JPH0368871B2 - - 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 is based on (1) general formula (In the formula, R represents H or CH _3. ) A di(meth)acrylic acid ester represented by: (2) Structural formula below This is a method for producing a di(meth)acrylic ester represented by the following general formula [], which is characterized by esterifying a compound having the following with acrylic acid or methacrylic acid. More specifically, the compound having the structural formula [] used in the present invention is obtained by condensation of 2,2-dimethyl-3-oxypropanal and diglycerin. 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, but preferably
It is 1.1-1.5. 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 approximately 100% relative to acrylic acid or methacrylic acid. 0.1-10 mol%, preferably 1-10 mol%
5 mol% is used. Advantageously, an azeotropic solvent is used to distill the water produced by the reaction. 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% of the reaction mixture.
~70% by weight. The reaction temperature is 60~
The temperature may be in the range of 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,
Examples include 2,5-dihydroxy-P-quinone, phenothiazine, N-nitrosodiphenylamine, and copper salts. The amount used is usually 0.01 to 1% by weight based on the reaction mixture. 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. It can be used as a vehicle by mixing with resins such as , epoxy acrylate, and urethane acrylate. The new di(meth)acrylic esters can also be polymerized by addition of organic peroxides. Examples will be described below. In the examples, parts indicate parts by weight. Example 1 In a 2 l reactor equipped with a stirrer, temperature regulator, thermometer, condenser and separator, 2,2-dimethyl-3
- 347.2 parts of a compound having the following structure, which is a condensate of oxypropanal and diglycerin 179.5 parts of acrylic acid, 20 parts of para-toluenesulfonic acid
1 part, 2 parts of hydroquinone, 480 parts of benzene, and 120 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 37.3 parts of water had been produced. The reaction temperature was 80-85°C. The reaction mixture is dissolved in 384 parts of benzene and 96 parts of cyclohexane, neutralized with 20% caustic Sozo aqueous solution, and washed three times with 300 parts of 20% brine. The solvent was distilled off under reduced pressure to obtain 401 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.1310 Viscosity (25℃) 3392CPS Saponification value 241mgKOH/g Acid value 0.06mgKOH/g Refractive index (20℃) Elemental analysis value C (%) H (%) 59.61 7.76 High resolution of the obtained product The results of absorption frequency measurements by nuclear magnetic resonance (NMR) are shown below. No. Absorption frequency (Hz) 1 2492.187 2 1972.656 3 1958.984 4 1929.687 5 1921.875 6 1650.390 7 1640.625 8 1615.234 9 1611.328 10 1564.453 11 1 550.781 12 1537.109 13 1433.593 14 1191.406 15 1158.203 16 1126.953 17 1121.093 18 1080.078 19 1076.171 20 1066.406 21 1044.9 21 22 1037.109 23 1027.343 24 1015.625 25 1011.718 26 1005.859 27 947.265 28 583.984 29 578.125 30 574.218 31 570.312 32 564.453 33 509.765 34 353.515 35 310.546 36 289.052 37 −1.953 In the above measurement, tetramethylsilane was used as the reference material and chloroform was used as the solvent. Using H ¹ ,
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, Nos. 14, 15, and 16 indicate the absorption peak positions of the solvent. Example 2 Into the same reactor as in Example 1, 347.2 parts of a compound having the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and diglycerin, was added. 214.4 parts of methacrylic acid, P-toluenesulfonic acid
20 parts of hydroquinone, 3 parts of hydroquinone, and 600 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 37.3 parts of water had been produced. The reaction temperature was 111°C to 118°C. The reaction mixture is dissolved in 500 parts of toluene, neutralized with 20% aqueous sodium hydroxide solution, and washed three times with 400 parts of 20% aqueous sodium chloride solution. The solvent was distilled off under reduced pressure to obtain 427.4 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.1070 Viscosity (25℃) 1200CPS Saponification value 213.1mgKOH/g Acid value 0.01 mgKOH/g Refractive index (20℃) Elemental analysis value C (%) H (%) 61.19 8.21 NMR measurement results No. Absorption Frequency (Hz) 1 2511.718 2 2050.781 3 2046.875 4 1892.578 5 1882.812 6 1654.296 7 1632.812 8 1619.140 9 1615.234 10 1568.359 11 1437 .500 12 1193.359 13 1160.156 14 1128.906 15 1123.046 16 1082.031 17 1078.125 18 1052.734 19 1046.875 20 1042.968 21 1017.578 22 1013.671 23 1007.823 24 984.375 25 964.843 26 583.984 27 578.125 28 572.265 29 568.359 30 366.406 31 511.718 32 312.500 33 291.015 34 275.390 35 0.000 Among the above absorptions, No. 12, 13, and 14 indicate the absorption peak positions of the solvent. Application Examples 1 and 2, Comparative Application Examples 1 to 3 To 60 parts of the novel di(meth)acrylic acid ester obtained in Examples 1 and 2, epoxy acrylate resin (Epicoat 828 (bisphenol manufactured by Ciel Petrochemical Co., Ltd.) 40 parts of resin (obtained by esterifying a type epoxy resin) with acrylic acid, 3 parts of IRGAKURE 184 (manufactured by Ciba Geigy) as a photosensitizer were added, and the mixture was coated on a steel panel, and a high-pressure mercury lamp (manufactured by Toshiba) was added. , 2KW). The results are shown in Table 1 below. As a comparative example, with the same composition as above, polyethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., product name:
The table below also shows the curing results of PEG400DA), 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). Shown in 1.

【table】

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

Claims (1)

[Claims] 1. General formula (In the formula, R represents H or CH _3. ) A di(meth)acrylic acid ester represented by: 2 Structural formula below A method for producing a di(meth)acrylic acid ester represented by the following general formula [], which comprises esterifying a compound having the following with acrylic acid or methacrylic acid.