JPH0580463B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention is directed to a novel di(metallic acid) that can be easily polymerized in the presence of heat, ultraviolet rays, ionization, radiation, or a radical initiator, and can be easily copolymerized with unsaturated group-containing compounds. ) This relates to an acrylic ester composition. (Prior Art) Various polycarbonate acrylic esters have been developed and are being considered as components of adhesives, paints, and the like. (Problems to be Solved by the Invention) However, polycarbonate acrylic esters that have been studied in the past, for example,
The polycarbonate acrylic acid ester disclosed in No. 52-104553 is useful as an adhesive, but the problem when using it is that it is solid or a highly viscous liquid at room temperature, making it difficult to handle and making it difficult to use as an adhesive. When used for this purpose, it may crystallize before use and must be heated and dissolved before use. (Means for Solving the Problems) The present invention provides a liquid with relatively low viscosity at room temperature, which is useful as a vehicle for ultraviolet curable or electron beam curable printing inks and paints, and which has excellent flexibility and curability. The object of the present invention is to provide a novel di(meth(acrylic acid ester) composition. That is, the present invention has the following general formula []

[Chemical formula] (In the formula, R ₁ represents an alkylene group having 4 to 10 carbon atoms, preferably 5 to 8 carbon atoms, R ₂ represents H or CH ₃ ,
The average value of a and b is each 0 to 5, preferably 0.
~2, and the average total value of a+b is 0.5~5
Preferably the number is 0.5 to 3, and the average value of 1 is 1
-10, preferably 3-8. ) It relates to a di(meth)acrylic acid ester composition represented by: This new di(meth)acrylic acid ester composition (general formula []) is represented by the following general formula []

[Chemical formula] (wherein R ₁ , a, b, l have the same meanings as above) (This is an ester of a diol composition, an adduct of epsilon caprolactone, and a diaryl carbonate or dialkyl carbonate) (obtained by exchange reaction, etc.) and acrylic acid or methacrylic acid at elevated temperature. This reaction will be discussed in more detail later. Specific examples of diol compounds that are raw materials of general formula [] include 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol,
1,8-octanediol, hexylene glycol, etc. can be used. The reaction between diol compound and epsilon caprolactone is 50-300℃
This can be easily carried out by using an effective amount of a catalyst (eg, stannous chloride, tetraisopropyl titanate, etc.) at a temperature of . The amount of catalyst used is 0.001-1.0% by weight based on the weight of caprolactone. In addition, specific examples of diaryl carbonate or dialkyl carbonate used as raw materials include:
For example, diphenyl carbonate, bis-chlorophenyl carbonate, dinaphthyl carbonate, phenyl-tolyl carbonate, phenyl-
Chlorophenyl carbonate, 2-tolyl-4-
tolyl carbonate, dimethyl carbonate,
Diethyl carbonate and the like can be mentioned.
The transesterification reaction of the diol composition, the adduct of epsilon caprolactone, and the diaryl carbonate or dialkyl carbonate is carried out under reduced pressure for 50 to 50 minutes.
The reaction is carried out by distilling off by-products such as phenol at a reaction temperature of 200°C. Preference is given to using transesterification catalysts (eg, tetrabutyl titanate, sodium phenolate), the amount of which is from 0.01 to 1% by weight, based on the diaryl carbonate or dialkyl carbonate. The carbonate diol represented by the general formula [] obtained in this way is a monocarbonate diol having one carbonate structure in the molecule or a polycarbonate diol having two or more carbonate structures in the molecule, and is easily available on the market. can be obtained. For example, DN-982 (manufactured by Nippon Polyurethane Co., Ltd., carbonate diol whose unit is a reactant of 1 mol of 1,6-hexanediol and an average of 0.83 mol of ε-caprolactone, average molecular weight 2000),
DN-983 (manufactured by Nippon Polyurethane Co., Ltd., average of 1 mol of 1,6-hexanediol and ε-caprolactone)
Carbonate diol with a unit of 0.71 mol of reactant, average molecular weight 1000), etc. Manufacture of di(meth)acrylic acid ester composition (general formula []) A di(meth)acrylic acid ester composition (general formula []) is made by combining carbonate diol of general formula [] with acrylic acid or methacrylic acid, or their Produced by reaction with a mixture. The amount of acrylic acid or methacrylic acid used is about 1 to 5 moles per 0.5 mole of carbonate diol (general formula []) charged. The reaction is (meta)
Preferably, it is carried out in the presence of a polymerization inhibitor to minimize or retard polymerization of the acrylic double bonds. The above polymerization inhibitors are well known to those skilled in the art and they are used in concentrations of 0.01 to 5% by weight of the mixture. Examples of these polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, p-benzoquinone, phenothiazine, N-nitrosodiphenylamine, thiourea, copper salts, etc. . The reaction is generally carried out at about 50°C to 130°C, preferably 65°C.
To ensure completion of esterification of carbonate diol (general formula []) with acrylic acid or methacrylic acid to produce di(meth)acrylic acid ester composition (general formula []) at a temperature of ~90°C be carried out for a sufficient period of time. This time will vary depending on the batch size, the respective reactants and catalyst and the reaction conditions employed. The esterification catalyst is also present in a concentration of 0.1 to 15 mol %, preferably 1 to 6 mol %, based on the acrylic acid or methacrylic acid used. Any known esterification catalyst can be used, examples of which include p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, sulfuric acid, and the like. It is desirable to have an inert solvent such as hexane, cyclohexane, benzene, toluene present to aid in the removal of water produced during the esterification reaction. The di(meth)acrylic ester compositions (general formula []) are useful as vehicles 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 by actinic radiation, many types of photoinitiators commonly known to those skilled in the art are included, such as benzophenone, N,N-dimethylbenzoic acid ethyl ester, and the like. 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 ester composition can be used alone or in combination with other monomers, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or unsaturated group-containing resins, such as , unsaturated polyester, polyester acrylate, epoxy acrylate, urethane acrylate, and other resins for use as a vehicle. When used in combination with other monomers or resins, the mixing ratio can be arbitrary and is not particularly limited. This novel di(meth)acrylate composition can also be polymerized by the addition of organic peroxides (eg, benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, etc.). (Example) In a typical embodiment, (meth)acrylic acid, a polycarbonate diol composition (general formula []), a catalyst, a solvent, and a polymerization inhibitor are charged into a reactor. The mixture is heated until esterification is substantially complete and then di(meth)
The acrylic ester composition (general formula []) is recovered. The invention is further illustrated by the following examples. In the following, parts refer to parts by weight unless otherwise specified. Example 1 A composition having the following structural formula was placed in two reactors equipped with a stirrer, a temperature controller, a thermometer, a condenser, and a separator.

[Chemical value] (However, the average total value of a + b is 0.71) (manufactured by Nippon Polyurethane Co., Ltd., DN-983, OH value 112.2 mg
KOH/g, average molecular weight approximately 1000) 700 parts, acrylic acid 121 parts, p-toluenesulfonic acid 14 parts, hydroquinone 1.0 parts, benzene 560 parts, cyclohexane
140 parts are charged and heated, the produced water is distilled and condensed together with the solvent, only the water is removed from the system in a separator, and the solvent is returned to the reactor. Cooling occurred when 25.2 parts of water had been produced. The reaction temperature was 80-86°C. The reaction mixture was dissolved in 960 parts of benzene and 240 parts of cyclohexane and neutralized with a 20% aqueous solution of caustic soda.
Wash 3 times with 500 parts of saline. The solvent was distilled off under reduced pressure to obtain 690 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.1000 Viscosity (25℃) 2100cps Saponification value 414.4mgKOH/g Acid value 0.01mgKOH/g Refractive index (20℃) 1.4680 High resolution nuclear magnetic resonance (NHR) of the obtained product
The results of absorption frequency measurements are shown below. No. Absorption frequency (Hz) 1 2603.515 2 2495.140 3 2333.984 4 1958.984 5 1933.593 6 1199.218 7 1166.015 8 1134.865 9 1015.625 10 966.796 11 96 2.890 12 935.546 13 511.718 14 490.234 15 429.687 16 382.812 17 369.140 18 0.000 However, for the above measurement, Using tetramethylsilane as a reference material, the coupling measurement of H ¹ and C ^13-H was performed, and the final identification result of the D couple of C ¹³ was shown. Among the above absorptions, Nos. 6, 7, and 8 indicate the absorption peak positions of the solvent. No. 18 indicates the peak position of tetramethylsilane. Example 2 A composition having the following structural formula was placed in the same reactor as in Example 1.

[Chemical value] (However, the average total value of a + b is 0.83) (Manufactured by Nippon Polyurethane Co., Ltd., DN-982, OH value 56
mgKOH/g average molecular weight approx. 2000) 700 parts, acrylic acid 61 parts, p-toluenesulfonic acid 6 parts, hydroquinone 0.4 parts, benzene 560 parts, cyclohexane
140 parts were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 12.6 parts. Reaction temperature is 81-86℃
It was hot. The reaction mixture was dissolved in 1200 parts of benzene and 300 parts of cyclohexane, and as in Example 1,
Neutralization, washing, and solvent removal were performed to obtain 654 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.1060 Viscosity (25℃) 13750cps Saponification value 415.7mgKOH/g Acid value 0.03mgKOH/g Refractive index (20℃) 1.4700 NMR measurement results No. Absorption frequency (Hz) 1 2607.421 2 2333.987 3 1960.937 4 1933.593 5 1195.312 6 1164.062 7 1130.859 8 1017.578 9 964.843 10 511.718 11 429.687 12 382.812 13 369.140 14 0.000 Of the above absorptions, No. .5, 6, and 7 indicate the absorption peak positions of the solvent. No. 14 indicates the peak position of tetramethylsilane. Example 3 A composition having the following structural formula was placed in the same reactor as in Example 1.

[Chemical value] (However, the average total value of a + b is 0.71) (Manufactured by Nippon Polyurethane Co., Ltd., DN-983, OH value
112.2mgKOH/g, average molecular weight approximately 1000) 700 parts,
145 parts of methacrylic acid, 4.5 parts of sulfuric acid, hydroquinone
1.1 parts of toluene and 700 parts of toluene were charged, and the reaction was carried out in the same manner as in Example 1 until the amount of produced water became 25.2 parts. The reaction temperature was 105-116°C. The reaction mixture was dissolved in 1000 parts of toluene, and the solution was neutralized, washed, and desolventized in the same manner as in Example 1 to obtain 723 parts of a pale yellow liquid. This material has the following properties. Specific gravity (25℃) 1.0940 Viscosity (25℃) 1900cps Saponification value 400.0mgKOH/g Acid value 0.02mgKOH/g Refractive index (20℃) 1.4680 NMR measurement results No. Absorption frequency (Hz) 1 2601.562 2 2509.765 3 2333.984 4 2052.734 5 1878.906 6 1201.171 7 1167.968 8 1136.718 9 1015.625 10 968.750 11 962.890 12 933.593 13 509.765 14 429.687 15 382.812 16 369.140 17 273.437 18 0.000 Among the above absorptions, Nos. 6, 7, and 8 are the absorption peak positions of the solvent. show. No. 18 indicates the peak position of tetramethylsilane. Comparative Example 1 A composition having the following structural formula was placed in the same reactor as in Example 1.

[Formula] (manufactured by Nippon Polyurethane Co., Ltd., DN-981, OH value
112.2mgKOH/g, average molecular weight 1000) 700 parts, acrylic acid 121 parts, p-toluenesulfonic acid 14 parts,
1.0 part of hydroquinone, 560 parts of benzene, and 140 parts of cyclohexane are charged and heated. The water produced is distilled and condensed together with the solvent, and only the water is removed from the system using a separator. The solvent is returned to the reactor. Cooling occurred when 25.2 parts of water had been produced. The reaction temperature was 80-86°C. The reaction mixture was mixed with 960 parts of benzene and 240 parts of cyclohexane.
After neutralizing with 20% caustic soda aqueous solution, wash three times with 500 parts of 20% saline. The solvent was distilled off under reduced pressure to obtain 667 parts of a pale yellow solid. This material has the following properties. Melting point: 43°C Acid value: 0.02 mgKOH/g Application Examples 1 to 3, Application Comparative Example 1 A photopolymerization initiator was added to 100 parts of the di(meth)acrylic acid ester composition obtained in Examples 1 to 3 and Comparative Example 1. KAYACURE BP (manufactured by Nippon Kayaku Co., Ltd.)
benzophenone) 5 parts and as an accelerator
After adding 10 parts of KAYACURE EPA (manufactured by Nippon Kayaku Co., Ltd., N,N-dimethylbenzoic acid ethyl ester) and coating it on a PVC sheet with a roll coater to a film thickness of 25μ, it was coated with a high-pressure mercury lamp (manufactured by Toshiba Corporation, 2KW). UV cured. In the table, the coating film was bent by 180° with the coating film on the outside, and the condition was visually judged. Curing time was expressed in seconds until dry to the touch.

【table】

[Table] (Effects of the Invention) The di(meth)acrylic acid ester composition of the present invention is liquid at room temperature, easy to handle, and useful as a vehicle for printing inks and paints, and when the compound of the present invention is used, The resulting coating film has excellent flexibility.

Claims (1)

[Claims _{] 1} General _formula 5, the average total value of a+b is a number from 0.5 to 5, and the average value of 1 is from 1 to 5.
The number is 10. ) A di(meth)acrylic acid ester composition represented by: