JPH0128764B2 - - Google Patents

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 supplied in the form of an alkyd resin synthesized from unsaturated dibasic acids, saturated dibasic acids, or their anhydrides and polyhydric alcohols, and dissolved in vinyl monomers. Ru.
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 in a solvent-free form and molded at room temperature and pressure. It is also possible to perform heat-curing molding. In addition, the cured product has excellent physical and chemical properties and is easy to use, so it can be used as a decorative board.
It is used in a wide variety of applications, including paints, molded products, and FRP. However, unsaturated polyester resin compositions have the disadvantage that the curing reaction is inhibited by oxygen in the air. The molded product surface may be delayed and remain sticky for a long time, the surface hardness may be insufficient, or the surface of the molded product may turn white when exposed to water. Conventionally, in order to eliminate such defects, wax was added to unsaturated polyester resin, and a physical method was used to form a wax layer on the resin surface during curing to prevent contact with air, and alkyd resin components. Chemical methods using allyl glycidyl ether, tetrahydrophthalic anhydride, etc., which easily react with oxygen, have been used. However, these methods have various practical obstacles. In the method of adding wax, wax remains on the surface of the cured product, which may cause the surface to lose its luster, and if an adhesive process such as secondary lamination is required after primary lamination with FRP etc., the primary lamination surface and the secondary lamination may Since the adhesion to the surface is significantly reduced, processing treatments such as buffing and sanding are required. In addition, methods using components that easily react with oxygen (allyl ethers) such as allyl glycidyl ether tend to gel during alkyd resin synthesis, complicating the process. It is difficult to dry and the surface hardness is not sufficient. The object of the present invention is to provide an unsaturated polyester resin composition that improves these drawbacks. The present invention is characterized by: (a) an unsaturated polyester obtained by reacting an allyl ether, a polyhydric alcohol, an αβ-unsaturated polybasic acid, and, if necessary, a saturated polybasic acid; (b) a general formula: (l, m, n are integers of 1 or 2, and these may be the same or different) One or more unsaturated bonds between some or all of the hydroxyl groups of the isocyanurate and carbon-carbon Contains an isocyanurate derivative having an unsaturated bond in the side chain obtained by carrying out an esterification reaction with an unsaturated monobasic acid or a lower alkyl ester thereof, and optionally a polymerizable monomer c. The present invention relates to an unsaturated polyester resin composition. Examples of unsaturated polyesters include allyl ethers such as trimethylolpropane diallyl ether, pentaerythritol diallyl ether, glycerin monoallyl ether, allyl glycidyl ether, and monoallyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and penta- Erythritol, glycerin, trimethylolpropane, neopentyl glycol, sorbitol, polybutadiene glycol,
Polyhydric alcohols such as 1,3-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and αβ-alcohols such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid A saturated dibasic acid and, if necessary, a saturated polybasic acid such as phthalic anhydride, isophthalic acid, terephthalic acid, glutaric acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic anhydride, etc. by a known method. Unsaturated polyester obtained by reaction can be used. The isocyanurate derivative having an unsaturated bond in the side chain used in the present invention has the general formula (l, m, n are integers of 1 or 2, and these may be the same or different) One or more unsaturated bonds between some or all of the hydroxyl groups of the isocyanurate and carbon-carbon It is obtained by carrying out an esterification reaction between an unsaturated basic acid having the following or a lower alkyl ester thereof. The esterification reaction between the above isocyanurate and the above unsaturated monobasic acid or the above unsaturated monobasic acid lower alkyl ester is known. Although the above esterification reaction can be carried out without using a solvent, it is preferable to use a solvent such as toluene or benzene. Preferably, a catalyst such as para-toluenesulfonic acid or concentrated sulfuric acid is used. The reaction temperature is preferably in the range of 60 to 130°C. The above-mentioned isocyanurate derivative is an isocyanurate that undergoes an esterification reaction with the above-mentioned unsaturated monobasic acid by changing the molar ratio of the above-mentioned isocyanurate and the above-mentioned unsaturated monobasic acid or its lower alkyl ester. The number of hydroxyl groups can be varied. For example, if 3 moles of the above unsaturated monobasic acid or its lower alkyl ester are reacted with 1 mole of the above isocyanurate,
All of the hydroxyl groups of the isocyanurate are esterified with the above-mentioned unsaturated monobasic acids or lower alkyl esters thereof. If 1 mol of the above unsaturated monobasic acid or its lower alkyl ester is used per 1 mol of isocyanurate, on average one hydroxyl group of the isocyanurate will be the above unsaturated monobasic acid or its lower alkyl ester. An esterified product is obtained. Usually, the unsaturated monobasic acid or its lower alkyl ester is used in an amount of 0.5 to 5 moles per mole of the isocyanurate. Furthermore, the number of hydroxyl groups to be esterified in the isocyanurate can be changed by changing the reaction time. In the esterification reaction, it is not necessary to use only one type of unsaturated monobasic acid or its lower alkyl ester, and two or more types of unsaturated monobasic acids or lower alkyl esters thereof may be used. Isocyanurate derivatives are usually obtained not as a single compound but as a mixture, but in the present invention they may be used in the form of a mixture. Examples of unsaturated monobasic 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, angelic acid, undecylenic acid, oleic acid, linoleic acid, lyleric acid, etc. are used. As the lower alkyl of the unsaturated monobasic acid having one or more unsaturated bonds between carbon and carbon, the lower alkyl esters of the above-mentioned unsaturated monobasic acids are used, such as ethyl acrylate, butyl acrylate, Examples include methyl methacrylate and methyl oleate. An unsaturated monobasic acid having one or more unsaturated bonds between carbons or a lower alkyl ester thereof may be used alone or in combination of two or more. The heat resistance, interlayer adhesion, and adhesion to metal foil of the laminate obtained by changing the type of unsaturated monobasic acid or its lower alkyl ester, the combination thereof, and the molar ratio to the above isocyanurate. You can change your gender. To obtain excellent heat resistance, interlayer adhesion, and adhesion with metal foil, use tris(2-hydroxyethyl)isocyanuric acid acrylate and/or tris(2-hydroxyethyl)isocyanuric acid methacrylate ester. is preferred. Polymerizable monomers used as necessary include styrene monomer, chlorostyrene, divinylbenzene, tertiarybutylstyrene, styrene bromide, diallyl phthalate, methyl methacrylate, acrylic acid, acrylamide, phenylmaleimide, maleimide, Examples include vinyl acetate monomer. Although the effect of imparting air-drying properties to the isocyanurate derivative having an unsaturated bond in the side chain in the present invention is not clear, the trishydroxyalkyl isocyanurate derivative quickly absorbs oxygen that reacts with the generated radicals, which inhibits curing. It is considered difficult to accept. In addition, although the effect of improving grindability and surface hardness is not clear, since isocyanurate derivatives have three double bonds per molecule, the crosslinking density increases, which increases the elastic modulus of the cured resin and increases the surface hardness. It is believed that the hardness is high and therefore the grindability is 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 are added and the composition is cured at room temperature or by heating. It's okay. Alternatively, a photosensitizer or the like may be added and photocured. moreover,
It is also possible to add auxiliary materials such as colorants, fillers, internal mold release agents, and lubricants. In the present invention, from the above characteristics and workability, it is preferable that the amount of the unsaturated polyester is in the range of 30 to 90% by weight based on the unsaturated polyester resin composition. This will be explained below using examples. In the examples, "parts" means parts by weight. Example 0.01% by weight of hydroquinone was added to 0.5 mol of fumaric acid, 0.5 mol of phthalic anhydride, 0.95 mol of propylene glycol, and 0.2 mol of trimethylolpropane diallyl ether, and heated to 190°C in an inert gas stream to form an acid value of 20. An unsaturated polyester was synthesized. This was dissolved in styrene monomer and the styrene content was adjusted to 30% 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 allyl ether. On the other hand, 3% by weight of phosphoric acid based on the total weight of both was added to 0.33 mol of tris(2-hydroxyethyl) isocyanurate and 1 mol of acrylic acid, and the mixture was reacted for about 2 hours at a temperature of 130°C in a nitrogen gas stream. ,
Tris(2-hydroxyethyl)isocyanuric acid acrylate (C) (melting point 59-60°C, white powder) was obtained. Using these, air drying properties and grindability were investigated under the following conditions, and the results shown in the following table were obtained. In both cases, 1.0% by weight of Permec N (containing 55% methyl ethyl ketone peroxide, trade name of NOF Corporation) and 0.5% by weight of cobalt octenoate with a metal content of 6% by weight were added to the unsaturated polyester resin composition. , measured at 25°C. The thickness was adjusted to 200 microns using a percoater and coated on a glass plate.

【table】

[Table] It is a thing.
The unsaturated polyester resin composition of the present invention has excellent surface hardness and grindability of the cured product, and has excellent air drying properties.

Claims (1)

[Claims] 1 a Allyl ether, polyhydric alcohol, αβ
- Unsaturated polyester obtained by reacting an unsaturated polybasic acid and, if necessary, a saturated polybasic acid, b General formula (l, m, n are integers of 1 or 2, and these may be the same or different) One or more unsaturated bonds between some or all of the hydroxyl groups of the isocyanurate and carbon-carbon Contains an isocyanurate derivative having an unsaturated bond in the side chain obtained by carrying out an esterification reaction with an unsaturated monobasic acid or a lower alkyl ester thereof, and optionally a polymerizable monomer c. An unsaturated polyester resin composition. 2 The isocyanurate derivative is tris(2-hydroxyethyl)isocyanuric acid acrylic ester and/or tris(2-hydroxyethyl)
The unsaturated polyester resin composition according to claim 1, which is an isocyanuric acid methacrylate.