JPH02180849A - Novel (meth)acrylate compound - Google Patents

Abstract

NEW MATERIAL:A (meth)acrylate compound shown by formula I (R is H or CH3; n1 and n2 are average number of mols added; n1 and n2=1-10). EXAMPLE:A compound shown by formula II. USE:The compound can be readily polymerized alone by heat, ultraviolet rays, electron rays or in the presence of a radical polymerization initiator or copolymerized with another unsaturated group-containing compound and useful as vehicle of various coatings and ink composition, optical material such as lens, dental material, crosslinking agent of polymer, etc. The compound has low shrinkage factor of curing, low water absorption characteristics and excellent light resistance. PREPARATION:A compound shown by formula III is esterified with acrylic acid or methacrylic acid to give a compound shown by formula I. The compound shown by formula III is synthesized by adding epsilon-caprolactone to hydrogenated bisphenol A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel (meth)acrylate compound represented by the following general formula [1].

(In the formula, R represents H or CHi. 'I + '2 represents the average number of moles added, nl + n2 = 1 to I O) [1] The (meth)acrylate compound represented by the formula It can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of a radical polymerization initiator, and can be used as a vehicle for various coatings and ink compositions.
It is useful as optical materials such as lenses, electronic component materials, dental materials, polymer crosslinking agents, etc.

[Conventional technology]

Various polyfunctional (meth)acrylate compounds have been known. For example, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate,
These include ethylene oxide-modified bisphenol A di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

These polyfunctional (meth)acrylates are polymerized (cured)
The volumetric shrinkage is large, the water absorption is large, and the water resistance is poor.
Many of them have drawbacks such as insufficient light resistance and discoloration when exposed to sunlight.

[Problem to be solved by the invention]

The present invention provides various coatings, inks, optical materials, electronic component materials, dental materials, and various polymers that have excellent polymerizability, especially curability with ultraviolet rays and electron beams, low curing shrinkage and water absorption, and good light resistance. The purpose of this invention is to provide a novel polyfunctional (meth)acrylate compound that can be used as a monomer for crosslinking agents and the like.

[Means to solve the problem]

The present inventors have discovered that common polyfunctional (meth)acrylates exhibit large shrinkage during polymerization (curing), coloration due to light,
As a result of intensive study to solve problems such as lack of water resistance due to high water absorption, we discovered a compound represented by the general formula [1] as a new (meth)acrylate compound,
The present invention has now been completed.

1(-〇; Cl-12 [l] (in the formula, ■( indicates ■1 or CI-h. nl, ng indicate the average number of added moles, nl + ng = l ~ 10
Preferably 1 to 5) The compound represented by the general formula (1) is the following - Monna (It)
It can be obtained by esterifying the compound represented by with acrylic acid or methacrylic acid.

(In the formula, nl+n! indicates the average number of added moles, n, +
n2=l~10) Also, the compound represented by -Momonanarll) is hydrogenated bisphenol AK! -obtained by adding caprolactone.

Although the number of moles of ξ-caprolactone added can be adjusted freely, the average number of moles added is preferably 1Qmol or less.

If the average number of moles added exceeds 10 mol, the curing speed will be slow and the result will be impractical.

In general, the hydroxyl group 1 of alcohol (compound of -Momon [D])
The molar ratio of carboxylic acid to equivalent weight is between 1.0 and 2.0, preferably between 1.1 and 1.5.

The reaction is accelerated by using a catalyst and by distilling the water produced. Such a catalyst is an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid, and the amount used is 0.1 to 10 mol%, preferably 1 to 5 mol%, based on acrylic acid or methacrylic acid. . Advantageously, an azeotropic solvent is used to distill the water produced by the reaction. Such azeotropic solvents can be used as long as they have a boiling point of 60°C to 130°C and can be easily separated from water, but aliphatic hydrocarbons such as n-hexane and n-hebutane, benzene, and toluene are Suitable are aromatic hydrocarbons, hydrogen atoms, and alicyclic hydrocarbons such as cyclohexane. The amount used is usually 5 to 70 percent by weight of the reaction mixture. The reaction temperature is 60
The temperature may range from 130°C to 130°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°C to 120°C.

Although a polymerization inhibitor is usually already added to acrylic acid or methacrylic acid, the polymerization inhibitor may be added again during the reaction.

Such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiol, α-nitroso-β
-naphthol, p-benzoquinone, 2,5-dihydro-axy-p-quinone, phenothiazine, N-nitrosodiphenylamine, copper salts and the like. The amount used is usually 0.01 to 1% by weight based on the reaction mixture.

caprolactone-modified hydrogenated bisphenol A di(
The meth)acrylate is used for industrial purposes by washing it with water or an aqueous alkali solution, if necessary, or separating it from the solvent by a method such as vacuum distillation. This caprolactone-modified hydrogenated bisphenol A di(meth)acrylate is useful as a vehicle for various coatings and ink compositions, as a monomer for optical materials such as lenses, dental materials, electronic components, various polymer crosslinking agents, etc. It 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 commonly known in the art are included.

Radiation curing techniques and heat curing techniques are well known to those skilled in the art;
Curing can be done with each of them, so there is no difficulty in making it 5.

The caprolactone modified hydrogenation and suphenol A di(meth)
Acrylates can be used alone or in admixture with other monomers or polymers. This novel caprolactone-modified hydrogenated bisphenol A di(meth)
Acrylates can also be polymerized by acetic acid addition of organic peroxides.

(Example) Examples will be described below. Parts indicate parts by weight.

Example 1 Compound 70 having the following structure, which is a condensate of hydrogenated bisphenol A and ε-caprolactone, was added to a three-stone reactor equipped with a stirrer, a temperature controller, a thermometer, a condenser, and a separator.
9 parts mountain + 12 = 1 345.8 parts of acrylic acid, 11.8 parts of sulfuric acid, 3 parts of hydroquinone, 400 f of benzene! S, cyclohexane 10
・Prepare 0 parts, heat, and distill the resulting water together with the sol.
Only the water is condensed and removed from the system using a separator, and the solvent is returned to the reactor. Cooling occurred when 72 parts of water had been produced. The reaction temperature was 82°C to 90'C.

The reaction mixture was mixed with 800 parts of benzene and 20 parts of cyclohexane.
After dissolving in 0 parts and neutralizing with 20% caustic soda aqueous solution,
Wash three times with 400 parts of 20% saline. The solvent was distilled off under reduced pressure to obtain 786 parts of a pale yellow liquid having the following structure.

This material has the following properties.

Specific gravity (25℃) 1.0579 viscosity
degree (25℃) 2550 cps refractive index (2
0°C) 1.495 The absorption frequency of the obtained product was measured by high-resolution nuclear magnetic resonance (NN), and the results are shown below.

Absorption frequency (Hz) 1 173.091 2 166.203 3 165.683 4 130.467 5 130.077 6 129.168 7 128.648 8 79.268 9 77.188 10 74.980 11 7.3 ,81.0 12 69.652 13 64.324 % Absorption frequency (Hz) 14 43.402 15 43.012 16 36.645 17 34.566 18 32.226 19 30.667 20 28.328 21 25.469 22 24.819 23 21.180 24 20.531 25 0.000 In the above measurements, tetramethylsilane was used as the base material and chloroform was used as the solvent.
-H coupling measurements were performed, and the results finally showed the identification of the 01s D couple.

Among the above absorptions, Nn8,9.10 is of the solvent, Nn25
indicates the absorption peak position of tetramethylsilane.

l-Hydroxycyclohexylphenylketone (photosensitizer) 0.5 F, &% was added to a portion of the product and coated on a glass plate, then the coating was exposed to UV light to dry transparent. A film-like coating was obtained. This film-like coating has the following properties.

Specific gravity (25°C) 1.1051 Curing shrinkage rate (25°C) 4.27% Refractive index (20
"C) 1.514 Water absorption rate (23°C) 0.33% Curing shrinkage rate was determined as follows from the specific gravity d1 of the monomer before curing and the ratio N d2 of the film after curing.

The water absorption rate was expressed as the percentage weight increase after the coating film was immersed in pure water at 23° C. for 24 hours.

Example 2゜Hydrogenated bisphenol A and C-
A compound having the following structure which is a condensate of caprolactone 583 parts Formula: 173 parts of acrylic acid, 6 parts of sulfuric acid, 2 parts of hydroquinone,
320 parts of benzene and 80 parts of cyclohexane were charged, heated, and the same 89 parts as in Example 1 was obtained. When the reaction was busy and 36 parts of water was produced, the mixture was cooled. The reaction temperature was 82°C to 90°C. The reaction mixture was mixed with 800 parts of benzene and 2 parts of cyclohexane.
00 parts, neutralized with 20% aqueous caustic soda solution, and washed three times with 300 parts of 20% saline. The solvent was distilled off under reduced pressure to obtain 587 parts of a pale yellow liquid having the following structure.

HC=CHz nl + n, = 3 Absorption frequency (Hz) 173.475 173.091 166.203 130.467 129.038 128.518 79.268 77.188 74.980 73.420 69.262 64.064 43.012 36.645 Absorption frequency (I(Z) 15 36.125 16 34.435 17 34.045 18 32.226 19 30.667 20 28.328 21 25.469 22 24.819 23 21.180 24 20.531 25 0.000 Among the above absorptions, Nl'7.Fl, (l indicates the absorption peak position of the solvent. r+25 indicates the absorption peak position of tetramethylsilane.

0.5% by weight of 1-hydroxycyclohexylphenylketone (photosensitizer) was added to a portion of the product and cured for 5K as described in Example IK to obtain a clear dry film coating. . This film-like coating has the following properties: specific gravity (25℃>1.1173 cure shrinkage rate (25℃)
5℃) 4.48% Refractive index (20℃3 1.507% Water absorption rate (23℃)
> 0.72% [Effects of the Invention] According to the present invention, a novel polyfunctional (metal) compound is produced which has excellent polymerizability, particularly curability by ultraviolet rays and electron beams, has low curing shrinkage and water absorption, and has good light resistance. ) acrylate is provided.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents H or CH_3. n_1 and n_2 represent the average number of added moles, n_1 + n_2 = 1 to 10) (meta) acrylate compound