JPS61148140A - (meth)acrylic acid ester and diluent - Google Patents

Abstract

NEW MATERIAL:The di - tetra(meth)acrylic acid ester of formula I (R is H or CH3; averages of m and n are 1-5, each; average of p is 1-4; averages of q and r are 0-2; average of s is 0-3; p+q+r+s is 4; p+r is 0-2; p+s is 2-4; average of the sum of mp+np is 1-20) which is an addition condensate of ditrimethylolpropane and epsilon-caprolactone. USE:Diluent for ultraviolet-curing or electron beam-curing printing ink or paint having excellent flexibility, high hydrophobic property and excellent curability. PREPARATION:The compound of formula I can be prepared by reacting the addition condensate of ditrimethylpropane and epsilon-caprolactone and expressed by formula I (average of a is 1-5; average of x is 1-4; average of y is 0-3; x+y=4, average of the sum of ax is 1-20) with acrylic acid or methacrylic acid under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is directed to a novel (industrial field of application) which copolymerizes easily with unsaturated group-containing resins in the presence of heat, ultraviolet rays, ionization, radiation, and radical initiators. This invention relates to meth)acrylic acid ester and a diluent for printing ink or paint containing the same as a component.

(Prior Art) Conventionally well-known polyfunctional (meth)acrylic esters include, for example, trimethylolpropane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate.
meth)acrylate, pentaerythritol tetraacrylate.

Examples include tetraacrylate, which is a compound obtained by adding propylene oxide or ethylene oxide to pentaerythritol.

When tramethylolmethane triacrylate and pentaerythritol tetraacrylate are used as diluents for UV-curable paints or printing inks, although the curing speed is fast, the resulting film is brittle because the crosslinking density is too high. It also has five drawbacks: it is inflexible. on the other hand,
Tetraacrylate, a compound made by adding propylene oxide or ethylene oxide to pentaerythritol, has been proposed to improve these drawbacks (Japanese Patent Laid-Open No. 53-11925), but the brittleness and flexibility of the film have been improved. However, there are many ether groups in the molecule, making it hydrophilic. Therefore, when applied to offset printing inks, etc., it is not preferred from the viewpoint of emulsion resistance.

(Means for Solving the Problems) The present invention provides a novel (metallic) material with excellent flexibility, hydrophobicity, and good curability that is useful as a diluent for ultraviolet curable or electron beam curable printing inks and paints. ) to provide acrylic esters. That is, the present invention relates to the following general formula [III (wherein R is I4 or CH3: the average value of m and n is each a number of 1 to 5, preferably 1 to 3
, most preferably 1; the average value of p is a number from 1 to 4; the average value of q and r is each a number from 0 to 2, preferably 0; the average value of S is is a number from 0 to 3; p+q+r+s is 4; Q+r is a number from 0 to 2, preferably 0; p+s is a number from 2 to 4, preferably 4; The average total value is a number from 1 to 20, preferably from 1 to 4.

) and a printing ink or coating diluent containing the same as a component. This novel (meth)acrylic acid ester (general formula [■]) has the following general formula [I] (however, in formula [III, the average value of a is a number of 1 to 5, preferably 1 ~3, most preferably 1, X
The average value of is a number from 1 to 4, the average value of y is a number from 0 to 3, x -1 - y is 4, and the average total value of ax is a number from 1 to 20. , preferably 1 to 4. )
It is produced by the reaction of an addition condensate of ditrimethylolpropane and epsilon caprolactone represented by acrylic acid or methacrylic acid at elevated temperature. This reaction is discussed in more detail below. Further, the addition condensate of ditrimethylolpropane and nibucilone caprolactone of general formula [I] is produced by reacting ditrimethylol propane and nibucilone caprolactone.

Production of addition condensate (general formula [■]) of ditrimethylolpropane and nibsilone caprolactone During the reaction of ditrimethylol propane and nibsilone caprolactone, it is preferable to use an effective amount of a catalyst, and the amount used is the same as that of caprolactone. 0.001~ based on the weight of
1.0% by weight, preferably 0.01-0.2% by weight.

Examples of catalysts include organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, tin compounds such as tetraphenyltin, tetraoctyltin, dilauryltin oxide, di-n-butyltin dichloride, and stannous chloride. can. The reaction between ditrimethylolpropane and nibsilone caprolactone is 5
The reaction is carried out at a temperature of 0-300°C, preferably 110-200'C, for a time sufficient to complete the reaction between the charged reactants. The amount of nibsilone caprolactone charged in the reaction is about 1 mol to 20 mol per 1 mol of ditrimethylolpropane charged. In order to minimize oxidative side reactions, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen. At the end of the reaction, the product consisting of the mixture of addition condensation of ditrimethylolpropane and nibsilone caprolactone can be used as is for the esterification reaction.

Production of (meth)acrylic ester (general formula [■]) (meth)acrylic ester (general formula [■]) is an addition condensate of ditrimethylolpropane and nibsilone capro 1 lactone (general formula [I]) and acrylic acid ester (general formula [■]). Produced by reaction with acid or methacrylic acid or mixtures thereof. The amount of acrylic acid or methacrylic acid used is about 2 to 8 moles per mole of the addition condensate of dimethylolpropane and nibsilone caprolactone (general formula CI: ). For example p+s=
When obtaining compound 4, it is desirable to react a stoichiometric amount of 4 moles with the reactive hydrogen of the hydroxyl group of the addition condensate of citrimethylolpropane and nibsilone caprolactone (general formula [I]), but in practice It is preferable to charge a slight excess of the above so that the reaction can be carried out completely. The reaction is preferably 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
Examples include -1-butylphenol, p-benzoquinone, phenothiazine, N-nitrosodiphenylamine, copper salt, and the like. The reaction generally involves acrylic acid or methacrylic acid to form a (meth)acrylic ester (general formula [■]) at a temperature of about 5°C to 130°C, preferably 65°C to 90'C. The esterification of the addition condensate of ditrimethylolpropane and nibsilone caprolactone (general formula [I]) is carried out over a period of time sufficient to ensure completion of the esterification. This time will vary depending on the batch size, the respective reactants and catalyst and the reaction conditions employed. An esterification catalyst may also be 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 xane, cyclohexane, benzene, or toluene, present to aid in the removal of water formed during this esterification reaction.

This (meth)acrylic acid ester (general formula [TD) 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 generally known to those skilled 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. (meta)
Acrylic esters can be used alone or in combination with other monomers, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or resins containing unsaturated groups, such as unsaturated polyesters, It can be used as a vehicle by mixing it with resins such as polyester acrylate, epoxy acrylate, and urethane acrylate. This new (meth)acrylic ester can also be polymerized by the addition of organic peroxides.

When the (meth)acrylic acid ester of the present invention is used as a diluent, the amount used is usually 40 to 40% in the case of printing ink.
It is preferable to use 50%, and in the case of paints, 40 to 95%.

(Example) In a typical embodiment, acrylic acid.

Addition condensate of ditrimethylolpropane and nibsilone caprolactone (general formula [:I]), catalyst.

Charge the solvent and polymerization inhibitor into the reactor. This mixture is heated until esterification is substantially complete, and then (meth)acrylic acid ester (general formula [■]) is prepared by a conventional method.
Collect. The present invention will be further explained by the following synthesis example and examples of an addition condensate of ditrimethylolpropane and nibsilone caprolactone. In the following, the term “part” means:
Parts are by weight unless otherwise specified.

Synthesis example of addition condensate of ditrimethylolpropane and nibsilone caprolactone.

Synthesis Example 1゜1 and 6 equipped with a stirrer, temperature control device, thermometer, and condenser
In a reactor, 500 parts of ditrimethylolpropane, 228 parts of ε-caprolactone (trade name, Plaxel M, manufactured by Daicel Chemical Industries, Ltd.), and 0.0 parts of tetraisopropyl titanate were added.
1 part was charged, heated to 150 to 160°C in a nitrogen atmosphere, and reacted until unreacted ε-caprolactone became 1% by weight or less. The obtained condensate was a pale yellow liquid with a hydroxyl value of 6.
16.1, and the acid value was 2.9. As a result of molecular weight measurement, it was shown that the addition condensate of ditrimethylolpropane and ε-caprolactone had an average addition amount of about 1 ε-caprolactone in the molecule.

Synthesis Example 2゜In the same reactor as Synthesis Example 1, add 2 ditrimethylolpropane.
50 parts of ε-caprolactone, 228 parts of ε-caprolactone, and 0.11 parts of tetraisoglovir titanate were charged and heated to 150 to 1
The mixture was heated to 60°C and reacted until the amount of unreacted ε-caprolactone was 1% by weight or less. The obtained condensate was a pale yellow liquid with a hydroxyl value of 169.7 and an acid value of 3.4. Met. As a result of molecular weight measurement, it was shown that the addition condensate of ditrimethylol and ε-caprolactone had an average of about 2 ε-caprolactones in the molecule.

Example 1 509.6 of the condensate of ditrimethylolpropane and ε-caprolactone obtained in Synthesis Example 1 was placed in a 2-part 3-reactor equipped with a stirrer, a temperature controller, a thermometer, a condenser, and a separator.
1 part, 484.2 parts of acrylic acid, 14.6 parts of sulfuric acid, 3.68 parts 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 separated into a water-only system using a separator. The solvent is returned to the reactor.

Cooling occurred when 50 parts of water had been produced. Reaction temperature 83-8
The temperature was 8°C. The reaction mixture is dissolved in 960 parts of benzene and 440 parts of cyclohexane, neutralized with a 20% aqueous NaOH solution, and washed three times with 400 parts of a 20% aqueous NaCl solution. The solvent was distilled off under reduced pressure to obtain 654 parts of liquid. This one nails the properties below.

Specific gravity (25℃) 1.103 Viscosity (25℃) 577 cps Saponification value
482 ■KOH/ψ acid value
0.05 M<1lKOH/g - Refractive index (20°C) 1.4780 Elemental analysis value C (%) H (%) 62.30 7.57 High-resolution nuclear magnetic resonance (NMR) analysis of the obtained product The results of absorption frequency measurements are shown below.

% Absorption frequency (Hz) 1 11713, 1 2 11241.6 3 11215.1 4 8855.3 5 8831, 1 6 8701, 1 7 8679, 1 8 5266, 1 9 5233.0 10 5202.2 Nn Absorption frequency ( I(z > 11 4812.2 12 4519.1 13 4362.7 14 4347.2 15 4052.0 16 2875.4 17 2829.1 18 2822.5 19 2364.2 20 2300.3 21 1914.7 22 1725 .2 23 1659.1 24 1568.8 25 504, 6 26 0.0 Above, □11 constant 0., standard material and 5 pieces, 7.
Using 1 silane, Hl and C13H were coupled and measured, and the results finally showed the identification of C13 D-canozzle. Among the above absorptions, %8.9.10 indicates the peak position of absorption of the solvent.

Example 2 Into the same reactor as Example I, the condensate 47 of ditrimethylolpropane and ε-caprolactone obtained in Synthesis Example 2 was added.
8 parts of acrylic acid, 345.9 parts of acrylic acid, 10.4 parts of sulfuric acid, 2.6 parts of hydroquinone, 360 parts of benzene, and 90 parts of cyclohexane, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 72.3 parts. Ta. The reaction temperature was 83-88°C. The reaction mixture was dissolved in 960 parts of benzene and 240 parts of cyclohexane, neutralized with 20% NaOH aqueous solution, and washed three times with 400 parts of 20% NaCl aqueous solution.

The solvent was distilled off under reduced pressure to obtain 561 parts of a pale yellow liquid. This material has the following properties.

Specific gravity (25℃) 1.110 Viscosity (25℃) 522.5 cps Saponification value
483.5 mqKOH/P acid value
0.02 m9KOI(/S4 Refractive index (20℃) 1.4775 Elemental analysis value C (%) I-((%) 61.7 7.8O NMR measurement result slow absorption frequency (Hz) 1 11735.1 2 11710.9 3 11241.6 4 11215.1 5 8857, 5 6 8833, 37 8701, 18 5268, 3 10 5235.2 II 5235.2 II 5204.4 12 4810.0 13 '4342 4342 .8 15 4334.0 16 2875.4 East Absorption frequency (1-IZ) 17 2820. 318
2813, 7 1.9 2304.720
2298° J 21 1914.7 22 1725, 2 23 1661, 3 24 1566, 6 25 502.4 26 0.0 Among the above absorptions, N19.10.11 indicates the absorption peak position of the solvent.

Example 3 Condensate 47 of ditrimethylolpropane and ε-caprolactone obtained in Synthesis Example 2 was placed in the same reactor as in Example 1.
8 parts of methacrylic acid, 413.3 parts of methacrylic acid, 12.6 parts of sulfuric acid, 31 parts of hydroquinone, 360 parts of benzene, and 90 parts of cyclohexane, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 72.3 parts. After the reaction was completed, the reaction mixture was dissolved in 960 parts of benzene and 7240 parts of chlorhexa, and 2
After neutralization with 0% NaOH aqueous solution, 20% NaCl
Wash three times with 400 parts of aqueous solution. The solvent was distilled off under reduced pressure to obtain 603 parts of a pale yellow liquid. This material has the following properties.

Specific gravity (25℃) 1.078 Viscosity (25℃) 368.6 cps Soap price
446.9 rnqKOH/P acid value
0.07 mgKOI-l/'
j.

Refractive index (20° C.) 1.4765 The absorption frequency of the obtained product was measured by high-resolution nuclear magnetic resonance (NMR), and the results are shown below.

Near absorption frequency (Hz) 1 11739.6 2 11715.3 3 11327.5 4 11296, 7 Near absorption frequency (Hz) 5 9236, 5 6 9218°9 7 8500, 6 8 8476, 4 9 5266, 1 10 5235 .2 11 5202.2 12 4823.2 13 4816.6 14 4371.5 15 4360.5 16 4349.5 17 4336.2 18 2844.5 19 2829.1 20 2818.1 21 2309.1 22 2302. 5 23 1919.1 Katsu Absorption frequency (Hz) 24 1734.1 25 1663.5 26 1582.0 27 1571.0 28 1240.5 29 509,0 30 0.0 Among the above absorptions, N[L 9.10. 11 indicates the peak position of absorption of the solvent.

In Example 1, an addition condensate of ditrimethylolprobant ε-caprolactone was synthesized by following the procedure of the synthesis example described above and having an average addition amount of about 4 ε-caprolactones in the molecule. , this addition condensate was placed in the same reactor as in Example 1, containing 3177 parts of acrylic acid, 155.7 parts of acrylic acid, and 4.68 parts of sulfuric acid.
1.2 parts of hydroquinone, 280 parts of benzene, and 70 parts of cyclohexane, and the reaction was carried out in the same manner as in Example 1 until the amount of water produced was 32.4 parts. After the reaction was completed, the reaction mixture was dissolved in 560 parts of benzene and 140 parts of cyclohexane, neutralized with 20% NaOH aqueous solution, and then dissolved in 20% NaOH.
Wash three times with 300 parts of Cl aqueous solution. The solvent was distilled off under reduced pressure to obtain 342 parts of a pale yellow liquid.

This material has the following properties.

Specific gravity (25℃)], 0995 viscosity
degree (25°C) 620.2 c
ps saponification value 485.7 m9KOH/P acid
Value 0.02 mzKO
H154 refractive index (20°C) 1.4770 Elemental analysis value C (%) H (%) 62.10 8.11 NMR measurement result % Absorption frequency () (z) 1 11735.1 2 11710.9 3 11241.6 4 11215.1 5 8857, 5 6 8833, 3 Storm absorption frequency (1-Iz) 7 8701, 1 8 8679, 1 9 5268, 3 10 5235.2 11 5204, 4 12 4810.0 13 4347. 2 14 4342.8 15 4334.0 16 2820.3 17 2813.7 18 2304.7 19 2298, 1 20 1914.7 21 1725, 2 22 1661, 3 123
1566.6 24 502.4 25 0.0 Of the above absorption, $9.10.11 is due to the absorption peak of the solvent.
Indicates the work position.

Application Examples 1-41, Comparative Examples 5-7.
Noepoxy acrylate [Epicoat 828 (Shi)
11 Koru Petrochemical Co., Ltd. Bisphenol type epoxy resin] Resin obtained by esterifying 1 with acrylic acid] ・30 parts of the (meth) obtained in Examples 1 to 4
Acrylic ester, trimethylolpropane triacrylate, tetramethylolmethane triacrylate,
70 parts of each tetraacrylate, which is a compound obtained by adding 5 moles of ethylene oxide to pentaerythritol, was dissolved and used as a photopolymerization initiator.
5.0 parts of Geigy Co., Ltd.) was added, and the mixture was applied to a steel plate coated with an acrylic primer to a film thickness of 25 μm using a roll coater, and then cured with ultraviolet rays using a high-pressure mercury lamp (manufactured by Toshiba Corp., 2KW).

In Table I, the bendability of the coating film was determined by bending the coating film to the outside at a right angle and visually observing the condition.

Curing time was expressed in seconds until dry to the touch.

Hydrophilicity method: Hydrophilicity is determined by the titration value of methanol in which the oils and fats used for offset printing are actually insoluble (
This can be easily evaluated using the drop volume (dropping volume). That is, sample 1.
00! i' to toluene 4.00. Melt methanol in P and dropwise add methanol until the sample solution becomes cloudy. The cloudy point is the end point. It is so hydrophobic that the amount of methanol added dropwise is small.

(Effect of the invention) Nistelha (meth)acrylate of the present invention is useful as a diluent for printing inks and paints, and when the compound of the present invention is used, the resulting coating film has excellent flexibility and good curability. Moreover, the printing ink has excellent hydrophobicity.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. is a number from 1 to 4, the average values of q and r are each a number from 0 to 2,
The average value of s is a number from 0 to 3, and p+q+r+s is 4
q+r is a number from 0 to 2, p+s is a number from 2 to 4, and the average total value of mp+nq is a number from 1 to 20. ) (meth)acrylic acid ester. 2. General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. The average values of q and r are each a number from 0 to 2, the average value of s is a number from 0 to 3, p+q+r+s is 4, q+r is a number from 0 to 2, and p+s is a number from 2 to 4, and the average total value of mp+nq is a number from 1 to 20.