JPH0477024B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a low-odor resin composition that has excellent storage stability and good curing and drying properties. [Technical background of the invention and its problems] Conventionally, unsaturated polyester resins made by mixing unsaturated polyesters with polymerizable monomers are heat- or ultraviolet-curable resins that proceed with curing reactions using radical polymerization initiators. It has been widely used for coil impregnation and casting. However, styrene, which is commonly used as a polymerizable monomer, has a relatively low boiling point, and the polymerizable monomer evaporates both in the form of varnish and during heat curing, and has a strong odor, which significantly impairs workability. , there is a risk of causing air pollution and environmental pollution due to bad odors. In contrast, low-odor resin compositions that use acrylic esters or methacrylic esters as polymerizable monomers that have almost no odor either in the form of varnish or during curing, and that are less volatile during curing are in practical use. This contributes to improving the working environment in processing workplaces that do not have deodorizing equipment. However, as a characteristic of acrylic resins, low-odor resin compositions are stable for long periods of time due to the influence of oxygen in the air when they come into contact with air or have a large amount of dissolved air; It becomes unstable in a cured state, and furthermore, since it generally contains a curing accelerator such as a metal salt, there is a strong tendency for storage stability to be shortened. In order to avoid this phenomenon, there are methods to improve stability by adding polymerization inhibitors such as quinones and phenol derivatives, but if storage stability is significantly improved, curing and drying properties will deteriorate. It has been very difficult to simultaneously improve both of these properties in a low-odor resin composition using an acrylic acid ester polymerized monomer. [Object of the invention] The present invention was made in view of the above circumstances, and an object of the present invention is to provide a low-odor resin composition that has excellent storage stability and pot life, and has good curing and drying properties. . [Summary of the Invention] As a result of extensive research in order to achieve the above object, the present invention has discovered that the above object can be achieved by adding a special carboxylic acid. That is, the present invention provides an unsaturated polyester resin composition consisting of an unsaturated polyester and an acrylic ester or a methacrylic ester in a blended amount as a polymerizable monomer, and 2-pyridinecarboxylic acids and 2-quinoline. This is a low-odor resin composition characterized by containing 0.001 to 0.1% by weight of one or more compounds selected from carboxylic acids. The unsaturated polyester used in the present invention is the same as that commonly used, and consists of an unsaturated carboxylic acid and, if necessary, a saturated carboxylic acid as an acid component, a polyol as an alcohol component, and a modifying component added as necessary. . Unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid are used as unsaturated polybasic carboxylic acids, and examples of saturated polybasic carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, and tetrahydroanhydride. Saturated dicarboxylic acids such as phthalic acid, adipic acid, and sebacic acid are used.
Polyols mainly include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol,
Neopentyl glycol, 1,6-hexanediol, hydrogenated bisphenol A, alkylene oxide adduct of bisphenol A, glycerin,
Glycols such as pentaerythritol are used. In addition, modified components include those in which rosin, ester gum, drying oil fatty acids, semi-drying oil fatty acids, etc. are used as part of the acid component of unsaturated polyesters, those modified with isocyanate compounds, epoxy compounds, etc., cyclopentadienated oils, Those to which epoxidized oil or the like is added, and those to which various other petroleum resins, thermoplastic resins, etc. are added can be used as appropriate. Furthermore, it is also possible to use a mixture of other fillers, pigments, dyes, etc. Acrylic esters or methacrylic esters are used as polymerizable monomers in the present invention, but specifically, esters of lower alcohols such as methyl esters or butyl esters, lauryl (meth)acrylate, stearyl (meth)acrylate, )
Esters of higher alcohols such as acrylates,
2-hydroxyethyl (meth)acrylate, 2
-Esters of polyhydric alcohols with a hydroxyl group such as hydroxypropyl (meth)acrylate, esters of polyhydric alcohols such as ethylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc., and one type of these Or used as a mixture of two or more. Since (meth)acrylic ester is used as a polymerizable monomer, the amount of (meth)acrylic ester used is approximately 0.1 to 4 mol per mol of the acid component of the unsaturated polyester. It is copolymerized using a wide range of mole fractions, that is, almost arbitrary, relative to the unsaturated polyester. The one or more compounds selected from 2-pyridinecarboxylic acids and 2-quinolinecarboxylic acids used in the present invention include pyridine-2-carboxylic acid, pyridine-2,3-dicarboxylic acid, and pyridine-2,4-dicarboxylic acid. , pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid,
Examples include quinoline-2-carboxylic acid, 4-oxyquinaldic acid, quinoline-2,3-dicarboxylic acid, quinoline-2,8-dicarboxylic acid, and alkali metal salts thereof. These compounds are one of them
You may use one type or a combination of several types. The amount used is preferably 0.001 to 0.1% by weight based on the unsaturated polyester resin. If it is less than 0.001% by weight, it will have little effect on improving storage stability, and if it exceeds 0.1% by weight, curing and drying properties will deteriorate, which is not preferred. It is also possible to use polymerization inhibitors such as well-known quinones and phenol derivatives in combination. The low odor resin composition prepared as above is
Curing can be carried out by methods such as redox curing using a combination of a peroxide and a curing accelerator, ultraviolet curing using a known photosensitizer, and far infrared curing. Examples of this peroxide include benzoyl peroxide, methyl ethyl ketone peroxide,
Examples include ditertiary butyl peroxide, lauroyl peroxide, cumene hydroperoxide, and tertiary butyl peroxide. In addition, as a curing accelerator, for example, cobalt,
Examples include metal soaps such as copper, manganese, and lead, and tertiary amines. [Embodiments of the Invention] Next, embodiments of the present invention will be described. In the following "Examples", "parts" means "parts by weight". Further, the present invention is not limited to the following examples. Examples 1 to 5 An unsaturated polyester was obtained by reacting 95 parts of linseed oil fatty acid, 66 parts of maleic anhydride, 66 parts of adipic acid, and 103 parts of ethylene glycol. To this, 0.05 part of hydroquinone was added, and further 200 parts of 2-hydroxy methacrylate and 150 parts of stearyl methacrylate were mixed and diluted, and further 2.5 parts of 6% manganese naphthenate solution was added to obtain an unsaturated polyester resin composition. I got (). Obtained unsaturated polyester resin composition ()
Pyridine-2-carboxylic acid was added to 100 parts as shown in Table 1 to obtain a low odor resin composition. The storage stability, pot life, gelling time, and surface drying properties of the obtained compositions were tested and are shown in Table 1. Examples 6-7 An unsaturated polyester was produced by reacting 90 parts of soybean oil fatty acid, 69 parts of maleic anhydride, 44 parts of phthalic anhydride, 70 parts of propylene glycol, and 30 parts of glycerin. Add 0.05 part of hydroquinone to this, and add 2-hydroxypropyl methacrylate.
Mix 150 parts of ethylene dimethacrylate and dilute with 200 parts of ethylene dimethacrylate, and then add 6% cobalt naphthenate solution.
2.5 parts were added to obtain an unsaturated polyester resin composition (). A low odor resin composition was obtained by adding 0.03 part of pyridine-2,6-dicarboxylic acid or quinoline-2-carboxylic acid shown in Table 1 to 100 parts of the obtained resin composition (2). The obtained products were subjected to the same tests as in Examples 1 to 5, and the results are shown in Table 1. Comparative Example 1 The unsaturated polyester resin compositions () produced in Examples 1 to 5 were used as low odor resin compositions, and tests were conducted in the same manner as in Examples 1 to 5, and the results are shown in Table 1. Comparative Example 2 The unsaturated polyester resin compositions () produced in Examples 6 and 7 were used as low-odor resin compositions, and tests were conducted in the same manner as in Examples 1 to 5, and the results are shown in Table 1.

【table】

[Table] [Effects of the invention] The low odor resin composition of the present invention has storage stability,
It has an excellent pot life and has well-balanced properties without reducing curing and drying properties, and has great practical advantages.

Claims (1)

[Claims] 1. 2-pyridinecarboxylic acids and 2-pyridinecarboxylic acids are added to an unsaturated polyester resin composition consisting of an unsaturated polyester and an acrylic ester or a methacrylic ester in a blended amount as a polymerizable monomer.
- A low-odor resin composition containing 0.001 to 0.1% by weight of one or more compounds selected from quinoline carboxylic acids.