JPH0368873B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel (meth)acrylic acid ester and a method for producing the same. In recent years, ultraviolet curable printing inks, paints, etc. have become popular. Many types of acrylic esters are used as vehicles in these printing inks and paints. As a result of intensive research, the present inventors have obtained a novel (meth)acrylic acid ester that has a fast curing speed and is useful as a vehicle for ultraviolet curable printing inks and paints. That is, the present invention provides (1) general formula (In the formula, R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ,
C ₄ H ₉ or

[Formula] R ₇ is H or CH ₃ ; The average value of m is a number from 0 to 10, preferably a number from 1 to 5, and n represents 0 or 1. ) (meth)acrylic acid ester. (2) Structural formula below (In formula [], R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ ,
C ₃ H ₇ , C ₄ H ₉ or

[Formula]; The average value of m is a number from 0 to 10, preferably a number from 1 to 5, and n is
Indicates 0 or 1. This is a method for producing a (meth)acrylic acid ester represented by the following formula [], which is characterized by esterifying a compound represented by the following formula with acrylic acid or methacrylic acid. (However, the symbols in formula [] are the same as in the above formula [], and R ₇ represents H or CH _3. ) To explain in more detail, the compound having the general formula [] used in the present invention is a compound represented by the general formula [] (However, the symbols in formula [] are the same as in the above formula [].)] and epsilon caprolactate are esterified with acrylic acid or methacrylic acid. The compound represented by the general formula [] is 2,2-dimethyl-3-oxypropanal and the general formula [] (However, the symbols in formula [] are the same as those in formula []). Diols having the general formula [] include, for example, ethylene glycol, propylene glycol, 1,3-propanediol,
Neopentyl glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, hexylene glycol, 2-methyl-2
-phenyl-1,3-propanediol, 2,
2,4-trimethyl-1,3-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-
Such as propanediol. The condensate of the compound represented by the general formula [] and epsilon caprolactone used in the present invention is obtained by adding the compound represented by the general formula [] and epsilon caprolactone. Therefore, m in the formula is
This is the average amount of epsilon caprolactone added. Further, acrylic acid or methacrylic acid is usually used in an amount greater than the stoichiometric ratio. In the general formula, the molar ratio of carboxylic acid to alcohol is 1.0~
2.0, preferably 1.1 to 1.5. The reaction is promoted by using a catalyst and distilling the water produced. Such catalysts are acidic catalysts such as sulfuric acid and P-toluenesulfonic acid, and the amount used is in proportion to acrylic acid or methacrylic acid. It is used in an amount of 0.1 to 10 mol%, preferably 1 to 5 mol%. Advantageously, an azeotropic solvent is used to distill the water produced by the reaction. Such an azeotropic solvent is 60℃
Anything that has a boiling point of ~130°C and can be easily separated from water can be used, but aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as benzene and toluene, and cyclohexane can be used. Alicyclic hydrocarbons are suitable. Its usage is usually
5-70% by weight of the reaction mixture. The reaction temperature is
The temperature range may be from 60 to 130°C, but from the viewpoint of shortening the reaction time and preventing polymerization, it is advantageous to carry out the reaction at a temperature of 75 to 120°C. Although a polymerization inhibitor has already been added to acrylic acid or methacrylic acid, the polymerization inhibitor may be added again during the reaction. Such polymerization inhibitors include hydroquinone, P-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, α-nitroso-β-naphthol, p-benzoquinone, phenothiazine, N-nitrosodiphenylamine, Examples include copper salts. The amount used is usually 0.01 to 1% by weight based on the reaction mixture. The (meth)acrylic acid ester of the present invention can be used for industrial purposes by washing it with water or an aqueous alkali solution, or separating it from a solvent by a method such as vacuum distillation, if necessary. This (meta)
Acrylic acid is useful as a vehicle for coating and ink compositions, which can be cured by radiation or by thermal means. Radiation curing can be carried out by particulate radiation, such as ionizing or electron beams, or by actinic radiation, such as ultraviolet radiation. When curing is carried out with actinic radiation, many types of photosensitizers or photoinitiators are generally included which are known to those skilled in the art. Radiation curing techniques and heat curing techniques are well known to those skilled in the art, and curing can be accomplished by each of them. The (meth)acrylic ester is
itself or with other monomers, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or resins containing unsaturated groups, such as unsaturated polyesters, polyester acrylates, epoxy acrylates,
It can be used as a vehicle by mixing with a resin such as urethane acrylate. This novel (meth)acrylic ester can also be polymerized by adding an organic peracid compound. Examples will be described below. In the examples, parts indicate parts by weight. Example 1 411.2 parts of a compound having the following structure were added to a 2 l reactor equipped with a stirrer, temperature regulator, thermometer, condenser and separator. 112.5 parts of acrylic acid, P-toluenesulfonic acid
13 parts of hydroquinone, 1.0 part of hydroquinone, 400 parts of benzene, and 100 parts of cyclohexane are charged and heated. The produced water is distilled together with the solvent, condensed, and only water is removed from the system using a separator. The solvent is returned to the reactor. Cooling occurred when 23.4 parts of water had been produced. The reaction temperature was 79°C to 88°C. The reaction mixture is dissolved in 504 parts of benzene and 126 parts of cyclohexane, neutralized with 20% aqueous NaOH, and washed three times with 200 parts of 20% aqueous NaCl. The solvent was distilled off under reduced pressure to obtain 406.8 parts of liquid. This material has the following properties. Specific gravity (25℃) 1.0175 Viscosity (25℃) 68.6CPS Saponification value 301.9mgKOH/g Acid value 0.06mgKOH/g Refractive index (20℃) 1.4560 Absorption of the obtained product by high-resolution nuclear magnetic resonance (NMR) The results of frequency measurements are shown below. No. 1 2607.421 2 2607.421 2 2605.468 3 2496.093 4 2027.343 5 1960.937 6 195.078 7 1935.546 8 1931.640 9 1466.796 10 1191.406 11 1160.156 12 1128. 906 13 1068.359 14 1066.406 15 1046.875 16 1029.296 17 962.890 18 654.296 19 578.125 20 574.218 21 513.671 22 474.609 23 425.781 24 382.812 25 369.140 26 332.031 27 326.171 28 298.828 29 291.015 30 0.000 In the above measurement, tetramethylsilane was used as the reference substance and chloroform was used as the solvent.
The coupled measurements of H' and C ¹³ -H were performed, and the results finally showed the identification of the D couple of C ¹³ . Among the above absorptions, Nos. 10, 11, and 12 indicate the absorption peak positions of the solvent. Example 2 Into the same reactor as in Example 1, 744.2 parts of a compound having the following structural formula was added. 103.3 parts of methacrylic acid, 10 parts of P-toluenesulfonic acid, 2.0 parts of hydroquinone, and 750 parts of toluene were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 18 parts. The reaction temperature was 106-116°C. Dissolve the reaction mixture in 1200 parts of toluene and add 20
After neutralization with 20% caustic soda aqueous solution, 20% NaCl aqueous solution
Wash 3 times with 300 parts. The solvent was distilled off under reduced pressure to obtain 666.8 parts of a waxy substance. This material has the following properties. Saponification value 420.7mgKOH/g Acid value 0.02mgKOH/g Elemental analysis value C (%) H (%) 63.23 8.81 Measurement result by NMR No. Absorption frequency (Hz) 1 2605.468 2 2603.515 3 2511.718 4 1878.906 5 1562.500 6 1191.406 7 1158.203 8 1126.953 9 1089.843 10 1044.921 11 1041.015 12 998.046 13 964.843 14 958.984 15 933.593 16 576.171 17 509.765 18 494.140 19 421.875 20 380.859 21 365.234 22 324.218 23 292.968 24 271.484 Among the above absorptions, No. 6, 7, and 8 are due to the solvent. Absorption peak position is shown. Example 3 Into the same reactor as in Example 1, 624.5 parts of a compound having the following structure was added. 129.8 parts of acrylic acid, P-toluenesulfonic acid
15 parts of hydroquinone, 700 parts of benzene, and 175 parts of dichlorohexane, and the reaction was carried out in the same manner as in Example 1 until the amount of produced water became 27 parts. The reaction temperature is
The temperature was 81-87℃. The reaction mixture was dissolved in 840 parts of benzene and 210 parts, neutralized with 20% aqueous sodium hydroxide solution, and washed three times with 300 parts of 20% NaCl water. The solvent was distilled off under reduced pressure to obtain 646.5 parts of liquid. This material has the following properties. Specific gravity (25℃) 1.052 Viscosity (25℃) 261.5 Saponification value 355.9mgKOH/g Acid value 0.02mgKOH/g Refractive index (20℃) 1.4600 Elemental analysis value C (%) H (%) 63.49 8.97 NMR measurement results No. Absorption frequency (Hz) 1 2605.468 2 2496.093 3 1960.937 4 1957.031 5 1931.640 6 1568.359 7 1193.359 8 1160.156 9 1128.906 10 1041.015 11 9 62.890 12 585.937 13 580.078 14 576.171 15 511.711 16 453.125 17 451.171 18 425.781 19 382.812 20 369.140 21 343.750 22 326.171 23 292.768 Among the above absorptions, Nos. 7, 8, and 9 indicate the absorption peak positions of the solvent. Example 4 Into the same reactor as in Example 1, 664.4 parts of a compound having the following structure was added. 43.2 parts of acrylic acid, 5 parts of P-toluenesulfonic acid
1 part, 0.3 parts of hydroquinone, 720 parts of benzene, and 180 parts of dichlorohexane, and the reaction was carried out in the same manner as in Example 1 until the amount of produced water became 9 parts. The reaction temperature is 79
It was ~87℃. The reaction mixture is dissolved in 640 parts of benzene and 160 parts of cyclohexane, neutralized with 20% NaCl aqueous solution, and washed three times with 500 parts of 20% NaCl aqueous solution. The solvent is distilled off under reduced pressure to form a wax-like substance at room temperature.
Obtained 564.8 copies. Saponification value 445.8mgKOH/g Acid value 0.01mgKOH/g Elemental analysis value C (%) H (%) 63.52 8.92 NMR measurement results No. Absorption frequency (Hz) 1 3119.140 2 2607.421 3 2605.468 4 2602.515 5 2496.093 6 1960.937 7 1931.640 8 1568.359 9 1193.359 10 1160.156 11 1128.906 12 1042.968 13 962.890 14 578.125 15 576.171 16 511.718 17 453.125 18 425.781 19 382.812 20 369.140 21 343.750 22 326.171 23 292.968 24 0.000 Of the above absorptions, No. 9, 10, and 11 are absorption peaks of the solvent Show location. Example 5 Into the same reactor as in Example 1, 603.5 parts of a compound having the following structure, 129.8 parts of acrylic acid, P-toluenesulfonic acid
15 parts of phenothiazine, 420 parts of benzene, and 105 parts of cyclohexane were added, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 27 parts. The reaction temperature was 82-88°C. Benzene reaction mixture
Dissolved in 880 parts and 220 parts of cyclohexane, 20%
After neutralizing with NaOH aqueous solution, wash three times with 300 parts of 20% NaCl water. The solvent was distilled off to obtain 617.9 parts of liquid. This material has the following properties. Specific gravity (25℃) 1.0610 Viscosity (25℃) 111.9CPS Saponification value 367.7mgKOH/g Acid value 0.01mgKOH/g Refractive index (20℃) 1.4590 Elemental analysis value C (%) H (%) 62.98 8.79 Measurement by NMR Result No. Absorption frequency (Hz) 1 11779.2 2 8859.7 3 8855.3 4 8738.6 5 8716.5 6 7290.9 7 7255.7 8 5292.5 9 5283.7 10 5250.6 11 4790.1 12 4728.4 1 3 4715.2 14 4708.6 15 4367.1 16 4353.9 17 2580.1 18 2317.9 19 1927.9 20 1771.5 21 1736.3 22 1672.4 23 1222.0 24 1315.4 25 665.4 Among the above absorptions, Nos. 8, 9, and 10 indicate the absorption peak positions of the solvent. Example 6 Into the same reactor as in Example 1, 402.3 parts of a compound having the following structure was added. 129.8 parts of acrylic acid, P-toluenesulfonic acid
15 parts of hydroquinone, 1.0 parts of hydroquinone, 424 parts of benzene, and 106 parts of cyclohexane, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 27 parts. The reaction temperature was 82-88°C. Benzene reaction mixture
Dissolved in 880 parts and 220 parts of cyclohexane, 20%
After neutralizing with NaOH aqueous solution, wash three times with 300 parts of 20% NaCl water. The solvent was distilled off to obtain 573.1 parts of liquid. This material has the following properties. Specific gravity (25℃) 1.0605 Viscosity (25℃) 172.1CPS Saponification value 366.5mgKOH/g Acid value 0.03mgKOH/g Refractive index (20℃) 1.4620 Elemental analysis value C (%) H (%) 63.11 8.78 Measurement by NMR Result No. Absorption frequency (Hz) 1 11777.0 2 11772.6 3 11283.5 4 8859.7 5 8853.1 6 8736.4 7 7213.8 8 7191.8 9 7141.1 10 5413.7 11 5341.0 12 5281.3 13 5250.6 14 5217.6 15 5096.4 16 5047.9 17 4719.6 18 4710.8 19 4706.4 20 4699.8 21 4364.9 22 4351.7 23 2606.6 24 2531.7 25 2525.1 26 2342.2 27 2315.7 28 1925.7 29 1912.5 30 1734.1 31 1723.0 32 1668.0 33 1324.2 34 1319.8 35 1311.0 36 1306.6 37 1167.8 38 1117.1 39 1033.4 40 960.7 Of the above absorptions, No. 12, 13, and 14 are The absorption peak position of the solvent is shown. Example 7 Into the same reactor as in Example 1, 548.5 parts of a compound having the following structure was added. 173 parts of acrylic acid, 20 parts of P-toluenesulfonic acid
1.3 parts of hydroquinone, 480 parts of benzene, and 120 parts of cyclohexane were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 36 parts. The reaction temperature was 81-87°C. Benzene reaction mixture 800
The solution was dissolved in 200 parts of cyclohexane, neutralized with a 20°C aqueous solution of caustic soda, and washed three times with 300 parts of a 20% aqueous NaCl solution. The solvent was distilled off under reduced pressure to obtain 569.7 parts of liquid. This material has the following properties. Specific gravity (25℃) 1.0700 Viscosity (25℃) 73.5CPS Saponification value 340.5mgKOH/g Acid value 0.04mgKOH/g Refractive index (20℃) 1.4510 Elemental analysis value C (%) H (%) 62.09 8.57 Measurement by NMR Result No. Absorption frequency (Hz) 1 11783.6 2 11287.9 3 8888.4 4 8864.2 5 8848.7 6 8743.0 7 8736.4 8 8716.5 9 7112.5 10 5274.9 11 5248.4 12 5244.0 13 5211.0 14 4724.0 15 4713.0 16 4554.4 17 4369.3 18 4353.9 19 4151.1 20 4137.9 21 4133.5 22 2630.8 23 2622.0 24 2324.6 25 2317.9 26 2311.3 27 1925.7 28 1903.7 29 1760.5 30 1734.1 31 1674.6 32 1670.2 33 1328.6 No. of the above absorptions .10, 12, and 13 indicate the absorption peak positions of the solvent. Application Examples 1 to 7 Epoxy acrylate resin (Epicote 828 (bisphenol type epoxy resin manufactured by Ciel Petrochemicals) was added to 60 parts of the new (meth)acrylic acid ester obtained in Examples 1 to 7 with acrylic acid. Resin obtained by esterification) 40 parts, 5 parts of Irga and Cure 184 (manufactured by Ciba Geigy) as photosensitizers.
It was applied onto a steel plate panel and cured with ultraviolet light using a high-pressure mercury lamp (manufactured by Toshiba Corporation, 2KW). The results are shown in Table 1 below.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ,
C ₄ H ₉ or [Formula]; R ₇ is H or CH ₃ ; The average value of m is a number from 0 to 10, and n represents 0 or 1. ) (meth)acrylic acid ester. 2 General formula below [] (In formula [], R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ ,
C ₃ H ₇ , C ₄ H ₉ or [Formula]; The average value of m is a number from 0 to 10, and n represents 0 or 1. A method for producing a (meth)acrylic acid ester represented by the following general formula [], which comprises esterifying a compound represented by the following with acrylic acid or methacrylic acid. (However, the symbols in formula [] are the same as in the above formula [], and R ₇ represents H or CH _3. )