JPH07216006A - Production of cured product of photo-setting type unsaturated polyester composition - Google Patents

Abstract

PURPOSE:To produce a light-colored or a yellow and transparent cured product curable at normal temperatures without using a polymerization initiator at a low cost by photo-setting an unsaturated polyester resin prepared by reacting dicyclopentadiene with an acid containing an unsaturated dibasic acid/an alcohol. CONSTITUTION:This method for producing a cured product of a photo-setting type unsaturated polyester composition is to cure a composition consisting essentially of an unsaturated polyester prepared by reacting dicyclopentadiene with an acid component containing an unsaturated dibasic acid and an alcohol component and, as necessary, water by irradiation thereof with light. An unsaturated polyester obtained by reacting the unsaturated dibasic acid with dicyclopentadiene at 1:(0.1-2) molar ratio is used as the polyester. A cross-linking monomer may further be added to the polyester composition for use. The wavelength of the light used for irradiation is preferably 200-4000Angstrom .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cured product of a photocurable unsaturated polyester composition.

[0002]

2. Description of the Prior Art Conventionally, a method for curing an unsaturated polyester resin is to add a polymerization initiator and heat to cure the resin.
There are a method of adding an accelerating agent together with a polymerization initiator and curing it at a heating or normal temperature, and a method of adding a photopolymerization initiator and curing it in the presence of light. Of these, the method of curing at room temperature is not only economically desirable, but is a method particularly necessary for the production of processed products such as wood products, in which heating should be avoided. Combinations have been proposed.

As a combination of a polymerization initiator and an accelerator, for example, a combination of benzoyl peroxide and a dialkylaniline or toluidine derivative, a combination of methylethylketone peroxide and cobalt naphthenate, or a combination thereof with a dialkylaniline or toluidine derivative is known. Has been. However, when these accelerators are used, there is a drawback that the hue of the cured product is yellowish brown or light reddish purple, and the hue of the cured product, such as buttons and decorative boards, is particularly problematic. So could not be used in the product. On the other hand, the method of adding a photopolymerization initiator and curing in the presence of light can be cured even at room temperature to obtain a light-colored or light-yellow cured product, but the cost becomes high and it is difficult in industrial production. There was a problem.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, is a polyester resin which can be cured at room temperature, can obtain a hue of a light-colored or light-yellow transparent cured product, and is inexpensive in cost. It is intended to provide a method for producing a cured product of a photocurable polyester composition capable of producing a cured product.

[0005]

The present inventors have found that an unsaturated polyester in which dicyclopentadiene is added as a reaction component meets the above object, and completed the present invention. That is, the present invention is dicyclopentadiene, an acid component containing an unsaturated dibasic acid and an alcohol component,
Further, the present invention relates to a method for producing a cured product, which comprises curing a photocurable unsaturated polyester composition containing an unsaturated polyester as a main component, which is obtained by reacting water as necessary, with irradiation of light.

The unsaturated polyester used in the present invention is obtained by reacting dicyclopentadiene, an acid component containing an unsaturated dibasic acid and an alcohol component and, if necessary, water by a known method. As the acid component, for example, maleic anhydride, maleic acid, fumaric acid,
One or more unsaturated dibasic acids such as itaconic acid are used, and if necessary, saturated phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, etc. An acid other than the dibasic acid such as dibasic acid, benzoic acid and trimellitic acid may be used in combination. As the alcohol component, one kind or two or more kinds of glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol, and 1,6-hexazinediol are used. ,
If desired, alcohols other than glycols such as glycerin and pentaerythritol can be used in combination.

The unsaturated polyester used in the present invention is obtained by reacting dicyclopentadiene at a molar ratio of unsaturated dibasic acid: dicyclopentadiene of 1: 0.1 to 2 from the viewpoint of photocurability. It is preferable that the

In order to produce the unsaturated polyester used in the present invention, dicyclopentadiene, an acid component and an alcohol component may be mixed and reacted to polymerize, but dicyclopentadiene and an unsaturated dibasic acid may be mixed. After mixing and heating for addition polymerization, it is preferable to add an alcohol component and esterify. Here, a polymerization inhibitor such as hydroquinone may be used in the addition polymerization.
Also, water can be used as the reaction material. Esterification is an acid value of 20 for polyester produced from photocurability.
It is preferably in the range of -40.

The unsaturated polyester composition of the present invention may further contain a crosslinkable monomer. Here, examples of the crosslinkable monomer include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, vinyl acetate, and diacrylic phthalate. To be The compounding amount of the crosslinkable monomer is not particularly limited and can be adjusted according to various purposes such as reactivity, workability and the like, but generally, the total amount of the unsaturated polyester composition is set to 100 parts by weight. It is preferable to use the crosslinkable monomer in an amount of 0 to 60 parts by weight with respect to 100 to 40 parts by weight of the saturated polyester.

The unsaturated polyester composition obtained as described above can be cured by irradiation with light.
That is, the unsaturated polyester composition of the present invention undergoes photopolymerization at room temperature or high temperature only in the presence of light to produce a light-colored or light-yellow transparent cured product without using a photopolymerization initiator.

Therefore, the unsaturated polyester composition of the present invention is suitable as various molding materials and paints, and if necessary, various additives, for example, reinforcing agents such as glass fibers, curing of naphthenate cobalt and the like. An accelerator, a thixotropic agent such as erosile, a surface drying property-imparting agent such as wax, and the like can be contained.

For example, when the unsaturated polyester composition of the present invention is used as a coating material, after the desired additive is added according to the purpose, the composition is sprayed, brushed, or flow coated on a substrate. After coating with a method such as a roll coater or dipping, it can be cured by irradiation with light in an atmosphere of an inert gas such as nitrogen gas, an air atmosphere, or an atmosphere of an inert gas and air. Light sources used at this time include sunlight, carbon arc lamps composed of artificial light sources, mercury vapor lamps, etc., and those with a wavelength of 200 to 7500 Å, especially 200 to 4000 Å are used and can be cured by electron beams. Is.

[0013]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 1.0 mol of maleic anhydride, 1.0 mol of dicyclopentadiene and 1 water of water were placed in a 1-liter reaction kettle equipped with a heating device, a thermometer, a nitrogen gas blowing device and a condensation water distilling device. ．
0 mol and 0.07 g of hydroquinone were charged, the mixture was heated to 140 ° C. with stirring in a nitrogen atmosphere to carry out addition polymerization, and then 0.1 mol of propylene glycol and 0.5 mol of diethylene glycol were further charged. The mixture was heated to 210 ° C. and reacted at this temperature until the acid value reached about 25 to synthesize unsaturated polyester. 70 parts of this unsaturated polyester was dissolved in 30 parts of styrene monomer to obtain an unsaturated polyester composition.

Example 2 Maleic anhydride 0.9 mol, phthalic anhydride 0.1 mol,
An acid value of 0.6 mol of dicyclopentadiene, 0.2 mol of propylene glycol, 0.85 mol of ethylene glycol and 0.03 g of hydroquinone was operated in the same manner as in Example 1 using the same synthesizer as in Example 1. 30 unsaturated polyesters were obtained. 70 parts of this unsaturated polyester was dissolved in 30 parts of styrene monomer to obtain an unsaturated polyester composition.

Comparative Example 1 Maleic anhydride 0.5 mol, phthalic anhydride 0.5 mol,
Propylene glycol (0.8 mol), ethylene glycol (0.3 mol) and hydroquinone (0.03 g) were treated in the same manner as in Example 1 using the same synthesizer as in Example 1,
An unsaturated polyester having an acid value of 33 was obtained. 70 parts of this unsaturated polyester was dissolved in 30 parts of styrene monomer to obtain an unsaturated polyester composition.

The unsaturated polyester compositions obtained in the above Examples and Comparative Examples were evaluated for hue and hardness of a cured product by irradiation with light by the following methods, and the results are shown in Table 1. Hue After putting 5 g of each unsaturated polyester composition in a metal petri dish having a diameter of 6 cm, it was left outdoors for 4 hours on a sunny day, and the hue was visually observed. Hardness 120 g of each unsaturated polyester composition was impregnated into 3 layers of chopped strand mats cut out to 20 × 20 cm, left for 4 hours outdoors on a sunny day, and the hardness was measured with a Barcol hardness meter GYZ-J935.

[0018]

[Table 1]

[0019]

EFFECTS OF THE INVENTION According to the production method of the present invention, it can be cured by irradiation of light without using a photopolymerization initiator, the obtained cured product is transparent in light color or pale yellow, and the cost is low. . Therefore, the unsaturated polyester composition according to the present invention can be applied to various casting materials, buttons, decorative boards, FR
It is useful for molding materials such as P and paints.

Claims (3)

[Claims] 1. A photocurable unsaturated polyester composition comprising an acid component containing dicyclopentadiene, an unsaturated dibasic acid and an alcohol component, and an unsaturated polyester obtained by reacting water if necessary, as a main component. A method for producing a cured product, characterized in that the composition is cured by irradiation of light. 2. The unsaturated polyester is an unsaturated polyester obtained by reacting dicyclopentadiene at a molar ratio of unsaturated dibasic acid: dicyclopentadiene of 1: 0.1-2. A method for producing the cured product described. 3. The method for producing a cured product according to claim 1, wherein the unsaturated polyester composition is an unsaturated polyester composition further containing a crosslinkable monomer.