JPS5874708A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:An unsaturated polyester resin composition good in air driability, grindability and surface hardness, comprising an unsaturated polyester, a specified isocyanurate derivative and, if necessary, a polymerizable monomer. CONSTITUTION:The titled composition is prepared by mixing an unsaturated polyester obtained by reacting an allyl ester with a polymerizable alcohol, an alpha,beta-unsaturated polybasic acid and, if necessary, a saturated polybasic acid, preferably, in an amount of 30-90wt% based on unsaturated polyester resin composition, with an isocyanurate derivative having an unsaturation in the side chain, obtained by esterification between part or the whole of the hydroxyl groups in an isocyanurate of the formula, wherein l, m and n are each 1 or 2, and an unsaturated monobasic acid containing at least one carbon-to-carbon uusaturated bond, or a lower alkyl ester thereof and, if necessany, a polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to unsaturated polyester resin compositions.

An object of the present invention is to provide an unsaturated polyester resin composition that has good air drying properties, good grindability, and good surface hardness.

Generally, unsaturated polyester resin compositions are produced by synthesizing an alkyl E resin from unsaturated dibasic acids, saturated dibasic acids, or their anhydrides and polyhydric alcohols, dissolving this in vinyl monomer, and supplying it in round form. be done. This unsaturated polyester resin is crosslinked by copolymerization of the unsaturated bonds in the alkyd resin and the polymerizable monomer, and an insoluble and infusible cured product is obtained, so it is used without a solvent and can be used at room temperature. Pressure molding and heat curing molding are possible. First, the cured product has excellent physical and chemical properties, and is easy to use, so it is used in a wide variety of applications, such as rounded decorative boards, Ik materials, cast products, and FRP.

However, unsaturated polyester resin compositions.

The curing reaction has the disadvantage that it is inhibited by oxygen in the air, so even after the inside of the resin is sufficiently cured, the surface of the molded product that is exposed to the air is slow to cure and becomes sticky over a long period of time. 1) The surface hardness was insufficient, and the surface of the molded product turned white when exposed to water.

Conventionally, the ninth method for eliminating such defects has been the physical method of adding wax to unsaturated polyester resin to form a wax layer on the resin surface during curing to prevent contact with air, and alkyd resin components. Chemical methods have been used to react with oxygen and use penta-allyl glycidyl ether, tetrahydrophthalic anhydride, etc. However, these methods have some practical difficulties. In the method of adding wax, the wax remains on the surface of the cured product, resulting in loss of gloss on the first surface, and when an adhesion process such as secondary lamination is required after primary lamination with FRP etc. Since the adhesive strength with the surface gradually decreases, processing such as puffing or sanding is necessary.

In addition, in the method using a component that easily reacts with oxygen such as allyl glycidyl ether (oryl ether #I), gelation tends to occur during alkyd resin synthesis.

The process becomes complicated, and therefore, if the amount of allyl ethers used is reduced, air-drying properties are less likely to be achieved, and the surface hardness is also sufficient.

The object of the present invention is to provide an unsaturated polyester resin composition that improves these drawbacks.

The present invention is.

a, unsaturated polyester obtained by reacting allyl ether, polyfdfiflucol, αβ-unsaturated polybasic acid and, if necessary, saturated polybasic acid, b, general formula % formula %) (z, rn, n are l or 2, which may be the same or different) An incyanurate conductor having an unsaturated bond in the side chain obtained by an esterification reaction with an acid or a lower alkyl ester thereof, and optionally a C0 polymerizable monomer. The present invention relates to a saturated polyester resin composition.

Examples of unsaturated polyesters include trimethylolpropane diallyl ether, pentaerythritone, ludiallyl ether, glycerin monoallyl ether, allyl glycidyl ether, monoallyl alcohol nato allyl ether, ethylene glycol, phlopylene gelicol, diethylene glycol, and trimethylalcohol. Ethylene glycol, dipropylene glycol, pentaerythritol.

Glycerin, trimethylolpropane, neopentyl glycol, sorbitol, polybutadiene glycol,
Polyhydric alcohols such as 1.3-7'tanediol, 1.6-hexanediol, 1.4-cyclohexane dimetatool, hydrogenated bisphenol A, and αβ- such as maleic anhydride, maleic acid, fumaric acid, itaconic acid, etc. Unsaturated dibasic acids and, if necessary, basic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, glutaric acid, adipic acid, cepatine, trimellitic acid, pyromellitic acid, and tetrahydrophthalic anhydride. An unsaturated polyester obtained by reacting with a known method can be used.

The incyanurate derivatives having an unsaturated bond in the side chain used in the present invention have the general formula (%) (j, m, and n are integers of 1 or 2 and may be the same or different) An esterification reaction is carried out between a part of the human xyl group of the isocyanurate shown in (9) and an unsaturated basic acid having one or more carbon-carbon unsaturated bonds or a lower alkyl ester thereof. There are things you can gain by doing this.

The esterification reaction between the above incyanurate and the above unsaturated basic acid or the above unsaturated basic acid lower alkyl ester is known.

The above esterification reaction can be carried out without using a solvent, but it is preferable to use a toluene or benzene solvent. Preferably, a catalyst such as radruene sulfonic acid or concentrated sulfuric acid is used.Reaction temperature strain 60-130
A range of 0.degree. C. is preferred.

The above incyanurate derivative can be produced by changing the molar ratio of the above incyanurate and the above unsaturated basic acid or its lower alkyl ester.
The number of hydroxyl groups in incyanurate that undergoes an esterification reaction with a basic acid can be changed. For example, if 3 moles of the above unsaturated basic acid or its lower alkyl ester are reacted with 1 mole of the above incyanurate,
All of the hydroxyl groups of the incyanurate are esterified with the supra-pi unsaturated-basic acid or its lower alkyl ester.

If 1 mol of the above unsaturated basic acid or its lower alkyl ester is used per 1 mol of incyanurate, on average, one hydroxyl group of the incyanurate is Varnish with ester'
A chilled product is obtained.

Usually, the above-mentioned unsaturated basic acid or its lower alkyl ester is used in the range of α5 mol to 5 mol per 1 mol of the above incyanurate.

Moreover, the number of hydroxyl groups to be esterified in 4-in cyanurate can be changed depending on one reaction time.

In the esterification reaction, it is not necessary to use only one type of unsaturated basic acid or its lower alkyl ester, and two or more types of unsaturated basic acids or lower alkyl esters thereof may be used.

Although incyanurate derivatives are usually obtained as a mixture rather than a single compound, they may be used in the form of hot metal products in the present invention.

Examples of unsaturated basic acids having one or more unsaturated groups between carbon and carbon used in the present invention include acrylic acid,
Methacrylic acid, crotonic acid, isocrotonic acid, tiglic acid, angelica II, +5'y'silenoic acid, oleic acid, I)/-luic acid.

Lilelenic acid and the like are used.

Unsaturated - having one or more unsaturated bonds between carbon and carbon
As the lower alkyl of the basic acid, the above-mentioned lower alkyl esters of unsaturated basic acids are used, such as ethyl acrylate, butyl acrylate, methyl methacrylate,
Examples include methyl oleate.

Unsaturated - having one or more unsaturated bonds between carbon and carbon
The basic acid or its lower alkyl ester may be used alone or in combination.

When the type of the above unsaturated basic acid or its lower alkyl ester, the combination thereof, and the molar ratio to the above incyanurate are changed, the heat resistance of the resulting laminate 9 Interlayer adhesion and adhesion to metal foil You can change your gender.

K for excellent heat resistance, single-layer adhesion, and adhesion with metal foils
It is preferable to use tris(2-hydroxyethyl)inocyanuric acid acrylic ester and/or tris(2-hydroxyethyl)inocyanuric acid methacrylic ester.

Polymerizable monomers used as necessary include house styrene monomer, chlorstyrene, divinylbenzene, tert-butylstyrene, styrene bromide, diallyl phthalate, methyl methacrylate, acrylic acid, acrylamide, phenylmaleimide, maleimide, vinyl acetate. There are seven tsumas, etc.

Although the effect of imparting air drying properties to the isocyanurate flange conductor having an unsaturated bond in the side chain in the present invention is not clear, the trishydroxyalkyl isocyanurate derivative quickly absorbs the oxygen that reacts with the generated radicals. It is thought that it is less susceptible to curing inhibition.

Although the effect of improving grindability and surface hardness is not clear, since the isocyanurate trout conductor has three double bonds per molecule, the crosslinking density increases, which increases the elastic modulus of the cured resin. 1. It is thought that the surface hardness is hard and therefore the grindability is also improved.

When using the unsaturated polyester resin composition of the present invention, organic peroxides, curing accelerators, curing retarders, etc. well known to those skilled in the art may be added and curing may be performed at room temperature or by heating. .

Alternatively, a photosensitizer or the like may be added and photocured.

Furthermore, auxiliary materials such as a coloring agent, a filler, an internal mold release agent, and a lubricant can also be added.

In the present invention, from the above characteristics and workability, it is preferable that the unsaturated polyester has a weight of 30 to 90 times the weight of the unsaturated polyester resin composition.

This will be explained below using examples. In the examples, "parts" means parts by weight.

Example 0.5 mole of fumaric acid, 0.5 mole of phthalic anhydride, 0.95 mole of propylene glycol, 0.2 mole of trimethylolpropane diallyl ether and 0.0 mole of hydroquinone.
1 weight of the mixture was added, and the reaction was heated to 190° C. in an inert gas stream to synthesize an unsaturated polyester having an acid value of 20. This was dissolved in a styrene monomer and adjusted to have a styrene content of 30 parts by weight to obtain an unsaturated polyester resin composition (A).

An unsaturated polyester resin composition (B) was obtained by using 0.1 mol of diethylene glycol in place of 0.2 mol of trimethylolpropane diallyl ether.

On the other hand, tris(2-hydroxyethyl)incyanuride
) 0.33 mole and 1 mole of acrylic acid were added with 3 weight of phosphoric acid based on the total weight of both 1, and 13% of phosphoric acid was added in a nitrogen gas stream.
Tris(2-hydroxyethyl)incyanuric acid acrylic ester (melting point 59-60°C) was reacted for about 2 hours at a temperature of 0°C.

A white powder) was obtained.

Using these, air drying properties and grindability were investigated under the following conditions, and the results shown in the first table were obtained.

In both cases, the unsaturated polyester resin composition was cured using Permec N (methyl ethyl ketone (-oxide 5).
5% content (NOF Co., Ltd. product name) 1.0% by weight,
0.5 weight of cobalt octenoate with a metal content of 6 weight gm was added, and the measurement was carried out at 25°C.

The thickness was adjusted to 200 microns using a percoater and coated on a glass plate.

The ease of polishing was examined below when sanding with a completely white (cloudy*1) sandpaper (S400).

*2 The composition of the wax is O and Oa parts of paraffin wax with melting points of 135″F and 1251, respectively (0.06 parts in total).
It is a mixture of

The unsaturated polyester resin composition of the present invention is as follows.

The cured product has excellent surface hardness and grindability, and has excellent air drying properties.

Claims (1)

[Claims] 1, a, 79 k: An unsaturated polyester obtained by reacting I--fl, a polyhydric alcohol, an αβ-unsaturated polybasic acid, and, if necessary, a saturated polybasic acid. b, general formula % formula %) (A, m, n are integers of 1 or 2 and they may be the same or different) - an unsaturated basic acid having one or more unsaturated bonds between carbons or a lower alkyl ester thereof; An unsaturated polyester resin composition comprising an incyanurate derivative having an unsaturated bond in a side chain obtained by carrying out an esterification reaction, and optionally a C0 polymerizable monomer. The unsaturated polyester resin composition according to claim 1, wherein the λ incyanurate derivative is tris(2-hydroxyethyl)incyanuric acid acrylic ester and/or tris(2-hydroxyethyl)incyanuric acid methacrylic ester. thing.