JPS62240647A - Isophthalic acid derivative - Google Patents

Abstract

NEW MATERIAL:An isophthalic acid derivative of formula I (R is H or methyl; A is -OCH2CH2-, group of formula II or formula III; n is 1-4). EXAMPLE:5-Chloro-2,4,6-trifluoro-bis(acryloyloxyethyl)isophthalate. USE:Useful as a material for a solventless radiation polymerization. The com pound effectively reduces the viscosity of viscous radiation-curable resin. A radiation-curable composition containing the compound can be wholly cured by high-energy radiation (e.g. ultraviolet ray, electron ray, X-ray, gamma-ray, etc.) without emitting volatile component and is suitable as a coating agent for wood, paper, card board, etc., impregnation agent, offset ink, adhesive and electronic raw material such as photo-resist, etc. PREPARATION:The compound of formula I can be produced e.g. by reacting the compound of formula IV with 5-chloro-trifluoroisophthalic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel compound having the following general formula that has not been described in any literature.

ROO (In the formula, R represents hydrogen or a methyl group, and n represents an integer from 1 to 4.) (Prior art) Using radiation polymerization reactions such as photopolymerization reactions, wood, paper, plastics, metals, etc. It is well known to form polymer thin films on the surfaces of various materials to produce coatings, paints, adhesives, etc. Conventionally, radiation-polymerizable substances or compositions have been used as thin film-forming materials using suitable volatile solvents. It was dissolved in water and applied or sprayed onto the object.

However, in recent years, materials that do not contain volatile components have been desired in order to avoid environmental pollution caused by solvent release into the atmosphere. A combination of an oligomer or polymer having a double bond and a monofunctional or polyfunctional acrylic ester, such as ethylene glycol diacrylate, triethylene glycol diacrylate, glycerin, trimethylolpropane, or polyacrylate of pentaerythritol natono-polyhydric alcohol. Attempts are being made to make it into a low-viscosity liquid so that it can be applied over a wide range of applications. The content of these acrylic groups in solvent-free radiation polymerization materials naturally depends on reactivity, viscosity and hardness, adhesiveness,
This affects various physical properties such as the elasticity of the cured film and its toxicity to the human body, but the acrylates that have been proposed so far cannot necessarily be said to have sufficient performance, so radiation polymerization materials with even better physical properties are needed. is desired.

(Problems to be Solved by the Invention) The present inventors have conducted various studies in order to develop a compound with excellent physical properties as a solvent-free radiation polymerization material. I found that it was suitable for

(Means for Solving the Problems) That is, the present invention provides isophthalic acid represented by the formula % (wherein R represents hydrogen or a methyl group, and A represents an integer of 1 to 4, respectively). The purpose is to provide rust conductors.

The compounds of the present invention will be explained in more detail below.

Although the compound of the present invention is a new compound that has not been described in any literature, various methods can be applied to its production as methods for synthesizing organic compounds. A typical method is
For example, as above. ) and 5-chloro-trifluoroisophthalic acid or its acid halide.

b) After reacting a compound represented by the formula HO(CH2CHO)nH (wherein R and n are as defined above) with 5-chloro-trifluoroisophthalic acid or its acid halide, the product is converted into acrylic A method of reacting with acid or methacrylic acid or its acid halide. C) A method of reacting 5-chloro-trifluoroisophthalic acid with ethylene oxide or propylene oxide or with its acid halide.

d) A method of reacting 5-chlorotrifluoroisophthalic acid and glycidyl (meth)acrylate.

etc.

5-chlorotrifluoroisophthalic acid or its acid halide in method (a) and method (b) and (meth)
The reaction with the acrylic ester or diol can be carried out without a solvent or by mixing in the presence of a solvent. As a solvent, an aprotic solvent is used in one example,
hydrocarbons such as benzene, toluene, xylene, hexane, methylera chloroform chloride, carbon tetrachloride,
Chlorinated hydrocarbons such as ethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane and other ethers, acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, acetonitrile, propio Examples include nitriles such as nitrile and benzonitrile, dimethylformamide, and dimethyl sulfoxide.

In methods (,) and (b), when using 5-chlorotrifluoroisophthalic acid = the molar ratio of (meth)acrylic acid ester or diol to 5-chlorotrifluoroisophthalic acid is not necessarily limited, but is usually 1
．． 5 to 10.0, preferably 2.0 to 3.0. (
If the molar ratio of the meth)acrylic acid ester or diol is less than 1.5 or more than 10.0, unreacted raw materials remain or by-products are generated, which is not preferable because a purification step is required. As a method for esterification reaction,
Conventional methods can be used. That is, in the presence or absence of a solvent such as benzene, toluene, xylene, tetrahydrofuran, or methylene chloride, and in the presence of a catalyst such as sulfuric acid, para-toluenesulfonic acid, or a sulfonic acid type ion exchange resin, usually at 70°C to 180°C. , preferably 80°C
Esterification is carried out at ~160°C.

When using 5-chlorotrifluoroisophthalic acid halide = The molar ratio of (meth)acrylic acid ester or diol to 5-chlorotrifluoroisophthalic acid halide is not necessarily limited as described above, but is usually 0.
5 to 5.0, preferably 0.7 to 3.0. The esterification reaction can be carried out by a conventional method, for example, usually at -10°C to 80°C in the presence or absence of the above-mentioned solvent.
Preferably, the reaction is carried out at -5°C to 60°C. At this time, alkalis such as caustic potash and caustic soda, alkaline salts such as potassium carbonate and soda carbonate, tertiary amines such as pyridine, triethylamine, and DBU ≧〒 React in the presence of quaternary ammonium salts such as ethylbenzylammonium chloride. It can be performed.

The amount of these alkalis, alkaline salts, and tertiary amines to be used is usually 0.5 to 3.5 mol, preferably 1.0 to 3.0 mol, per 1 mol of acid halide.

The amount of (meth)acrylic acid or its acid halide used in the reaction product of 5-chlorotrifluoroisophthalic acid or its acid halide with diols is usually 1.0 to 3.0 mol per 1 mol of the former. , preferably 1.5-2
．． It is 5 moles. A conventional method can be used for the esterification reaction. That is, when using 5-chlorotrifluoroisophthalic acid halide, the temperature is usually -10°C in the presence or absence of the above-mentioned solvent.
The reaction is carried out at 80°C, preferably -5°C to 60°C.

At this time, the reaction can be carried out in the presence of an alkali such as caustic potash or caustic soda, an alkaline salt such as potassium carbonate or sodium carbonate, or a tertiary amine such as pyridine, triethylamine, or DBU. These alkalis, alkaline salts, 3
The amount of grade amines used is usually 0.00% per mole of acid halide.
5 to 3.5 moles, preferably 1.0 to 3.0 moles are used.

In method (c), the method for adding ethylene oxide or propylene oxide to 5-chlorotrifluoroisophthalic acid includes an alkali catalyst such as caustic soda, caustic potash, sodium methylate, triethylamine, D
BU,) in the presence of an amine catalyst such as lyethylenediamine, a quaternary ammonium salt catalyst such as tetramethylammonium chloride, etc., at a temperature of usually 50°C to 170°C and under a pressure of normal pressure to 10 Wc4. be able to. Benzene, toluene, methylene chloride, ethylene dichloride, acetonitrile, diglyme, and other solvents can be used in this reaction.

In method (d), 5-chlorotrifluoroisophthalic acid and glycidyl (meth)acrylate are reacted in the presence or absence of a solvent that can be used in method (,), and a catalyst that can be used in method (c). Usually 50 to 150°C, preferably 60 to 130°C in the presence of
An example is a method of reacting at °C.

When producing the compound of the present invention, it is usually preferable to use a polymerization inhibitor in the process in which (meth)acrylic acid and its derivatives are used. Polymerization inhibitors include hydroquinone, methylhydroquinone, benzoquinone,
Commonly used materials such as hydroquinone monomethyl ether, phenol, phenothiazine, nitrobenzene, sulfur, various copper salts, and amines can be used.

Typical examples of methods for producing the compounds of the present invention are shown below.
We will explain more specifically, but these are just examples.
Therefore, it goes without saying that the manufacturing method is not limited to these.

Synthesis Example 1 5-chloro-2,4,6-)lifluoro-bis(acryloyloxyethyl)inphthalate 5-chloro-2,
4,6-)lifluoroisophthalic acid 25.51 (10
0 mmol) and a catalytic amount of dimethylformamide were added to thionyl chloride 50- and refluxed for 2 hours. Thionyl chloride was distilled off under reduced pressure, and 5-chloro-2,
4,6-)lifluoroisophthalic acid chloride in 26.
I got 2g. (Yield 90%). Tetrafluoroisophthalic acid chloride 2.92. ! 9 (10 mmol) was dissolved in 20 mmol of dry methylene chloride, and 2.55 mmol of hydroxyethyl acrylate containing 2000 ppm of methylhydroquinone as a polymerization inhibitor was prepared under a nitrogen stream.
2 mmol). Pyridine after water cooling 1.741
(22 mmol) was added dropwise. After further stirring for 2 hours at room temperature, water was added, extracted with methylene chloride, washed with water, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by aluminum oxide column chromatography using a developing solution (n-hexane/ethyl acetate = 171) to obtain 2.88 g of the title compound. (Purity 94%, yield 60%) 19Fn
mr (CDCty/DMSO-do): δ28.
5 (d, 2F, Jrr=4.3 Hz) 31
．． 5(d,IP,Jrr=4.3Hz)IR(nea
t): 1735 (C=0), 1
640 (C=C).

1780 (C=C) In the synthesis example, "F'nmr" indicates the analysis by nuclear magnetic resonance (NMR) spectroscopy of 19p, and δ indicates the intramolecular content of the compound measured using trifluoroacetic acid as an external standard. In the chemical shift value (ppm) of F, d indicates that the absorption peak at the chemical shift value is a doublet, and S indicates that it is a singlet.

JFF represents a coupling constant based on spin coupling between F atoms in a molecule, and Hz represents a frequency in Hertz.

IR indicates the wave number (cIn-1) of the main absorption band among the results of infrared spectroscopic analysis using the KBr tablet method.

Synthesis Example 2 5-Chloro-2,4,6-)lifluoro-bis(acryloyloxyethoxyethyl)isophthalate In Synthesis Example 1, 3.521 (22 mmol) of hydroxyethoxyethyl acrylate was used instead of hydroxyethyl acrylate. ) to obtain 3.46 # of the title compound in the same manner as in Synthesis Example 1.

(Purity 95%, yield 61cm) 19Fnmr (CDCl2): δ29.0 (d
, 2F, JFF=4.3Hz) 32.0 (
d, I F, JFF=4.3H2)IR(n
eat): 1735 (C=C), 1640
(C=C).

1780 (C=C) Synthesis Example 3 5-Chloro-2,4,6-trifluorobis(methacryloyloxyisopropyl)isophthalate In Synthesis Example 1, hydroxyisozorobyl methacrylate was substituted for hydroxyethyl acrylate. 3
．． Using 48.9, the title compound 3.279 was obtained in the same manner as in Synthesis Example 1. (Purity 93chi.

Yield 60%) 19Fnmr (CDCl2): δ28.8 (d,
2F, JFF=4.5Hz) 31.8 (d, I
F, JPIP=4.5Hz)IR(neat)
:1740(C=C), 1650(C=C)
.

1780 (C=C) Synthesis Example 4 5-chloro-2,4,6-trifluoro-bis(methacryloyloxy-2-hydroxyzolobyl) inphthalate 5-chloro-2,4,6-)lifluoroisophthalate acid 2
5.4 fi (100 mmol) in acetonitrile #
Glycidyl methacrylate 31.2JF (220 mmol) containing 2000 ppm of methylhydroquinone as a polymerization inhibitor was dissolved in 200-glycidyl methacrylate under a nitrogen stream.
) and 0.45 g (2 mmol) of triethylbenzylammonium chloride as a catalyst. After stirring for 8 hours under reflux, water was added, extracted with methylene chloride, washed with water, and dried over magnesium sulfate. The solvent was distilled off and purified by aluminum oxide column chromatography.Developing solution: n-hexane/ethyl acetate = 1/1
) The title compound 27.1.9 was obtained.

(Purity 95cm, yield 48cm) 19Fnmr (CDC43): δ47.1 (d
, JFF=18.55Hz )81.6 (d a d
# Jyv=9.93Hz +18.55Hz) IR (neat): 1730 (C=C)-16
40 (C=C).

1770 (C=C), 3450 (0-H) Specific examples of compounds that can be synthesized according to the above production method are shown in Table-
1, but this is merely an example, and it goes without saying that the compound examples are not limited to this. In addition, in the subsequent explanation, the compound numbers in Table 1 may be used.

Although the compound of the present invention can be used alone as a cured coating material, it is usually used in combination with a binder, which is a film-forming resin, to lower the viscosity of the resin.

The bonding agent used in the present invention is a high molecular weight compound containing at least one polymerizable reactive group such as (meth)acryloyl group in the molecule, epoxy type, ester type, urethane type, or ether type (meth). ) acrylates, and oil- and fat-modified products thereof, (meth)acrylate-modified products of polybutadiene.

Examples include unsaturated polyester. For example, ester-based (meth)acrylates include polyester (meth)acrylates obtained from polybasic acids and polyhydric alcohols, and representative examples include the following.

The compounds of the invention may be 1 to 100% by weight, preferably 5 to 7% by weight.
It can be present in the radiation-curable composition in a proportion of 0% by weight.

The compounds of this invention effectively reduce the viscosity of viscous radiation curable resins. Furthermore, radiation-polymerizable compositions using the compounds of the present invention may be treated with high-energy radiation, such as ultraviolet radiation,
The entire body is cured by electron beams, X-rays, gamma rays, etc., preferably ultraviolet rays, and volatile components are not released.

When polymerization is carried out using ultraviolet light, a photopolymerization initiator is usually used, but any compound commonly used for this purpose may be used. For example, acetophenones (acetophenone,
pt-butyltrichloroacetophenone, 2,2-soethoxyacetophenone, trichloroacetophenone,
2,2-dimethoxy-2-7enylacetophenone, etc.), thioxanthone (thioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, 2-isobutylthioxanthone, etc.), Michler ketones (4,4
'-bisdimethylaminobenzophenone, etc.), benzine ethers (benzoin methyl ether, benzoin butyl ether, etc.), benzyl dimethyl ketal, etc. can be used.

The above-mentioned photoinitiators may be used in a radiation-polymerizable composition using a compound of the present invention, depending on the intended use of the composition.
．． It can be used in amounts of 2 to 20%, preferably 1 to 8% by weight, which can be used alone or in combination with each other for synergistic effect. Useful additives to further increase polymerization reactivity include tertiary amines (such as triethylamine), phosphine or thioethers. These substances are added to the composition of the present invention in a range of 0 to
Preferably, it is used in an amount of 5% by weight.

In order to obtain a high degree of storage stability of the compounds of the present invention, as with any other system capable of carrying out vinyl polymerization, it is preferable to add a polymerization inhibitor. Examples of the polymerization inhibitor used here include p-methoxyphenol, hydroquinone, di-
Examples include phenolic compounds such as t-butyl-p-luzole, hydroquinone monomethyl ether, and phenothiazine. The amount added is determined by the required stability and the tolerance for loss of reactivity caused by the addition of the stabilizer. The type and optimum amount of stabilizer may be determined by occasional concentration tests at varying concentrations of stabilizer. Stabilizers are generally used in radiation curable compositions.
It is added in an amount of ooi to 1.0% by weight.

Radiation-curable compositions prepared using the compounds of the present invention can be used as coatings, impregnation agents, offset inks, gravure inks for wood, paper, card dates, plastics, leather, metals, textiles, ceramics, electronic components, printed circuit boards, etc. Suitable for use as inks and adhesives, photoresists, and other electronic materials. In addition, in these applications, a slip agent, a matting agent, an antifoaming agent, a leveling agent, etc. can also be used in combination, if necessary.

(Effects of the Invention) Representative test examples will be shown below to specifically explain the effects of the compounds of the present invention. However, these are merely examples, and it goes without saying that the application examples of the present invention are not limited to these.

Test Example 1 Darocure-1173 was added to each monomer as a photopolymerization initiator.
(Merck & Co., Ltd. 2-hydroxy-2-methyl #-1-phenylzoronone-1-one) 4.8 weight percent and 1.2 weight percent of benzophenone were added and dissolved uniformly, and the solution was mixed with 3 mil. Apply it on the glass plate with an applicator,
The curing properties were tested by irradiating ultraviolet rays and measuring the number of irradiations until the tackiness (dryness to the touch) disappeared. The results are shown in the table below.

Irradiation conditions Two pump output crabs 80W/l-m (lamp with ozone) Rung height: 1255m Conveyor speed: 15m/min [Equipment used: Uniqui Air System UVC-183 (manufactured by Ushio Inc.)] Test example-2 The same formulation and treatment as in Test Example 1 were performed, and the same test was conducted. However, among the irradiation conditions of Test Example-1, the lamp output was 160 W/crn (lamp with ozone).

Test Example 3 60 parts of the compound of the present invention or 60 parts of the comparative compound triethylene glycol diacrylate, 3 parts of benzophenone, and Dalochea-1173 (3 parts) were uniformly added to 40 parts of urethane oligomer Photomer 6008 (product of Diamond Jamrock Chemicals). It was blended. The viscosity of each mixture was measured at 20° C. using a B-type viscometer. Abrasion resistance was measured by applying the mixture on a degreased tin plate with a 3 mil applicator and immediately applying it under a high-pressure mercury lamp with an intensity of 160 W/cm at 10 m/Se at 12.53 m/Se.
After the coating was passed through the test tube, the coated surface was rubbed with absorbent cotton soaked in methyl ethyl ketone.The number of times of rubbing until a change occurred on the surface was measured. Water resistance was indicated by the presence or absence of a change in the surface condition of the resulting coating film after it was immersed in boiling water for 10 hours. The results are shown in the table below.

Test example-4 The same formulation as in Test Example 3 was used, and the same test was conducted.

However, among the irradiation conditions of Test Example-3, the number of irradiations was 4 times. The results are shown in the table below.

Claims (1)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is hydrogen or methyl group, A is -OCH_2CH_2- group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups or ▲ Numerical formulas, chemical formulas, tables, etc. isophthalic acid derivatives represented by ▼ group, n each represents an integer from 1 to 4).