenzyl allyl carbonate, paracyanobenzyl allyl carbonate, phenyl allyl carbonate, etc. are preferably used. The amount of monoallyl carbonate having an aromatic ring to be used is based on a mixed composition consisting of bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof and diallyl ester having an aromatic ring, or other monomers that can be copolymerized if necessary. It is generally preferable to select the amount in the range of 0.5 to 20% by weight, particularly 1 to 15% by weight. In addition, in the present invention, in order to obtain the desired high refractive index resin with excellent impact resistance, it is effective to further use polyoxyalkylene polyol polyallyl carbonate in combination. Examples of such polyoxyalkylene polyol polyallyl carbonate include diethylene glycol bis(allyl carbonate), and particularly those having a molecular weight of 150 or more,
It is very effective to use polyallyl carbonate of polyoxyalkylene polyol preferably having a molecular weight of 20 to 1,200. In order to produce a high refractive index resin with excellent impact resistance, which is the object of the present invention, it is necessary to use bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, diallyl ester having an aromatic ring, and if necessary, copolymerization. It can be obtained by using known radical polymerization methods such as the presence of a radical polymerization initiator and irradiation with ultraviolet rays or radiation, using monoallyl carbonate having an aromatic ring as an essential component along with other possible monomers. Note that the polymerization method in the present invention is not particularly limited, and any known polymerization method can be employed. An example of a typical polymerization method is a cast polymerization method. For example, the monomer containing a radical polymerization initiator may be injected between molds held by elastomer gaskets or spacers, cured in an air oven, and then taken out. Alternatively, the monomer can be preliminarily polymerized in the presence of a polymerization initiator to increase the viscosity of the monomer, and then cast polymerization can be carried out. Of course, during the polymerization, mold release agents, ultraviolet absorbers, antioxidants, color inhibitors,
Various stabilizers and additives such as antistatic agents and fluorescent dyes can be selected and used as required. In the present invention, the allyl carbonate polymer described above is molded into a desired shape and subjected to pretreatment. (Function) In the present invention, amines represented by the general formula RnH ₃ − _o N (where R is C ₁ to C ₆ aliphatic or C ₆ to _{C 10} aromatic are the same or different hydrocarbon groups, n is an integer of 1, 2, or 3), alkali metals such as lithium, sodium, potassium, rubidium, and cesium. Examples include solutions consisting of basic compounds such as hydroxides, alcoholates, and ammonia alone or in mixtures of two or more thereof. In particular, alkaline solutions containing strongly basic sodium and potassium hydroxides or alcoholates are particularly effective in treating the surfaces of allyl carbonate-based high refractive index resin molded products by forming durable hard coatings with excellent adhesion. It is suitably used for pretreatment to form. 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.
It can also be used as a mixed solvent system with water. Therefore, the alkali metal alcoholates may be used in alcoholic solutions and 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
A 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 preferable in terms of workability and the like. 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 thoroughly degreased and cleaned in advance in order to effectively promote contact with the alkaline solution. In the present invention, the allyl carbonate 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. The curable substance used in the present invention is a so-called crosslinkable substance that reacts with heat, a catalyst, a curing agent, light, radiation, etc. to form a three-dimensional network structure to form a hard film, and can be used without particular restrictions. can. For example, melamine-based curable compositions made of melamines and other reactive substances such as formaldehyde, acrylic curable compositions made of acrylic esters and acrylamides, epoxies and other reactive substances such as bisphenol A, etc. Epoxy-based curable composition consisting of reactive substances, etc.
Silicone-based curable compositions made of organosilicon compounds such as methyltrimethoxysilane, or curable compositions composed of these are 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 0.1 μ to 50 μ. Further, the curing of the curable substance may be carried out as appropriate depending on the type thereof. (Effects) 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 the allyl carbonate-based high refractive index resin molded product 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 Kikai Kogyo Co., Ltd., and visually check the degree of scratches on the surface after moving the sample surface back and forth 10 times under a load of 1 kg. It was observed and evaluated on a five-point 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 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. After coating the specified molded product by immersing it in the substance and thoroughly air-drying it at room temperature,
It was cured by heating at 130°C for 1 hour. () 20 parts by weight of bis(γ-triethoxysilylpropyl) 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, 0.05 standard 10 parts by weight of hydrochloric acid, 0.25 ammonium perchlorate as curing catalyst
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. () A prescribed molded article is dipped and coated in a curable composition prepared by dissolving 50 parts by weight of trimethylolpropane triacrylate, 50 parts by weight of triethylene glycol diacrylate, and 1 part by weight of benzophenone in 50 parts by weight of isopropyl alcohol. After thoroughly drying with nitrogen air, the film 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 cured by heating at 130°C for 1 hour. Example 1 As an allyl carbonate-based high refractive index resin molded product, 70 parts by weight of 2,2-bis[4-(2-allyloxycarbonyloxy)ethoxy-3,5-dibromophenyl]propane and 30 parts by weight of diallyl isophthalate. A plate-like body produced by ordinary cast polymerization by adding 1.5 parts by weight of diisopropyl peroxydicarbonate (hereinafter abbreviated as IPP) as a polymerization initiator to a mixed solution of 5 parts by weight and 5 parts by weight of benzialyl carbonate was used. there was. The refractive index of the plate-like body is
It was 1.585 (measured at 20°C). First, as a pretreatment, the plate-shaped body was washed with acetone and sufficiently air-dried to a clear state, and then 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] Example 2 A film was formed in the same manner as in Example 1 except that NaOH was used as the basic compound. NaOH
The processing conditions and film evaluation results are shown in Table 2.

[Table] Example 3 The plate-shaped body of the allyl carbonate high refractive index synthetic resin of Example 1 was washed with acetone and thoroughly air-dried to a clear state, and then treated with an alkaline solution for 10 minutes.
% NaOH aqueous solution for 10 minutes at 20°C, 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. The evaluation results of the coating are shown in Table 3.

[Table] Example 4 As an allyl carbonate-based high refractive index resin molded product, predetermined amounts of various bis(oxyalkylene phenyl) diallyl carbonates and diallyl esters having an aromatic ring as shown in Table 4 were added, and Regarding a plate-shaped body produced by cast polymerization by adding 1.5 parts by weight of IPP to a mixed solution containing a predetermined amount of monoallyl carbonate having an aromatic ring shown in Table 4,
After thoroughly washing with acetone and air-drying it to a clear state, it was immersed in a 10% NaOH aqueous solution at 20°C for 10 minutes.
Then, it was washed with water and dried. This plate-shaped body was coated by dip coating using a curable substance treatment method () to obtain a hard coating. For both plates, the scratch resistance of the cured film is B, and the initial adhesion, hot water resistance, and weather resistance are all B.
It was 100.

【table】

[Table] Other abbreviations in Table 4 indicate the following compounds. DAIP = diallyl isophthalate DAP = diallyl phthalate DATP = diallyl terephthalate BzAc = benzyl allyl carbonate PEAc = phenoxyethyl allyl carbonate P-CBzAc = parachlorobenzyl allyl carbonate Example 5 As an allyl carbonate-based high refractive index resin molded product, diallyl 40 parts by weight of terephthalate, 2,2
- Added 60 parts by weight of bis[4-(2-allyloxycarbonyloxy)ethoxy-3,5-dibromophenyl]propane, and further added 10 parts by weight of polyethylene glycol 200 bis(allyl carbonate) as other monomers, Phenyl allyl carbonate 3 as a monoallyl carbonate having an aromatic ring
A plate-shaped body was obtained in the same manner as in Example 4, except that 3.5 parts by weight of di-2-ethylhexyl peroxydicarbonate was added as a polymerization initiator, and treated with alkali to form a hard film. I let it happen. The scratch resistance of the resulting 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 synthetic resin plate in No. 2 of Table 3 of Example 3, polycarbonate made of bisphenol A (Comparative Example 1) and poly(diallyl isophthalate) were used. ) (Comparative Example 2) was used in the same manner as in Example 3. However, since the polycarbonate was soaked in acetone, its surface was cleaned with methanol. The results were as shown in Table 5.

【table】

Claims (1)

[Claims] 1 Consisting of a copolymer containing at least three components: (i) bis(oxyalkylene phenyl) diallyl carbonate or a derivative thereof, (ii) diallyl ester having an aromatic ring, and (iii) monoallyl carbonate having an aromatic ring. A method for producing a high refractive index resin molded product, which comprises previously contacting the surface of the molded product with an alkaline solution and then coating the surface with a curable substance.