JPH0248551A - (meth)acrylic ester mixture - Google Patents

Abstract

PURPOSE:To obtain the title novel composition suitable as a diluent for ink, coating compound, etc., producible from a reaction product of tripentaerythritol and/or tetrapentaerythritol and epsilon-caprolactone and a (meth)acrylic acid. CONSTITUTION:A novel (meth)acrylic ester mixture obtained by reacting a reaction product of tripentaerythritol and/or tetrapentaerythritol and epsilon- caprolactone with acrylic acid or methacrylic acid or a blend thereof. The mixture has low viscosity, has high curing rate and high hardness and excellent flexibility of cured material. The mixture can be readily polymerized by heat ultraviolet rays or radiation or in the presence of a radical initiator. Therefore, the mixture is especially useful as a diluent for ultraviolet-curing type or electron radiation curing type printing ink or coating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel (meth)acrylic acid ester mixture that can be easily polymerized in the presence of hot ultraviolet light, radiation, or a radical initiator.

(Prior Art) As a conventionally well-known polyfunctional (meth)acrylic acid ester, for example, the name opentyl glycol di(
meth)acrylate, 1,6-hexanethiol di(meth)acrylate, polyethylene glycol di(meth)
Acrylate, bisphenol A dioxyethyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Ellis Little Hexa (
Examples include meth)acrylate.

(Problems to be Solved by the Invention) These polyfunctional (meth)acrylic esters are used as UV-curable or electron beam-curable resins as vehicles for 2PO4 and UV-curable inks. .

Among these polyfunctional (meth)acrylic esters,
Examples of cured coatings with high hardness include pentaerythritol tetra(meth)acrylate and diventae IJ sultol hexa(meth)acrylate. However, there is a demand for materials with even higher hardness, and these materials have the drawbacks of being waxy and hot at room temperature, having a high viscosity, and being difficult to handle.

(Means for Solving the Problems) The present invention provides a novel (meth)acrylic acid ester mixture with low viscosity and excellent curability, which is particularly useful as a diluent for ultraviolet curable or electron beam curable printing inks and paints. Our goal is to provide the following. Furthermore, those that give a highly hard cured coating film generally have the disadvantage of being brittle, and those that give a soft cured coating film have a disadvantage of slow curing speed because they have a small number of functional groups. However, the novel (meth)acrylic ester mixture provided by the present invention is more flexible than the conventionally known (meth)acrylic esters, provides a coating film with high hardness, and has extremely high curability. Are better. Specifically, the present invention relates to a (meth)acrylic acid ester mixture of a reaction product of tripentaerythritol and/or tetrapentaerythritol and ε-caprolactone.

This novel (meth)acrylic acid ester mixture can be prepared by reacting a reaction product of tripentaerythritol and/or tetrapentaerythritol with ε-caprolactone and acrylic acid or methacrylic acid or a mixture thereof. For one hydroxyl group equivalent of tripentaerythritol and/or tetrapentaerythritol, ε
- The amount of caprolactone used is preferably 0.1 to 5 chemical equivalents, particularly preferably 0.5 to 2.0 chemical equivalents.

The reaction is preferably carried out using a catalyst under an inert gas (eg, nitrogen, carbon dioxide, etc.) atmosphere.

Specific examples of the catalyst include organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, and tin compounds such as tetraphenyltin, dilauryltin oxide, and stannous chloride.

The amount used is preferably 0.0001-1.0% by weight, particularly preferably 0.01-0.2% by weight, based on the weight of ε-caprolactone.

The reaction temperature may be in the range of 50 to 300°C, preferably 100 to 200°C.

The amount of acrylic acid or methacrylic acid used per 1 hydroxyl group equivalent of the reaction product of tripentaerythritol and/or tetrapentaerythritol and ξ-caprolactone is usually 1 to 2.0 chemical equivalents, preferably 1.1 to 1.
．． 5 chemical equivalents.

The reaction is accelerated by using a catalyst and by distilling off the water produced. Such catalysts are acidic catalysts such as sulfuric acid and P-toluenesulfonic acid, and the amount used is usually 0.1-10 mol%, based on acrylic acid or methacrylic acid.
Preferably it is used in an amount of 1 to 5 mol%. It is advantageous to use an azeotropic solvent to distill off the water produced by the reaction.

Such azeotropic solvents have a boiling point of 60-150°C,
Any substance that can be easily separated from water can be used, but aliphatic hydrocarbons such as n-hexane and n-hebutane, aromatic hydrocarbons such as henzene and toluene, and alicyclic hydrocarbons such as cyclohexane are suitable. ing. The amount used is usually 5-70% by weight of the reaction mixture.

The reaction temperature may be in the range of 60 to 150°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.
A polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, P-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, α-nitroso-β-naphthol, P -benzoquinone, 2,5-dihydroxy-P-quinone, phenothiazine, N-nitrosodiphenylamine, copper salts and the like. The amount used is usually 0.0 to the reaction mixture.
It is 1 to 1% by weight. The (meth)acrylic acid ester mixture of the present invention thus obtained can be used for industrial purposes by washing with water or aqueous alkaline solution, etc., or separating it from the solvent by a method such as residual pressure distillation, if necessary. used for. The (meth)acrylic ester mixtures are useful as paints, hard coats, ink compositions and electronic materials, 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, the photopolymerization initiator includes many types of photoinitiators known 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 acid ester mixture can be used alone or in combination with other monomers or polymers. This novel (meth)acrylic ester mixture can also be polymerized by addition of organic peroxides.

(Example) This will be explained below using examples.

Example 1 356 g of tripentaerythritol, 1026 g of ε-caprolactone and 0.3 g of stannous chloride were charged,
At a reaction temperature of 170°C, ε-caprolactone in the reaction solution was 0.
．． The reaction was continued until the concentration became 1% by weight or less to obtain a reaction product of tripentaerythritol and ε-caprolactone. This substance is a waxy substance with an OH value of 242 KOH.
/g.

691 g of the reaction product of tripentaerythritol and ε-caprolactone obtained above 346 g of acrylic acid, P-1
- 20 g of luenesulfonic acid, 3 g of hydroquinone, and 560 g of benzene are charged and heated. The produced water 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. 72g of water
Once formed, it was cooled. The reaction temperature was 84-89°C.The reactor mixture was dissolved in 1600g of benzene and 400g of cyclohexane, and 20% caustic soda water was added. After neutralizing with 8 liquid, wash 3 times with 400 g of 20x saline solution. The solvent was distilled off under reduced pressure to obtain 771 g of a pale yellow liquid. This material has the following properties.

Viscosity (25°C) 210° cps Refractive index (25°C) 1.4825 The results of nuclear magnetic resonance (NM) measurement of the obtained product are shown below.

No, absorption frequency (llz) 1
2607.421 2 2597.656 3 2556.640 4 2498.046 5 2488.281 6 1974.609 1960.937 1931°640 1921.875 1191.406 1158.203 1126.953 1 052.734 964.843 943.359 660.156 646.484 507.812 425.781 382.812 367.187 o, oo.

The above measurements were carried out by a proton decoupling method using tetramethylsilane as a reference substance and deuterated chloroform as a solvent.

Example 2 Mixture of tripentaerythritol and tetrapentaerythritol (tripentaerythritol 57.3χ, tetrapentaerythritol 25.6%, hydroxyl group content 33%) 200 g, ε-caprolactone 29
2.5 g of stannous chloride and 0.15 g of stannous chloride were charged, and at a reaction temperature of 170°C, ε-caprolactone in the reaction solution was reduced to 0.1
The reaction was continued until the concentration of tripentaerythritol and tetrapentaerythritol was reduced to ε
- A reaction product of caprolactone was obtained. This material is a wax-like substance and has a 011 value of 415 ■KOH/g. Reaction product 4 of the mixture of tripentaerythritol and tetrapentaerythritol obtained above and ε-caprolactone
03g acrylic acid 259g5P-1-luenesulfonic acid 15g, hydroquinone 2g1Hensen 400
g, 500 g of cyclohexane was charged, heated, and cooled when the produced water reached 54 g. The reactor mixture was dissolved in 1200 g of benzene and 300 g of cyclohexane, and 2
After neutralizing with ox caustic soda aqueous solution, 20x saline solution 40
Wash 3 times at 0g. The solvent was distilled off under reduced pressure to obtain 485 g of a pale yellow liquid.

This material has the following properties.

Viscosity (25℃) 3400 CP
S refractive index (25° C.) 1.4831 The results of nuclear magnetic resonance (NMR) measurement of the obtained product are shown below.

No, absorption frequency (It z ) 1
2607.421 2 2597.656 3 2498.046 4 2486.328 5 1974.609 6 1960.937 7 1931.640 8 1921.875 9 1191.406 IQ 1158.20311
1126.953 12 1052.734 13 964.84314
943.35915
660.15616
646.48417
507.81218
425.78119
382.81220
367.18721
0.000 Example 3 Mixture of tripentaerythritol and tetrapentaerythritol (tripentaerythritol 57.3χ, tetrapentaerythritol 25.6χ, hydroxyl group content 33% by weight) 200g, ε-caprolactone 44
3g and 0.22g of stannous chloride were charged, and the reaction temperature was 17.
ε-caprolactone in the reaction solution at 0°C is 0.1% by weight
The reaction was continued until the following reaction was achieved, and a reaction product of a mixture of tripentaerythritol and tetrapene erythritol and ε-caprolactone was obtained.

This substance is a waxy substance with an OH value of 320mgK.
OH/g. When the amount of the reactant obtained above was 350 g, 207 g of methacrylic acid, 12 g of P-toluenesulfonic acid, and 36 g of hydroxide, it was cooled. The reaction mixture was dissolved in 1500 g of toluene, neutralized with a 20x aqueous sodium hydroxide solution, and washed three times with 400 g of a 20x saline solution. ?
Agent 8 was distilled off under reduced pressure to obtain 403 g of pale yellow 11 compound. This material has the following properties.

Viscosity (25℃) 2090 CP
S refractive index (25° C.) 1.4827 The results of nuclear magnetic resonance (NMR) measurement of the obtained product are shown below.

No, absorption frequency (It z ) 1
2607.421 2 2597.656 3 2515.625 4 2503.906 5 2050.781 6 2042.968 7 1892.578 8 1880.8599
1191.40610
1158.20311
1126.95312
1054.68713
966.79614
962.89015
945.31216
662.10917
646.48418 50
7.81219 425.
78120 382.8
1221 367,. 18
722 273.4372
3 0.000 Application Examples 1 to 3 The compounds obtained in Examples 1 to 3 and photopolymerization initiators were blended as shown in Table 1, cured with ultraviolet light, and measured for pencil hardness, towability, and curability. .

Curability: Expressed in seconds until dry to the touch after irradiation with ultraviolet rays.

Pencil hardness: Pencil hardness measured in accordance with JIS 5651-1966 using a test piece coated with a roll coater to a thickness of 25 μm on a hard PVC board and cured by irradiation with ultraviolet rays.

Towability: It was coated on a hard PVC sheet with a roll coater to a thickness of 25 μm, cured by irradiation with ultraviolet rays, and the cured film was bent at 180° C. and the condition of the cured film was observed.

◎--・--No abnormality○ - Slight cracking × Cracking on the entire surface Table-1 (Effects of the invention) The (meth)acrylic acid ester mixture of the present invention has a low viscosity and a fast curing speed (, cured product It has high hardness and good towability.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] A (meth)acrylic acid ester mixture of a reaction product of tripentaerythritol and/or tetrapentaerythritol and ε-caprolactone.