JPS63280043A - Norbornanediol diester and production thereof - Google Patents

Abstract

NEW MATERIAL:A norbornanediol diester shown by formula I (R1 and R2 are each independently H or methyl). EXAMPLE:Norbornanediol diacrylate. USE:Useful as a curing component for printing ink of ultraviolet-curing type or electron beam curing type and for coating compounds. Having high curing rate and providing a cured material having excellent physical properties. PREPARATION:Norbornadiene is reacted with acrylic acid and/or methacrylic acid in the presence of an acid catalyst to give a compound shown by formula I. The reaction is preferably carried out in the presence of a polymerization inhibitor further by introducing molecular oxygen at about 20-130 deg.C, especially 40-90 deg.C. The amount of acrylic acid and/or methacrylic acid used is 2-10mol. based on 1mol. norbornadiene and the amount of the acid catalyst used is most suitably 1-20wt.%.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel norbornane diol diester that can be easily polymerized by heat, ultraviolet irradiation, ionizing radiation irradiation, or the presence of a radical initiator, and a method for producing the same. Regarding.

(Prior Art) In recent years, various acrylic esters or methacrylic esters have been used as curable components in ultraviolet curable or electron beam curable printing inks and paints. Among them, there are many examples of use of diester compounds, such as 1.6 hexanediol diacrylate and neopentyl glycol diacrylate.

Typical compounds include polyethylene glycol diacrylate. However, since these existing compounds do not necessarily have satisfactory properties such as surface hardening properties, surface hardness of cured products, and heat resistance, new G- or polyester compounds are being searched for. For example, JP-A-60-11
In Publication No. 78.

In JP-A-60-87280, the compound represented by the general formula (in formula 9, R1 is H or C, and n is 1 to 4) is described in JP-A-60-87280 (in formula 9, R1 is H or Cf- Compounds represented by It) have been disclosed, but none satisfy all of the required properties.

(Problems to be Solved by the Invention) The present invention provides a fast-curing compound that is useful as a curing component for ultraviolet curable or electron beam curable printing inks and paints.
The object of the present invention is to provide a new (meth)acrylic acid ester that provides embroidered products with excellent properties.

(Means for solving problems) The first invention is.

The present invention relates to a norbornane diol diester represented by the general formula (I) (wherein R1 and & each independently represent hydrogen or methyl group).

The norbornane diol diester according to the first invention is normal.

It is a mixture of two types of geometric isomers of the compound represented by and the compound represented by (in these formulas, IRI and & are the same as above). In this case, it is difficult, if not impossible, to obtain a purely single compound.

Therefore, it can be understood as a compound represented by the general formula t1), and in actual use, it is not necessary to use it alone, so it may be used in practice as a mixture of these isomers.

The second invention relates to a method for producing the norbornane diol diester.

That is, the second invention is a norbornane diol diester characterized in that a compound represented by the general formula (I) is synthesized by reacting norbornadiene and acrylic acid and/or methacrylic acid in the presence of an acid catalyst. Regarding manufacturing methods.

Examples of the acid catalysts include Lewis acids such as boron trifluoride, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as para-toluenesulfonic acid, heteropolyacids such as phosphotungstic acid and silicotungstic acid, and strong acidic ion exchange resins. can be mentioned. What is the amount of catalyst used?

1 to 20% by weight based on norbornadiene is preferred.

The entire amount of the catalyst may be added at once, but it may also be added in a number of portions. If the amount of catalyst is small, the reaction will not progress, and if the amount is large, there is no particular advantage.

In addition, the amount of acrylic acid and/or methacrylic acid used is
It is preferably 2 to 10 mol per mol of norbornadiene. If there is less than this, the 9 reactions will not proceed sufficiently, and
There is no particular advantage even if there are many.

In addition, in the actual reaction, the entire amount may be charged at once, or the norbornadiene may be added dropwise to the mixture of the acid catalyst and the acrylic acid and/or methacrylic acid, or conversely, the acrylic acid and/or Methacrylic acid may be added dropwise. Further, the reaction is preferably carried out in the presence of a polymerization inhibitor to prevent polymerization of the double bond of the acryloyl group and/or methacryloyl group.

The polymerization inhibitor is preferably used in the reaction solution at a concentration of 0.01 to 0.5% by weight. Examples of polymerization inhibitors include hydroquinone and p-methoxyphenol.

Examples include 4-dimethyl-6-t-butylphenol, p-benzoquinone, 45-diphenylbarabenzoquinone, phenothiazine, N-nitronediphenylamine, copper salt, and the like. In order to enhance the polymerization prevention effect, it is preferable to further blow molecular oxygen (or air) into the reaction solution. The reaction is generally carried out at a temperature of about 20-130°C, preferably 4°C.
The reaction is carried out at a temperature between 0 and 90°C for a time sufficient to reach equilibrium. Reaction times vary depending on the scale of production, type of raw materials, type of catalyst and reaction conditions employed.

In order to isolate the norbornane diol diester according to the present invention from the reaction solution after the completion of the reaction.

The following method may be used.

In other words, after the completion of the 9 reactions, the acid catalyst is neutralized by adding an equivalent or excess amount of alkali (sodium hydroxide, sodium methoxide, etc.), and then the excess alkali acid and/or methacrylic acid is recovered by distillation. . After this, the dinorbornane diol diester can be isolated by distillation. Also by distillation.

First, the catalyst neutralization salts are removed by water washing, P separation, etc.

It can be put to practical use, and distillation may be carried out after this.

Or make sure to use 9 reaction solutions! Depending on hexane.

After diluting with an organic solvent such as toluene, add an alkaline aqueous solution (
The acid catalyst and excess acrylic acid and/or methacrylic acid are removed by washing with an aqueous sodium hydroxide solution, etc., and when diluted with a solvent, the solvent is distilled off to obtain the norbornanediol diester. If necessary, it may be further purified by distillation.

The norbornane diol diesters of general formula (I) are useful as curable components in coating and ink compositions; they are resistant to radiation.

Alternatively, it can be cured 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 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. The norbornane diol diester may be used alone or with other monomers such as
Trimethylolpropane triacrylate.

For example, tri- or tetra-acrylates of pentaerythritol or resins containing unsaturated groups.

Unsaturated polyester, polyester acrylate.

It can be used as a curable component by mixing with resins such as epoxy acrylate and urethane acrylate.

This new norbornane diol diester can also be polymerized by addition of organic peroxides.

(Example) Hereinafter, "parts" means "parts by weight."

Example 1 345.6 parts of acrylic acid, 6.90 parts of boron trifluoride ethyl ether complex, and 0.91 parts of hydroquinone were charged into a reactor equipped with a stirrer, a temperature controller, a thermometer, and a cooling tube with 9 dropping funnels. The temperature was raised to 50°C. temperature 5
While maintaining the temperature at 0℃±5℃.

110.6 parts of norbornagene was added dropwise to the flask over about 15 minutes. Then, the temperature of the 9 reaction solution was raised to 80°C, and the reaction was continued at this temperature for 10 hours. After that, the reaction solution was cooled and the n-
It was dissolved in 400 parts of hexane, and neutralized with 500 parts of NaOH aqueous solution. After separating the aqueous layer, the oil layer was distilled off using a py-evaporator to obtain crude norbornane diol diacrylate. This was subjected to vacuum distillation at 120-122℃/0.5
189 parts of a mmHg fraction were obtained.

The norbornanediol diacrylate obtained here was analyzed by gas chromatography (column silicon 5g-522m
3φ, column temperature 00℃, injection temperature 250℃, carrier island approximately 50ml! /min, but as a result of mass spectrometry, both had a molecular weight of 9 and 236, and are considered to be two geometric isomers of norbornane diol diacrylate.

The following analytical data are for the isomer mixture described above.

Specific gravity (25℃): 1.117 Viscosity (25℃): 30.2 (CPS) Refractive index (20°C): 1.4889 Acid value: 0.08 mgKOH/g Elemental analysis value (chi): C,H Theoretical value 66.09 6.87 Actual value 65.98, 6.91 Infrared absorption spectrum: As shown in Figure 1.

Nuclear magnetic resonance spectrum: As shown in Figure 2.

Example 2 [Norbornanediol dimethacrylate] Into the same reaction apparatus as in Example 1 were added 4128 parts of methacrylic acid, 7.8 g of boron trisevenide ethyl ether complex, and 1.5 g of hihytroquinone.
049 was charged, and 921 parts of norbornagene was added dropwise at 50°C. The temperature was raised to 85°C and the reaction was continued for 6 hours. After the reaction, the treatment was carried out in the same manner as in Example 1, and the temperature was increased to 122-125°C/
192 parts of a 0.35 mmHg fraction were obtained. As in Example 1, mass spectrometry results showed that the molecular weight was 9 and 264.

It is believed to be two geometric isomers of norbornane diol dimethacrylate.

The following analytical data are for the isomer mixture described above.

Specific gravity (25℃): 1:080 Viscosity (25℃): 25.60PS Refractive index (20°C): 1.4840 Acid value: 0.07 mgKOH/g Elemental analysis value (%): C,,H Theoretical value 6 & 16 7.63 Actual value 6 & 20, 7.68 Infrared absorption spectrum: As shown in Figure 3.

Nuclear magnetic resonance spectrum: As shown in Figure 4.

Application Examples 1 to 2 60 parts each of norbornane diol diacrylate and norbornane diol dimethacrylate obtained in Examples 1 and 2, 40 parts of epoxy acrylate resin (Visco Toner 540 manufactured by Osaka Organic Chemical Co., Ltd.) and photosensitization. 1-hydroxycyclohexylphenyl ketone (
After mixing with 40 parts of Irgacure 184) manufactured by Chiha φ Geigy.

Film thickness: 100μm) e 21@
It was irradiated with a high-pressure mercury lamp from a distance of 10 cm for ultraviolet curing. The results are shown in Table 1.

Table 1 Note) 1) Number of seconds until dry to the touch 2) Tested according to JIS K-5400.

(Effect of the invention) Pertaining to the first invention. Alternatively, the norbornane diol diester represented by the general formula (I) obtained in the second invention is a new compound, and easily polymerizes under heat, ultraviolet irradiation, ionizing radiation irradiation, or the presence of a radical initiator, and can be used in inks, It is useful as a raw material for paints, etc.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of norbornane diol diacrylate obtained in Example 1, Figure 2 shows the nuclear magnetic resonance spectrum of the compound, and Figure 3 shows the infrared absorption spectrum of norbornane diol dimethacrylate obtained in Example 2. Spectrum and Figure 4 shows the nuclear magnetic resonance spectrum of the compound.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R_1 and R_2 each independently represent hydrogen or a methyl group) norbornane diol diester. 2. Norbornadiene and acrylic acid and/or methacrylic acid are reacted in the presence of an acid catalyst, and the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R_1 and R_2 are , each independently representing a hydrogen or methyl group) is synthesized.