JPS5911606B2 - Unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an amine-modified unsaturated polyester resin composition having excellent curability and stability.

Unsaturated polyester resins have a wide range of uses, including paints, cast products, primitives, and FRP, and many improvements have been made to fully utilize their excellent performance.

Unsaturated polyester resins used as moldings and undercoats are required to cure rapidly at low temperatures and to provide excellent mechanical properties of the cured product.

The mechanical properties can be improved by selecting dicarboxylic acids, diols, etc. constituting the unsaturated polyester resin, and the curing properties and stability can be improved by selecting the unsaturated polyester resin and the diol.
, and N-bis-(hydroxyalkyl)-arylamine have been proposed. However, cocondensates of unsaturated polyesters and N,N-bis-(hydroxyalkyl)-arylamines have the disadvantage that the curing rate decreases during storage, and are still unsatisfactory.

However, as a result of intensive studies to solve the drawbacks of the above-mentioned co-condensates, the present inventors have found that by using the above-mentioned co-condensates in combination with a specific curing accelerator, that is, phenothiazine and metal acetylacetonate, curing is possible. The present inventors have discovered that an unsaturated polyester resin composition that has a good balance between properties and o-stability and is excellent for moldings and as an undercoat has been completed, and the present invention has been completed.

15 phenothiazine as a curing accelerator for unsaturated polyester resin is usually 30 phenothiazine for unsaturated polyester resin.
Although it is used in the range of ~50 ppm, the balance between curability and stability is poor, and metal acetylacetonate is used up to about 1000 ppm, but it has poor stability and tends to be x.

Therefore, the purpose of the present invention cannot be achieved by using these alone. The amount of phenothiazine in the present invention is N, N-
The amount is 10 to 200 ppm based on the total amount of the unsaturated polyester resin cocondensed with bis-(hydroxyalkyl)-arylamine (abbreviated as amine 5 modified unsaturated polyester resin) and the copolymerizable vinyl compound.

When used in combination with metal acetylacetonate within the above range,
The drawback of increased stability but decreased curability when used alone is eliminated. The blending amount of metal acetylacetonate is 5% based on the total amount of resin and vinyl compound.
It is 0 to 5000 ppm.

When used in combination with phenothiazine within the above range, the curing properties are improved, but the disadvantages of using the composition alone, such as noticeable thickening of the composition and poor stone stability, are overcome. Examples of the metal acetylacetonate include vanadium acetylacetonate, cobalt acetylacetonate, iron acetylacetonate, aluminum acetylacetonate, and among them, iron acetylacetonate is preferred because it has a remarkable effect of improving the curing rate.

Since these metal acetylacetonates are in powder form, they are dissolved in various solvents or copolymerizable vinyl compounds, and added in a predetermined amount as a 1 to 10% by weight liquid, and stirred and mixed uniformly. The amount of amine in the amine-modified unsaturated polyester resin in the present invention is about 0.5 to 2.
5% by weight, and for unsaturated polyester resin compositions that also contain a copolymerizable vinyl compound, approximately 0.3% by weight.
-2.0% by weight, and about 0.02-0.3% by weight, expressed as the amount of active nitrogen in the amino groups, is used in the co-condensation. The amine is N,N-bis-(β-
hydroxyethyl)-aniline, N,N-bis-(β-
hydroxypropyl)-P-toluidine N,N-bis-
(β-hydroxyethyl)-P-toluidine, N,N-
Examples include bis-(γ-hydroxypropyl)-aniline. Examples of polybasic acids that are constituents of the unsaturated polyester resin in the present invention include unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid, phthalic anhydride, phthalic acid, isoptanic acid, and terephthalic acid. Acids, saturated dibasic acids such as tetrahydrophthalic anhydride, citraconic acid, endomethylenetetrahydrophthalic anhydride, head acid, adipic acid, sebacic acid, succinic acid, azelaic acid, trimellitic acid, pyromellitic acid, 5-xentricarboxylic acid and its anhydride.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-bentanediol, 1, Examples include 6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

Examples of the copolymerizable compound in the present invention include styrene, vinyltoluene, chlorostyrene, α-methylstyrene,
Divinylbenzene, (meth)acrylic acid ester, glycidyl methacrylate, vinyl acetate, diallyl phthalate, triallyl cyanurate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, tung oil, linseed oil, Examples include soybean oil, cottonseed oil, safflower oil, and coconut oil.

Curing agents include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide,
Peroxides such as tertiary butyl perbenzoate and cyclohexanone peroxide are mentioned, and as accelerators manganese naphthenate, vanadyl octoate, copper naphthenate, calcium naphthenate, barium naphthenate, zirconium naphthenate, zinc naphthenate, Cobalt naphthenate, cobalt octenoate, etc. may be used in combination.

Additives such as pigments and fillers can be added to the resin composition of the present invention depending on the intended use.

Examples of fillers include calcium carbonate, clay, talc, mica, asbestos powder, finely divided silica, barium sulfate, etc., and examples of pigments include titanium white, cyanine blue, chrome yellow, red iron, carbon black, and aniline black. Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" and "%" are based on weight. Example 1 In a four-necked 21 volume flask equipped with a stirrer and a condenser, 335 parts of maleic anhydride, 757 parts of phthalic anhydride, 688 parts of 1,2-propylene glycol, and N-bis-(β-hydroxyethyl)-P
-20 parts of toluidine and 0.27 parts of toluhydroquinone
A portion was taken and reacted at 190 to 200° C. for 9 hours while blowing nitrogen gas to obtain an amine-modified unsaturated polyester having an acid value of 37.1.

The resin was dissolved in styrene to obtain a resin liquid with a resin content of 70%. To this resin liquid, 150 ppm of toluhydroquinone and 30 ppm of copper naphthenate were added to prepare a resin liquid (4).

On the other hand, 50 ppm of phenothiazine and 300 ppm of iron acetylacetonate were additionally added to the resin liquid (A) to obtain a resin composition (B). Resin composition B) had the same degree of coloration as resin liquid (4), and was transparent with a viscosity of 2750 centipoise (25°C). Resin composition B)
To 100 parts, 4 parts of benzoyl peroxide (Naipa 1 BO, manufactured by NOF Corporation) was added to examine the curing properties and stability. The results are listed in Table 1. Examples 2 to 3 In Example 2, phenothiazine 100 ppm 1 iron acetylacetonate 1000 was added to the resin liquid (4) in Example 1.
In Example 3, 30 ppm of phenothiazine and 100 ppm of iron acetylacetonate were added to the resin solution (A).
ppm was added to obtain a resin composition, and a curing agent was added to each resin composition in the same manner as in Example 1, and the curability and stability were examined.

The results are listed in Table 1. Control Examples 1 to 2 Resin solution in Example 1 (5 ppm of phenothiazine in Control Example 1 to 8)
In Control Example 2, 300 ppm of phenothiazine and 7,500 ppm of iron acetylacetonate were added to the resin liquid, and a curing agent was added to these in the same manner as in the example to check hardenability and stability. Examined.

The results are listed in Table 1. Control example 3 200 ppm of benzyltriethylammonium chloride (BTAC) and 500 ppm of triphenylphosphin (TPP) were added to the resin liquid (4) in Example 1, and a curing agent was added in the same manner as in the example, and the curability and stability were determined. I looked into it.

The results are listed in Table 1. Control Examples 4 to 6 In Control Example 4, only a curing agent was added without adding an accelerator, in Control Example 5, only phenothiazine was added as an accelerator, and in Control Example 6, only iron acetylacetonate was added.

Claims (1)

[Claims] 1 (a) Unsaturated polyester resin copolymerized with N,N-bis-(hydroxyalkyl)arylamine, (b
) An unsaturated polyester resin composition comprising 10 to 200 ppm of phenothiazine, (c) 50 to 5000 ppm of metal acetylacetonate, and a copolymerizable vinyl compound as main ingredients.