JPH0319258B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a coating material composition capable of forming a crosslinked cured film with excellent wear resistance, flexibility, heat resistance, solvent resistance, adhesion to a substrate, weather resistance, etc. by irradiation with ultraviolet rays in an air atmosphere. The present invention also relates to a method of manufacturing a synthetic resin molded article having excellent wear resistance, weather resistance, etc. using the same. Synthetic resin molded products made from polymethyl methacrylate resin, polycarbonate resin, etc. are not only lightweight and have excellent impact resistance, but also have various advantages such as being inexpensive and easy to mold, and are used in many fields. The development of its use is progressing. However, on the other hand, these synthetic resin molded products lack surface wear resistance, so the surface is easily damaged by contact with other hard objects, friction, scratches, etc. There is a strong demand for improving the abrasion resistance of the surface because it significantly reduces its commercial value or makes it unusable in a short period of time. Furthermore, synthetic resin molded products with improved abrasion resistance using these coating materials may be used outdoors depending on the intended use, such as aircraft windshields, outdoor signboards, traffic signs, and automobile parts. There is a strong demand for weather resistance. Various methods have been studied to improve these drawbacks of synthetic resin molded products.
For example, a method of applying a coating material made of a silicone-based, melamine-based, etc. resin composition to the surface of a synthetic resin molded product and forming a crosslinked film through heat condensation to improve the wear resistance of the synthetic resin molded product, and a single molecule Inside 1
A polyfunctional monomer having three or more polymerizable groups is applied onto the surface of a synthetic resin molded product, and active energy rays are irradiated to form a crosslinked cured film on the surface of the synthetic resin molded product through radical polymerization, resulting in wear resistance. A method for manufacturing a synthetic resin molded product with excellent properties has been proposed (Japanese Patent Publications No. 48-42211 and No. 49-22951). Although these methods have improved the abrasion resistance of the surface of synthetic resin molded products to some extent, the former has insufficient durability against heat shocks, hot water, etc., and chemical resistance, while the latter has insufficient durability against heat shock, hot water, etc. Although it has excellent durability and chemical resistance, it has various drawbacks such as the need for expensive inert gas when manufacturing wear-resistant synthetic resin molded products, and it is not satisfactory in terms of weather resistance. Nakatsuta. In view of this situation, the present inventors have made many proposals for improving wear resistance (Japanese Patent Laid-Open No. 53-102936 and No. 53-104638, Japanese Patent Application No. 53-10463). No. 4079) As a result of intensive study to obtain a wear-resistant synthetic resin molded product with excellent weather resistance,
Synthesize a coating material composition in which a specific polyfunctional acrylate and a monofunctional acrylate are blended in a specific ratio, and a photosensitizer, preferably a specific photostabilizer, and a silicone surfactant are blended in a specific ratio. It has been found that by applying the composition onto a resin molded article and curing it with ultraviolet light, a synthetic resin molded article with excellent abrasion resistance and weather resistance can be obtained. That is, the present invention provides (a) the following general formula (In _the formula, at least three _of X ₁₁ , _{X 12} , X ₁₃ , X ₂₂ , 25 to 75% by weight of a polyfunctional monomer of polyacrylate of pentaerythritol having three or more acryloyloxy groups, and the following general formula: (In the formula, at least three R are CH ₂ = CH−COO
- group, the rest are -H or -OH groups, and n ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ and m ₄ are any numerical value of 0, 1 or 2. and x is a positive integer from 1 to 10. ) and one acryloyloxy group in one molecule, and the boiling point at normal pressure is 25 to 75% by weight.
a monomer mixture consisting of 10 to 50% by weight of a monomer having a viscosity of 20 centipoise or less at 150°C or higher and 20°C; (b) at least one type of monomer per 10 parts by weight of the monomer mixture; A coating material composition comprising: 0.01 to 6.0 parts by weight of a photosensitizer; and (c) 0.01 to 4.0 parts by weight of a photostabilizer having at least one type of cyclic hindered amine structure based on 100 parts by weight of the monomer mixture. The product and the coating composition are applied to the surface of a synthetic resin molded product and irradiated with ultraviolet rays in the air to produce a synthetic resin molded product with excellent abrasion resistance and weather resistance and a crosslinked cured film with a film thickness of 1 to 30 μm. It is related to the manufacturing method. The pentaerythritol polyacrylate used in the present invention is a polyfunctional monomer represented by the general formula (), and specific examples thereof include dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate. Examples include acrylate and dipentaerythritol hexaacrylate, and these monomers are particularly preferred in terms of polymerization activity by ultraviolet irradiation in air and ease of handling. The polyfunctional monomer represented by the general formula () has good polymerization activity and is crosslinked and cured by ultraviolet irradiation to form a highly crosslinked and cured polymer exhibiting high wear resistance and surface hardness. , poor weather resistance,
Due to long-term natural exposure or long-term accelerated exposure, the film deteriorates significantly, causing cracks, rough skin, and poor adhesion. Therefore, in the composition of the present invention, the polyfunctional monomer of general formula () is used in combination with the polyfunctional monomer of general formula (). On the other hand, the polyfunctional monomer represented by the general formula () used in combination with the polyfunctional monomer represented by the general formula () does not have particularly good weather resistance, and may be exposed to sunlight or accelerated by carbon, etc. Due to exposure, poor adhesion with the base material is particularly noticeable, and curing properties (drying properties and hardness development properties) due to ultraviolet irradiation in the air are also poor, so it cannot be used alone; It is necessary to use it in combination with a polyfunctional monomer represented by the general formula (), which has excellent curability by ultraviolet irradiation. The combined use of the polyfunctional monomers represented by the general formulas () and () not only solves the poor curing property of the polyfunctional monomers represented by the general formulas () by ultraviolet rays, but also It has been found that the polyfunctional monomer shown in ) has the unexpected effect of solving the drawback of poor weather resistance at once. In other words, if specific polyfunctional monomers represented by general formulas () and () are used together in a specific proportion, the weather resistance of the polyfunctional monomers themselves represented by general formulas () or () can be improved. This solves the problem of poor quality and prevents changes in appearance such as rough skin, cracks, flaking, and poor adhesion that occur with the deterioration of the weather resistance of wear-resistant synthetic resin molded products, making these synthetic resin molded products beautiful. It became possible to maintain it. Therefore, one or more of the polyfunctional monomers represented by the general formula () is present in the monomer mixture in an amount of 25 to 75% by weight, preferably 30 to 60% by weight. If the amount of the polyfunctional monomer represented by the general formula () is less than 25% by weight, a cured film with sufficient wear resistance cannot be obtained, and if the amount exceeds 75% by weight, This is not preferable because the weather resistance of the resulting synthetic resin molded product becomes poor and the smoothness of the coating film becomes poor. On the other hand, the polyfunctional monomer represented by the general formula () is also used in an amount of 25 to 75% by weight, preferably 30% by weight in the monomer mixture.
It is necessary to use it in a range of ~60% by weight; if the usage rate is less than 25% by weight, the effect of improving weather resistance will be poor, and if it exceeds 75% by weight, the curability of the coating material composition will deteriorate and it will not be sufficient. It becomes impossible to obtain wear resistance and surface hardness, and weather resistance also becomes inferior. As for the effect of improving the weather resistance of the cured film composed of the polyfunctional monomers represented by the general formulas () and (), the weathering prevention effect of the cured film is particularly large.
It prevents changes in appearance such as rough skin, cracks, and peeling of the film that occur as a result of weathering of the hardened film, and allows the wear-resistant synthetic resin molded product to remain beautiful for a long period of time. A specific example of the polyfunctional monomer represented by the general formula () is an esterification reaction product with the following composition, but the actual reaction requires an appropriate amount of raw materials within the range that satisfies the general formula (). The stoichiometry can be varied depending on the Ester compounds include malonic acid/trimethylolethane/acrylic acid, malonic acid/trimethylolpropane/acrylic acid, malonic acid/glycerin/acrylic acid, malonic acid/pentaerythritol/acrylic acid, succinic acid/trimethylolethane/acrylic acid. , succinic acid/trimethylolpropane/acrylic acid, succinic acid/
Glycerin/acrylic acid, succinic acid/pentaerythritol/acrylic acid, adipic acid/trimethylolethane/acrylic acid, adipic acid/trimethylolpropane/acrylic acid, adipic acid/pentaerythritol/acrylic acid, adipic acid/
Glycerin/acrylic acid, glutaric acid/trimethylolethane/acrylic acid, glutaric acid/trimethylolpropane/acrylic acid, glutaric acid/
Glycerin/acrylic acid, glutaric acid/pentaerythritol/acrylic acid, sepacic acid/trimethylolethane/acrylic acid, sepacic acid/trimethylolpropane/acrylic acid, sebacic acid/
Mention may be made of esterification reaction products of compound combinations such as glycerin/acrylic acid or sepacic acid/pentaerythritol/acrylic acid. In terms of weather resistance improvement effects, malonic acid/trimethylolpropane/acrylic acid, malonic acid/trimethylolpropane/acrylic acid, succinic acid/trimethylolethane/acrylic acid, succinic acid/trimethylolpropane/acrylic acid, adipic acid /
A polyfunctional monomer of the esterification reaction product synthesized from a combination of compounds such as trimethylolethane/acrylic acid or adipic acid/trimethylolpropane/acrylic acid is more preferred. These may be used alone or in combination of two or more. Contains one acryloyloxy group in one molecule used in combination with a polyfunctional monomer, and has a boiling point at normal pressure.
Monomers with a viscosity of 20 centipoise or less at 150°C or higher and 20°C (hereinafter simply referred to as monofunctional monomers) can be used on the coated surface formed after coating a molded product with a coating composition. This is necessary to give the cured film a smooth surface and to give the cured film flexibility and adhesion to the substrate. In other words, in order to obtain stable adhesion to the substrate against long-term natural exposure and long-term accelerated exposure, it is necessary to use a monofunctional monomer that has a large dissolving effect on the substrate and has excellent polymerization activity. In order to form a coated film with excellent smoothness and smoothness, it is desirable that the viscosity of the monomer mixture be 1000 centipoise or less, and for this purpose a monofunctional monomer that satisfies the above conditions must be used in combination. Must be. This monomer is not particularly limited as long as it satisfies the above conditions, but in the case of the present invention, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, ethoxyethyl acrylate, etc. acrylate, ethyl carbitol acrylate, butoxyethyl acrylate,
Monomers such as 1,4-butylene glycol monoacrylate that have a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond in their side chains have excellent polymerization activity in air. Particularly preferred. These monofunctional monomers may be used alone or in combination of two or more within the composition range. The proportion of the monomer used is 10 to 50% by weight, preferably 10 to 40% by weight, based on the entire monomer mixture. If the monofunctional monomer content exceeds 50% by weight, it is not preferable because a crosslinked cured coating having sufficient wear resistance cannot be obtained. Furthermore, the boiling point of the monofunctional monomer is
If the temperature is lower than 150°C, when the coating composition is applied to the surface of the molded product and cured, it will volatilize and escape, resulting in an increase in the viscosity of the coating composition, and on the other hand, the viscosity of the monofunctional monomer will increase. If it exceeds 20 centipoise at 20°C, it is not preferable because the viscosity of the monomer mixture cannot be effectively lowered. As described above, the object of the present invention can be fully achieved by using a monomer mixture composed of a polyfunctional monomer and a monofunctional monomer represented by the general formulas () and (). In order to improve weather resistance, it is more preferable to blend a small amount of a light stabilizer having a cyclic hindered amine structure into the monomer mixture. The light stabilizer having a cyclic hindered amine structure has the following general formula: In the formula, n represents an integer of 1 to 4; when n = 1, R is an acyl group derived from an aliphatic or aromatic monocarboxylic acid; when n = 2, an acyl group derived from an aliphatic or aromatic dicarboxylic acid; When n=3, it is a triacyl group derived from an aliphatic or aromatic tricarboxylic acid; When n=4, it is a tetraacyl group derived from an aromatic tetracarboxylic acid. ), specifically 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6-
Tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine,
4-stearoyloxy-2,2,6,6-tetramethylpiperidine, succinic acid-bis(2,2,
6,6-tetramethyl-4-piperidyl), sebacic acid-bis(2,2,6,6-tetramethyl-
4-piperidyl), phthalic acid-bis(2,2,6,
6-tetramethyl-4-piperidyl), trimesic acid-tris(2,2,6,6-tetramethyl-
4-piperidyl) and the like. In small amounts, these light stabilizers having a cyclic hindered amine structure are very useful for further improving and stabilizing the excellent weather resistance of the present invention. The blending amount is 0.01 to 2.0 per 100 parts by weight of the monomer mixture.
Parts by weight are preferred; if the amount is less than 0.01 parts by weight, the effect will not be significant, and if the amount exceeds 2.0 parts by weight, the resulting synthetic resin molded product may whiten or develop haze. This is not desirable as it may cause These compounds may be used alone or in combination of two or more. When using these light stabilizers having a cyclic hindered amine structure, it is preferable to further use an antioxidant. The reason for this is not clear, but the combination use of antioxidants with these light stabilizers has the effect of synergistically increasing the weather resistance improvement and stabilizing effect of light stabilizers with a cyclic hindered amine structure. There is. A small amount of antioxidant is sufficient, and monomer mixture
The amount is 0.01 to 2.0 parts by weight per 100 parts by weight. 0.01
If the amount is less than 2.0 parts by weight, there will be little synergistic effect with the light stabilizer, and if it exceeds 2.0 parts by weight, the resulting synthetic resin molded product may become white or develop haze, resulting in a deterioration in appearance. . Octadecyl-3-(3,
5-ditertyabutyl-4-hydroxyphenyl)-propionate, pentaerythrityl-tetrakis[3-(3,5-ditertyaliptyl-
4-hydroxyphenyl)-propionate],
1,6-hexanediol bis-3-(3,5-
diterciabutyl-4-hydroxyphenyl)
-propionate, 2,2'-thiodiethylbis-
[3-(3,5-dithyabutyl-4-hydroxyphenyl)-propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,
5-ditashyabutylanilino)-1,3,5
-triazine, 3,5-ditertyabutyl-4
- diethyl ester of hydroxybenzyl phosphate,
1,3,5-tris(4-tertiarybutyl-3
-Hydroxy-2,6-dimethylbenzyl)isocyanuric acid, 4-methyl-2,6-dithyabutylphenol, 4-methyl-2,6-bis(1-methylheptadecyl)-phenol, 2,
2'-methylenebis(4-ethyl-6-tertiarybutylphenol), 1,3,5-tris(4-
Hydroxy-3,5-ditertyabutylbenzyl)-2,4,6-trimethylbenzene and the like can be used. These may be used alone or in combination of two or more. It should be noted that these light stabilizers and antioxidants having a cyclic hindered amine structure are useful in small amounts to further improve and stabilize the excellent weather resistance of the present invention. If the functional monomer is not contained, the effect will be small. The silicone surfactant used in a preferred embodiment of the present invention is a necessary component for improving the smoothness of the crosslinked cured film and preventing whitening due to contact with organic solvents. Its amount is based on 100 parts by weight of the monomer mixture.
It ranges from 0.0001 to 2.0 parts by weight. Its usage is
If it is less than 0.0001 parts by weight, the effect is small;
If it exceeds 2.0 parts by weight, the smoothness of the coating will decrease, which is not preferable. The silicone surfactant is not particularly limited, but preferably has a molecular structure consisting of polydimethylsiloxane units, as described in Japanese Patent Application No. 54-4569, a part of which is modified with a polyoxyalkylene group. The degree of modification _is such that at least _one oxyalkylene group (-
OCH ₂ CH ₂ −,

[Formula] etc.) are preferably bonded within a range of 0.1 to 10.0 units. If the degree of modification by oxyalkylene groups is less than 0.1, the smoothness of the film will be worse than when no silicone surfactant is added, while if the degree of modification by oxyalkylene groups exceeds 10, the smoothness of the film will be worse. This is not preferable because it reduces the Examples of the photosensitizer used in the present invention include benzoin, penzoin methyl ether, penzoin ethyl ether, benzoin isopropyl ether, acetoin, ptyloin,
Toluoine, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, methyl phenyl glyoxylate, ethyl phenyl glyoxylate, 4,4 '-Bis(dimethylaminobenzophenone), carbonyl compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, and sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide. compounds, azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylpaleronitrile, benzoyl peroxide,
Examples include peroxide compounds such as ditertiary butyl peroxide. monomer mixture
The amount to be added per 100 parts by weight is preferably 0.01 to 6 parts by weight. If too much is added, the crosslinked cured film will be colored or the weather resistance will be deteriorated, which is undesirable. If the amount added is too small, it will be susceptible to ultraviolet rays. Curability deteriorates. The above are the essential components constituting the present invention. At least one other vinyl monomer may be used in combination. If necessary, antioxidant synergistic agents such as didodecyl-3,3'-thiobispropionate, dioctadecyl-3,3'-thiobispropionate, N,N',N''-hexane Methyl phosphoric triamide, etc., and other stabilizers can be appropriately blended in small amounts. Methods for applying the present composition include brush coating, flow coating, spray coating, spin coating, and dipping coating. However, from the viewpoint of coating workability of the coating material composition, smoothness and uniformity of the coating, and improvement of the adhesion of the cured coating to the substrate, it is best to apply by dipping using an appropriate organic solvent. This is a preferred method.The organic solvent used in the dip coating method is as described in JP-A-53-102936, etc., which is mixed with the entire composition of the coating material to form a uniform solution and then applied under normal pressure. It is preferable to use an organic solvent having a boiling point of 50°C or more and 200°C or less and a viscosity of 10 centipoise or less at room temperature.The amount of organic solvent used is 90 to 80 parts by weight of the coating material composition. 20 parts by weight (100 parts by weight in total).If the amount of organic solvent used is less than 20 parts by weight, it will not be possible to obtain a film with particularly excellent smoothness and uniformity; If the thickness exceeds 100%, the film thickness becomes too thin and the surface hardness decreases. Specific examples of organic solvents include alcohols such as ethanol, isopropanol, normal propanol, isobutyl alcohol, normal butyl alcohol, benzene, toluene, xylene, These organic solvents include aromatic hydrocarbons such as ethylbenzene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, and acid esters such as ethyl acetate, n-butyl acetate, and ethyl propionate. may be used alone, or two or more types may be used as a mixture as long as the boiling point and component ratio of the mixture are within the range that satisfies the above requirements.Synthetic resin of coating material composition It is necessary to apply the coating amount to the surface of the molded product so that the thickness of the cured film is in the range of 1 to 30μ, preferably 2.5μ to 20μ.If the thickness of the crosslinked cured film is less than 1μ, weather resistance Less effective in improving sex,
If it exceeds 30μ, the adhesion to the substrate may be reduced, cracks, haze, etc. may occur more easily, or the curing of the coating composition by ultraviolet irradiation may be impaired. As a means of curing the coating material composition of the present invention, it is possible to irradiate it with active energy rays such as electron beams normally taken out from an electron beam accelerator of 20 to 2000 KV, and radiation such as α rays, β rays, and γ rays. However, in order to obtain a highly hard crosslinked cured film by irradiating active energy rays in the air, which is a feature of the present invention, it is essential to irradiate ultraviolet rays, and using other active energy rays is not practical. The purpose of the invention is not achieved.
Although it is of course possible to irradiate ultraviolet rays in an inert gas such as nitrogen, carbon dioxide, or argon, this composition has the greatest advantage that a crosslinked cured film with high hardness can be obtained even in a normal air atmosphere. It has the following characteristics. In the present invention, synthetic resin molded products used in the production of synthetic resin molded products with excellent wear resistance and weather resistance include various synthetic resin molded products, regardless of thermoplastic resin or thermosetting resin, such as polymethyl acrylate resin. Sheet-shaped molded products and film-shaped products manufactured from polycarbonate resin, polyallyl diglycol carbonate resin, polyethylene resin, acrylonitrile-styrene copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, etc. Specific examples include molded products, rod-shaped molded products, and various injection molded products. Among these molded products, molded products made from polymethyl methacrylate resin, polycarbonate resin, etc. are often used to take advantage of their optical properties, heat resistance, impact resistance, etc., and are also wear resistant. Since there is a strong demand for improved properties and weather resistance, these molded products are particularly preferred as synthetic resin molded products used in the present invention. As described above, the coating material composition of the present invention and the synthetic resin molded product manufactured using the same with excellent wear resistance and weather resistance also have excellent performance such as smoothness, water resistance, chemical resistance, and durability. Its performance hardly deteriorates even under harsh conditions and environments such as oxygen, ozone, rainwater, heat, and various gases in the atmosphere, and it has excellent wear and weather resistance. It is extremely useful for applications in the required fields. The present invention will be explained in more detail below using Examples. Parts in the examples indicate parts by weight. In addition, the measurement evaluation in the examples was performed by the following method. (1) Abrasion resistance #000 steel wool was attached to the tip of a cylinder with a diameter of 25 mm, brought into contact with the horizontally placed sample surface, rotated 5 times (20 rpm) with a load of 1.0 kg, and visually observed the extent of scratches. do. ◎...No scratches on the sample surface〇...Slight scratches on the sample surface △...Significant scratches on the sample surface ×...Severe scratches on the sample surface (2) Adhesion Cross-cutting to the cross-linked cured film - Cellophane tape peel test. That is, make 100 1 mm 2 lines by inserting 11 film cutting lines vertically and horizontally into the film that reach the base material at ¹ mm intervals, then stick cellophane tape on top of it and peel it off rapidly. Cellophane tape peel test on the same location 1~
Do this 3 times. ◎……No peeling marks even after 3 tests〇……No peeling marks after the 1st test, but peeling marks from the 2nd test△…… 〃 Number of stitches 1 to 50 ×…… 〃 Number of stitches 51 to 100 (3) Surface smoothness ◎...Very good, almost mirror-like〇...Good△...Slight disturbance ×...Surface disturbance is large (4) Appearance a) Discoloration or haze◎... No discoloration (yellowing, whitening) or haze 〇...Slight discoloration or haze △...Discoloration or haze ×...Discoloration or haze noticeableb) Cracks, flaking, etc.◎...None〇...Hardly noticeable but a little Yes △...Yes
120 minutes) and ultraviolet carbon weather meter (Toyo Rika WE-2 model, rainfall 12 minutes/1 cycle 60
It was carried out using Reference Example 1 Synthesis of an ester compound 120.2 g of trimethylolethane was placed in a glass flask equipped with a thermocouple, a stirrer, and a water separator.
g (1 mol), succinic acid 65.0 g (0.55 mol), acrylic acid 158.6 g (2.20 mol), toluene 1000 g,
3 g of Cu ₂ Cl ₂ and 13.5 g of p-toluenesulfonic acid were charged. When the reaction was continued for 7 hours at an external temperature setting of 115°C, 52ml of water was distilled out. cool the reactor
It was washed twice with a 0.5% H ₂ SO ₄ aqueous solution and further washed three times with pure water. After washing, add hydroquinone monomethyl ether (MEHQ) to the reaction solution to a concentration of approximately 500 ppm.
0.14g was added and mixed, and the toluene was removed using a water jet pump at 50 to 60°C for 6 hours, and a viscous pale yellow compound (abbreviated as TAS) was obtained as a residue in the pot. This compound had a viscosity of 8500 cps/20°C, an acid value of 14.0, and a bromine value of 99. Reference Example 2 Synthesis of an ester compound In a reactor similar to Reference Example 1, 120.2 g (1 mol) of trimethylolethane, 80.4 g (0.55 mol) of adipic acid, 158.6 g (2.20 mol) of acrylic acid, and toluene were added.
1000g, Cu ₂ Cl ₂ 3g, p-toluenesulfonic acid
When 13.5 g was charged and reacted for 6 hours at an external temperature of 115°C, 53 ml of water was distilled out. 0.5% after cooling
It was washed once with an aqueous H ₂ SO ₄ solution and five times with pure water. After washing, add 0.15g of MEHQ to the reaction solution and mix.
When toluene was distilled off using a water pump at 50°C for 6 hours, a pale yellow viscous compound (abbreviated as TAA) was obtained as a residue. The obtained compound had a viscosity of 11,000 cps/20°C, an acid value of 8.5, and a prom value of 90. Reference Example 3 Synthesis of ester compound In a reactor similar to Reference Example 1, 134.2 g (1 mole) of trimethylolpropane and 80.4 g (0.55 g) of adipic acid were added.
(mol), acrylic acid 158.6g (2.20mol), toluene 1000g, Cu ₂ Cl ₂ 3g, p-toluenesulfonic acid
When 13.5 g was charged and reacted for 8 hours at an external temperature of 115°C, 51 ml of water was distilled out. 0.5% after cooling
Washed twice with H ₂ SO ₄ aqueous solution and three times with pure water, added and mixed 0.15 g of MEHQ to the reaction solution, and heated at 50°C for 8 hours.
When toluene was distilled off using a water pump,
A pale yellow viscous compound (abbreviated as TPA) was obtained as a residue. Viscosity of the obtained compound:
8800 cps/20°C, acid value: 25.1, bromine number: 82.1. Example 1 Dipentaerythritol hexaacrylate 15
Part, dipentaerythritol pentaacrylate
15 parts, dipentaerythritol tetraacrylate 10 parts, 25 parts of the ester compound (TAS) synthesized in Reference Example 1, 35 parts of tetrahydrofurfuryl acrylate, light stabilizer sepacic acid-bis(2,2,
6,6-tetramethyl-4-piperidyl) 1 part,
Antioxidant 0.2 part of octadecyl-3-(3,5-ditertyabutyl-4-hydroxyphenyl)-propionate, silicone surfactant 0.25
parts, benzoin isopropyl ether 1.5 parts, benzophenone 3 parts, isopropyl alcohol 120 parts
A methacrylic resin plate with a thickness of 4 mm was immersed in a coating material composition consisting of 50 parts of toluene and 50 parts of toluene to form a coating. After leaving this for 2 minutes, using a 2KW high pressure mercury lamp (ozone type) in the air,
UV rays for 1.1 seconds from a distance of cm (from the lamp),
Irradiated twice. The thickness of the cross-linked cured film of the obtained synthetic resin molded product was 3.5 μm, and the #000 steel wool abrasion resistance test results and initial appearance of adhesion, smoothness, and discoloration or haze were good (evaluation results). :◎). Furthermore, the appearance and adhesion after 1500 hours of accelerated sunlight exposure were good (evaluation results: both ◎). Examples 2 to 4, Comparative Examples 1 to 4 Curing liquids shown in the table were prepared, and a 3 mm thick methacrylic resin plate was immersed in it and pulled up to form a film. After leaving this for 3 minutes, in the air
Using a 2KW high-pressure mercury lamp (ozone type), both sides of the board were irradiated with ultraviolet rays for 13 seconds at a distance of 20cm from the lamp. The results obtained are shown in Table 1.

【table】

[Table] Examples 5 to 8, Comparative Example 5 The curing liquid shown in the table was prepared, and a 4 mm thick polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical, trade name: Iupilon) was immersed in it and pulled up to form a film. Ta. After leaving this for 3 minutes, in the air
Using a 2KW high-pressure mercury lamp (ozone type), apply ultraviolet rays to both sides of the board for 10 seconds at a distance of 20cm from the lamp.
It was irradiated once. The results obtained are shown in the table.

[Table] Example 9 Dipentaerythritol hexaacrylate 20
Part, dipentaerythritol pentaacrylate
20 parts, dipentaerythritol tetraacrylate 10 parts, 35 parts of the ester compound (TPA) synthesized in Reference Example 3, 5 parts of ethyl carbitol acrylate, 10 parts of 2-hydroxyethyl acrylate,
0.5 part of the light stabilizer of Example 1, 0.2 part of 1,3,5-tris(4-hydroxy-3,5-ditertyabutylbenzyl)-2,4,6-trimethylbenzene (antioxidant), silicon System surfactant 0.2
A coating composition consisting of 1.5 parts of benzoin ethyl ether and 1.5 parts of benzoin ethyl ether was applied onto a 5 mm thick polycarbonate injection molded plate using a bar coater. Using a 2KW high-pressure mercury lamp, do this 20cm from the lamp.
UV light was irradiated twice for 13 seconds at a distance of . The abrasion resistance, adhesion, and initial appearance of discoloration or haze of the obtained product were good.The abrasion resistance and adhesion were good after 800 hours of ultraviolet carbon weather meter exposure test, and no cracks were observed. I couldn't help it. Examples 10 to 13 A methacrylic resin plate with a thickness of 4 mm was immersed in the curing liquid shown in the table and pulled up to form a film.
A synthetic resin molded product was obtained in the same manner as in Examples 4 to 7. The results obtained are shown in the table.

【table】

Claims (1)

[Claims] 1 (a) The following general formula (In _the formula, at least three _of X ₁₁ , _{X 12} , X ₁₃ , X ₂₂ , 25 to 75% by weight of a polyfunctional monomer of dipentaerythritol polyacrylate having three or more acryloyloxy groups, and the following general formula: (In the formula, at least three R are CH ₂ =CH-
COO- group, the rest are -H or -OH groups, n ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ and m ₄
takes a value of 0, 1 or 2, and x
is a positive integer from 1 to 10. ), has one acryloyloxy group in one molecule, has a boiling point of 150°C or higher at normal pressure, and has a viscosity of 20 centipoise at 20°C. A monomer mixture consisting of 10 to 50% by weight of the following monomers, (b) 0.01 to 6.0 parts by weight of at least one photosensitizer per 100 parts by weight of the monomer mixture, and (c) A coating composition comprising 0.01 to 4.0 parts by weight of at least one light stabilizer having a cyclic hindered amine structure based on 100 parts by weight of the monomer mixture.