JPS60108461A - Low-odor resin composition - Google Patents

Abstract

PURPOSE:To provide a low-odor resin composition having high storage stability and hardening and drying properties, by adding a 2-pyridinecarboxylic acid compound or a 2-quinolinecarboxylic acid compound to a resin composition composed of an unsaturated polyester and a (meth)acrylic acid ester. CONSTITUTION:An unsaturated polyester resin composition composed of (A) an unsaturated polyester and (B) an acrylic acid ester, methacrylic acid ester, and/ or their substituted derivative [e.g. 2-hydroxy-(meth)acrylate, stearyl (meth)acrylate, etc.] is added with 0.001-0.1wt% one or more compounds selected from 2- pyridine-carboxylic acids (pyridine-2,3-dicarboxylic acid, etc.) and 2-quinolinecarboxylic acids (e.g. 4-hydroxyquinaldic acid). The additive may be combined with conventional polymerization inhibitor such as quinones, phenol derivatives, etc. The obtained composition can be cured e.g. by redox curing using a peroxide in combination with a cure accelerator.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention 1] 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 the curing reaction 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, due to the unique properties of acrylic-based resin compositions, low-odor resin compositions may be exposed to air or have a large amount of dissolved air.
Although it is stable for a long time due to the influence of oxygen in the air, it becomes unstable when cut off from the air.
There was a strong tendency for storage stability to be shortened. In order to avoid this phenomenon, there is a method 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 is 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. The purpose 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 comprising an unsaturated polyester and an acrylic ester or methacrylic ester or a substituted derivative thereof, and a compound selected from 2-pyridine carboxylic acids and 2-quinoline carboxylic acids. Species or more of compounds, from 0.001 to
This is a low odor resin composition characterized by containing 0.1% by weight.

The unsaturated polyester used in the present invention is the same as the one 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. . As unsaturated polybasic carboxylic acids, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid are used, and as saturated polybasic carboxylic acids, phthalic acid,
Saturated dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, and sebacic acid are used. The polyols mainly include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexanediol, hydrogenated bisphenol A1 bisphenol A
Glycols such as alkylene oxide adducts, glycerin, and pentaerythritol are used.

In addition, modified components include those using rosin, ester gum, drying oil fatty acids, semi-drying oil fatty acids, etc. as part of the acid component of unsaturated polyesters, those modified with isocyanate compounds, epoxy compounds, etc., and cyclopentagenated oils. , epoxidized oil, etc., and various other petroleum resins, thermoplastic resins, etc. can be used as appropriate.

Furthermore, it is also possible to use a mixture of other fillers, pigments, dyes, etc.

Acrylic esters, methacrylic esters, or substituted derivatives thereof are used in the present invention, and specific substituted derivatives include 2-hydroxy (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lauryl (meth)acrylate. , stearyl (meth)
Examples include acrylate, ethylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc., and these may be used alone or as a mixture of two or more.

51 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, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 4-oxyquinaldic acid, quinoline-2,3- Examples include dicarboxylic acid, quinoline-2,8-dicarboxylic acid, and alkali metal salts thereof. One type of these compounds may be used, or several types may be used in combination. Moreover, the amount used is o, ooi to 0.0.
It is preferable to contain 1% by weight. If it is less than 0.001% by weight, the effect on improving storage stability will be small, and if it exceeds 0.1% by weight, curing and drying properties will deteriorate, which is not preferable.
In addition, 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 described above can be cured by redox curing using a combination of peroxide and a curing accelerator, ultraviolet curing by adding a known photosensitizer, far-infrared curing, etc. It can be hardened by a method.
Examples of the peroxide include benzoyl peroxide, methyl ethyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, and tert-butyl peroxide.

Examples of hardening accelerators include metal soaps such as cobalt, copper, manganese, and lead, and tertiary amines.

"Embodiments of the Invention" Next, embodiments of the present invention will be described. In the following "Examples", "1 part" means "1 part by weight".

Further, the present invention is not limited to the following examples.

To Example 1-5 95 parts of linseed oil fatty acid, 66 parts of maleic anhydride, 66 parts of adipic acid, and 103 parts of ethylene glycol were reacted to obtain an unsaturated polyester. Add 0.05 part of hydroquinone to this, mix and dilute 1 to 200 parts of 2-hydroxymethacrylate, and 150 parts of stearyl methacrylate, and then add 2.5 parts of 6% manganese naphthenate solution. An unsaturated polyester resin composition (I) was obtained.

Pyridine-2-carboxylic acid was added to 100 parts of the obtained unsaturated polynisder resin composition (I) 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-
Mix and dilute 150 parts of hydroxypropyl methacrylate and 200 parts of ethylene dimethacrylate,
Furthermore, 2.5 parts of 6% cobalt naphthenate solution was added to obtain an unsaturated polyester resin composition (I). 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 (I). . 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 (I) 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.

-〇- -10- [Effects of the Invention] The low-odor resin composition of the present invention has excellent storage stability and pot life, and does not reduce curing and drying properties (
It has well-balanced characteristics and has great practical advantages.

Patent applicant: Toshiba Chemical Corporation 11-

Claims (1)

[Claims] 1. One or more compounds selected from 2-pyridine carboxylic acids and 2-quinoline carboxylic acids are added to an unsaturated polynisder resin composition consisting of an unsaturated polyester and an acrylic ester or methacrylic ester or a substituted derivative thereof. A low-odor resin composition characterized by containing o, ooi to 0.1% by weight of.