JPH0368872B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel di(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 is based on (1) general formula (In the formula, R is H or CH ₃ ; n represents an integer having a value of 1 to 4.) A di(meth)acrylic ester represented by: (2) Structural formula below (In formula [], n represents an integer having a value of 1 to 4.) This is a method for producing acrylic ester. (In the formula [], R is H or CH ₃ ; n represents an integer having a value of 1 to 4.) To explain in more detail, the compound having the general formula [] used in the present invention is 2,2 -dimethyl-
3-oxypropanal and general formula [] (In formula [], n represents an integer having a value of 1 to 4.) It is obtained by condensation with a triol having the following formula. Specifically, the triols having the general formula [ ] include 1,2,3-propanetriol, 1,2,4-butanetriol, 1,2,5
-pentanetriol, 1,2,6-hexanetriol. Further, acrylic acid or methacrylic acid is usually used in an amount greater than the stoichiometric ratio. Generally, the molar ratio of carboxylic acid to alcohol is 1.0 to 2.0, preferably 1.1 to 1.5. The reaction is accelerated by using a catalyst and the water produced is distilled. Such catalysts are acidic catalysts such as sulfuric acid, P-toluene, and sulfonic acid, and the amount used is the same as that of acrylic acid or methacrylic acid. hand
It is advantageous to use an azeotropic solvent to distill the water produced by the reaction, which is used in an amount of 0.1 to 10 mol %, preferably 1 to 5 mol %. Such azeotropic solvents can be used as long as they have a boiling point of 60°C to 130°C and are easily separated from water, but n
Suitable are aliphatic hydrocarbons such as -hexane and n-heptane, aromatic hydrocarbons such as benzene and toluene, and cycloaliphatic hydrocarbons such as cyclohexane. The amount used is usually 5 to 70 percent by weight of the reaction mixture. The reaction temperature may range 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. Usually, a polymerization inhibitor is already added to acrylic acid or methacrylic acid, but the polymerization inhibitor may be added again during the reaction. Such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiol, α-nitroso-β-naphthol, p-
-benzoquinone, 2,5-dihydroxy-p-quinone, phenothiazine, N-nitrosodiphenylamine, copper salts and the like. The amount used is usually 0.01 to 1% of the reaction mixture.
Weight%. The di(meth)acrylic acid ester of the present invention is used for industrial purposes by washing with water or aqueous alkaline solution, etc., if necessary, or by separating it from the solvent by a method such as vacuum distillation. This di(meth)acrylic acid ester [] is
Useful as vehicles for coating and ink compositions, they 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 commonly known in the art are included. 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 di(meth)acrylic acid esters of the present invention may be used alone or with other monomers such as trimethylolpropane polyacrylate, pentaerythritol polyacrylate, pentaerythritol tetraacrylate, or unsaturated group-containing resins such as unsaturated polyesters. , epoxy acrylate, urethane acrylate, and other resins for use as a vehicle. The new di(meth)acrylic esters can also be polymerized by addition of organic peracid compounds. Examples will be described below. In the examples, parts indicate parts by weight. Example 1 2,2-dimethyl-3-
A compound having the following structure that is a condensate of oxypropanal and 1,2,3-propanetriol
352.4 copies 345.9 parts of acrylic acid, para-toluenesulfonic acid
10 parts of hydroquinone, 2 parts of hydroquinone, 400 parts of benzene, and 100 parts of cyclohexane are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor. Cooling occurred when 72 parts of water had been produced. The reaction temperature was 79°C to 85°C. The reaction mixture is dissolved in 680 parts of benzene and 170 parts of cyclohexane, neutralized with 20% aqueous sodium hydroxide solution, and washed three times with 300 parts of 20% brine. The solvent was distilled off under reduced pressure to obtain 429.8 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.1450 Viscosity (25℃) 552.5CPS Saponification value 385.0mgKOH/g Oxidation 0.05mgKOH/g Refractive index (20℃) 1.4725 Elemental analysis value C (%) H (%) 59.01 7.12 Obtained The results of measuring the absorption frequency of the product using high-resolution nuclear magnetic resonance (NMR) are shown below. No. Absorption frequency (Hz) 1 2566.406 2 2554.687 3 2490.234 4 2486.328 5 2484.375 6 1970.703 7 1957.031 8 1927.734 9 1919.921 10 1615.234 11 1 609.375 12 1558.593 13 1189.453 14 1158.203 15 1148.437 16 1136.718 17 1123.046 18 1117.187 19 1105.468 20 1101.562 21 1070.3 12 22 1066.406 23 1054.687 24 1035.156 25 1025.390 26 1021.484 27 1009.765 28 1003.906 29 1000.000 30 990.234 31 958.984 32 939.4 53 33 931.640 34 892.578 35 578.125 36 572.265 37 564.453 38 562.500 39 519.531 40 501.953 41 318.359 42 285.156 43 39.062 Above Reference material for measurement H′, using tetramethylsilane as the solvent and chloroform as the solvent.
A coupled measurement of C ¹³ -H was performed, and the results finally showed the identification of the D couple of C ¹³ . Among the above absorptions, No. 13, 14, and 17 indicate the absorption peak positions of the solvent. Example 2 Into the same reactor as in Example 1, 352.4 parts of a compound having the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and 1,2,3-propanetriol, was added. 413 parts of methacrylic acid, P-toluenesulfonic acid
10 parts of hydroquinone, 3 parts of hydroquinone, and 500 parts of toluene are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor. Cooling occurred when 72 parts of water had been produced. The reaction temperature was 110°C to 118°C. The reaction mixture is dissolved in 900 parts of toluene, neutralized with a 20% aqueous sodium hydroxide solution, and washed three times with 400 parts of a 20% aqueous sodium chloride solution.
The solvent was distilled off under reduced pressure to obtain 535 parts of a pale yellow liquid.
This material has the following properties. Specific gravity (25℃) 1.0930 Viscosity (25℃) 66.4CPS Saponification value 349.6mgKOH/g Acid value 0.04mgKOH/g Refractive index (20℃) 1.4685 Elemental analysis value C (%) H (%) 61.43 7.84 Measurement by NMR Result No. Absorption frequency (Hz) 1 2509.765 2 2048.878 3 2044.921 4 2041.015 5 1892.578 6 1880.859 7 1615.234 8 1560.546 9 1189.453 10 1158.203 11 1152.343 12 1146.484 13 1126.953 14 1109.375 15 1105.468 16 1080.078 17 1041.015 18 1027.343 19 1011.718 20 1005.859 21 1000 .000 22 994.140 23 962.890 24 945.312 25 936.546 26 582.031 27 576.171 28 566.406 29 564.453 30 287.109 31 271.484 32 250.000 33 203.125 Among the above absorptions, Nos. 9, 10, and 13 indicate the absorption peak positions of the solvent. Example 3 Into the same reactor as in Example 1, 380.3 parts of a compound having the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and 1,2,4-butanetriol, was added. 345.9 parts of acrylic acid, P-toluenesulfonic acid
10 parts of hydroquinone, 3 parts of hydroquinone, 320 parts of benzene, and 80 parts of cyclohexane are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor. Cooling occurred when 72 parts of water had been produced. The reaction temperature was 83-87°C.
Add 800 parts of benzene and 200 parts of cyclohexane to the reaction mixture.
After neutralizing with 20% caustic soda aqueous solution, wash three times with 300 parts of 20% saline solution. The solvent was distilled off under reduced pressure to obtain 489 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.1140 Viscosity (25℃) 184.2CPS Saponification value 344.6mgKOH/g Acid value 0.03mgKOH/g Refractive index (20℃) 1.4700 Elemental analysis value C (%) H (%) 60.21 7.52 Measurement by NMR Result No. Absorption frequency (Hz) 1 2574.218 2 2492.187 3 1964.843 4 1958.984 5 1929.687 6 1925.781 7 1910.156 8 1611.328 9 1607.421 10 1601.562 11 1560.546 12 1189.453 13 1158.203 14 1138.671 15 1126.953 16 1113.281 17 1105.468 18 1060.546 19 1046.875 20 1039.067 21 1013 .671 22 990.234 23 984.375 24 919.921 25 896.484 26 576.171 27 568.359 28 523.437 29 484.375 30 480.468 31 417.109 32 335.937 33 287.109 34 -1.953 Among the above absorptions, No. 12, 13, and 15 indicate the absorption peak positions of the solvent. Example 4 Into the same reactor as in Example 1, 436.3 parts of a compound having the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and 1,2,6-hexanetriol, was added. 345.9 parts of acrylic acid, P-toluenesulfonic acid
10 parts of hydroquinone, 3 parts of hydroquinone, 320 parts of benzene, and 80 parts of cyclohexane are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor. Cooling occurred when 72 parts of water had been produced. The reaction temperature was 83-89°C. The reaction mixture is dissolved in 900 parts of benzene and 225 parts of cyclohexane, neutralized with 20% aqueous sodium hydroxide solution, and washed three times with 300 parts of 20% aqueous sodium chloride solution.
The solvent was distilled off under reduced pressure to obtain 539.6 parts of a pale yellow liquid.
This material has the following properties. Specific gravity (25℃) 1.0780 Viscosity (25℃) 73.5CPS Saponification value 318.8mgKOH/g Acid value 0.03mgKOH/g Refractive index (20℃) 1.4685 Elemental analysis value C (%) H (%) 62.31 8.14 Measurement by NMR Result No. Absorption frequency (Hz) 1 2492.187 2 1966.796 3 1958.984 4 1929.687 5 1644.531 6 1609.375 7 1601.562 8 1191.406 9 1158.203 10 1146.484 11 1138.671 12 1126.953 13 1060.546 14 1046.875 15 1039.062 16 962.890 17 576.171 18 570.312 19 568.859 20 525.390 21 486.328 22 453.126 23 425.781 24 332.031 25 287.019 26 251.953 27 248.046 Among the above absorptions, Nos. 8, 9, and 12 indicate the absorption peak positions of the solvent. Application Examples 1 to 4, Comparative Application Examples 1 to 3 To 60 parts of the novel di(meth)acrylic acid ester obtained in Examples 1 to 4, an epoxy acrylate resin (Epicoat 828 (manufactured by Ciel Petrochemical Co., Ltd.) was added. 40 parts of a resin obtained by esterifying a phenolic epoxy resin) with acrylic acid, 5 parts of Irgakiure 184 (manufactured by Ciba Geigy) as a photosensitizer.
It was applied onto a steel 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. As a comparative example, with the same composition as above, the di(meth)acrylic acid ester was replaced with polyethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., product name PEG400DA) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., product name HDDA). ) and neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., product name NPGDA), and the curing results are also shown in Table 1 below.

[Table] Number of times a mercury lamp passes until it is dry to the touch.

Claims (1)

[Claims] 1. General formula (wherein, R is H or CH ₃ ; n represents an integer having a value of 1 to 4). 2 General formula below [] (In the formula [], n represents an integer having a value of 1 to 4) is esterified with acrylic acid or methacrylic acid. Method for producing meth)acrylic acid ester. (In formula [], R is H or CH ₃ ; n represents an integer having a value of 1 to 4.)