JP2531864B2 - Unsaturated polyester resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition which accelerates curing of an unsaturated polyester resin at normal temperature to moderate temperature, and particularly to an unsaturated polyester resin which is suitable when the cured product requires a light color. It relates to a resin composition.

[0002]

2. Description of the Related Art Unsaturated polyester resins are widely used as fiber reinforced plastics (hereinafter abbreviated as FRP) in construction, housing equipment, boats, industrial materials, corrosion resistant equipment and the like. Further, it is well known that it is also used for applications using only unsaturated polyester resin, for example, paints, decorative boards, various castings, buttons and the like.

As a recent trend, unsaturated polyester resins are used especially for household appliances such as artificial marble bathtubs,
Significant expansion to fields requiring beauty, such as vanities and table tops. FRP with casting and molding materials (BMC) are used for these applications, but most of the high-grade products are FRP with casting. in this case,
The most problematic aspect in appearance is the amount of the organic acid salt of cobalt, which is a curing accelerator, required when the unsaturated polyester resin is cured with an organic peroxide at room temperature or a temperature close thereto. That is, since the organic acid salt of cobalt is reddish purple, coloring is unavoidable even if added in a small amount of about 0.3 phr, and it yellows over time in applications where it is exposed to hot water such as a bathtub. Is remarkable. Even when heat is not applied, such as a bathroom vanity, it is very often seen that a molded article that was originally white and beautiful changed its color to cream over time.

Although the cause of these discolorations is not one, it has been confirmed that the most influential one is the amount of the organic acid salt of cobalt used. Therefore, many attempts to reduce the amount of organic acid salt of cobalt have been studied in the past, and a typical example thereof is a keto-enol tautomer such as acetylacetone (the following formula).

[0005]

Embedded image Is known to be used in combination with an organic acid salt of cobalt as a curing accelerator. Further, in a similar example, it is known to use dimedone, acetylcyclopentanone, and an acetoacetoxy compound of a secondary amine together as a curing accelerator.

All of these keto-enol tautomers are extremely useful and have been successful in reducing the amount of cobalt organic acid salt used. However, since these keto-enol tautomers remain in the cured product as they are, the amount of 0.2 to 1.0 phr which is usually used is used, except when the amount is small. Then, for example, deterioration of boiling resistance or discoloration with time comes to be observed.
In particular, under conditions where a thin film such as a gel coat must be used, it becomes remarkable when an organic acid salt of cobalt is used in an amount of 0.1 phr or less and a keto-enol tautomer is used in an amount of 0.3 phr or more. In other words, the optimum combination range of the organic acid salt of cobalt and the keto-enol tautomer is narrow, and if this balance is lost, the defect tends to be emphasized rather.

[0007]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks found in the above-mentioned conventional curing agent systems and solves the problems of coloring and yellowing which occur when the unsaturated polyester resin is cured at room temperature or a temperature close thereto. It is an object of the present invention to provide an unsaturated polyester resin composition which prevents deterioration and is completely cured in a short time, and in which the physical properties of the cured molded product are not deteriorated at all.

[0008]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, acetoacetoxyethyl methacrylate represented by the following formula is given as an example.

[0009]

Embedded image Like an unsaturated group capable of radical polymerization in one molecule,
By using an acetoacetoxy compound of an unsaturated alcohol sharing a keto-enol type tautomeric structure as a curing accelerator, in combination with a curing accelerator of an organic acid salt of cobalt, and using an organic peroxide as a curing agent. In addition, the curing of an unsaturated polyester resin is significantly promoted without being affected by the fluctuation of the amount of the acetoacetoxy compound of the unsaturated alcohol, for example, even when the amount of the acetoacetoxy compound is used is large, for example, 1.0 phr or more, and the above-mentioned problems are caused. It was possible to complete the present invention by knowing that the above can be solved.

That is, the present invention provides (a) a polybasic acid component containing an α, β-unsaturated polybasic acid or an acid anhydride thereof and a saturated or unsaturated polybasic acid or an acid anhydride thereof, and a polybasic acid component. Unsaturated polyester resin obtained by dissolving unsaturated alkyd obtained by esterification with alcohol in a copolymerizable monomer, (b) an organic acid salt of cobalt and (c) 1
The present invention relates to an unsaturated polyester resin composition containing an unsaturated group and an acetoacetoxy compound of an unsaturated alcohol having a keto-enol type tautomeric structure in the molecule.

First, the component (a) in the present invention will be described. The unsaturated polyester resin used as the component (a) is a polybasic acid obtained by combining an α, β-unsaturated polybasic acid or an acid anhydride thereof with a saturated or unsaturated polybasic acid or an acid anhydride thereof. It is obtained by dissolving an unsaturated alkyd obtained by esterifying a component and a polyhydric alcohol in a copolymerizable monomer, and its composition does not need to be particularly limited.

The α, β-unsaturated polybasic acid and its acid anhydride used for synthesizing the unsaturated alkyd include maleic anhydride and fumaric acid.

Examples of the saturated or unsaturated polybasic acid or its acid anhydride used in combination include phthalic anhydride, isophthalic acid, terephthalic acid and dimethyl ester, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Examples include endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, het acid, succinic acid, adipic acid, sebacic acid and the like.

The polyhydric alcohol to be esterified with these polybasic acid components does not need to be particularly limited, and commercially available products can be used as they are. Specifically, for example, ethylene glycol, propylene glycol, butanediol 1,3, butanediol 1,4, neopentyl glycol, 2,2-diethylpropanediol 1,3, hexanediol 1,6, 3-methylpentane Examples thereof include diol 1,5, cyclohexane 1,4-dimethanol, hydrogenated bisphenol A and bisphenol A propylene oxide adduct. Alkylene monoepoxides, such as ethylene oxide, propylene oxide, phenylglycidyl ether, etc., can be treated similarly to glycols.

The copolymerizable monomer for dissolving the unsaturated alkyd to give the unsaturated polyester resin serves as both a solvent and a crosslinking agent, and styrene is typically mentioned, but other than that. , Vinyltoluene, chlorostyrene, methyl methacrylate and methacrylic acid esters.

The amount of the copolymerizable monomer used is usually 20 to 200 with respect to 100 parts by weight of the unsaturated alkyd.
Parts by weight, preferably in the range of 50 to 100 parts by weight.

In the present invention, examples of the organic acid salt of cobalt which is the curing accelerator used as the component (b) include cobalt naphthenate and cobalt octylate.
It is also possible to further enhance the curability by using an organic acid salt of another metal such as calcium naphthenate, strontium naphthenate, barium naphthenate, copper naphthenate, rare earth naphthenate, lead naphthenate, etc. . The amount of the organic acid salt of cobalt used is generally 0.5 to 1.0 part by weight based on 100 parts by weight of the unsaturated polyester resin, but the acetoacetoxy compound of the unsaturated alcohol of the component (c) is also used. In this case, 0.01 to 0.2 parts by weight will be sufficient.

Further, in the present invention, the acetoacetoxy compound of the unsaturated alcohol as the curing accelerator used as the component (c) has an unsaturated group and a keto-enol type tautomeric structure in one molecule. In general, it can be easily synthesized by reacting an unsaturated alcohol with diketene.

As an example, as the unsaturated alcohol, 2-
If hydroxyethylmethacrylate is used, acetoacetoxyethylmethacrylate (A
AEM) can be synthesized.

[0020]

Embedded image

As the unsaturated alcohol for synthesizing the acetoacetoxy compound of the unsaturated alcohol as the component (c), for example, 2-hydroxyethyl acrylate, 2-
Examples thereof include hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, trimethylolpropane diallyl ether, glycerin diallyl ether, and pentaerythritol triallyl ether. The types obtained by adding caprolactone to these unsaturated alcohols can be used as well, but the addition amount is inevitably large due to the high molecular weight, and it is a modifier of the cured product rather than a curing accelerator. Meaning increases. An adduct of (meth) acrylic acid and an alkylene monoepoxide (part of the above) can also be used.

The reaction between unsaturated alcohol and diketene is
The primary alcohol has a good reaction rate and is almost completely acetoacetoxylated, but in the case of the secondary alcohol, the yield is limited to about 85 to 90% in spite of the increased reaction conditions.
However, it does not matter for the present invention. The reaction of unsaturated alcohol with diketene proceeds at 50-60 ° C in the presence of a catalyst such as dibutyltin dilaurate.

The amount of the acetoacetoxy compound of the unsaturated alcohol as the component (c) is such that the unsaturated polyester resin 1 is used.
0.1 to 10 parts by weight is preferable with respect to 00 parts by weight.

The organic peroxide used as a curing agent in the present invention does not need to be particularly limited, and commercially available ones can be used. Typical examples include methyl ethyl ketone peroxide, acetylacetone peroxide, cumene hydroperoxide and the like. The amount of the organic peroxide used is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the unsaturated polyester resin.

The unsaturated polyester resin composition of the present invention is useful in the field of curing an unsaturated polyester resin at room temperature or a temperature close to room temperature, such as FRP, paint, lining, and casting. Further, the unsaturated polyester resin composition of the present invention is obtained by adding an organic acid salt of cobalt of component (b) and an acetoacetoxy compound of unsaturated alcohol of component (c) to the unsaturated polyester resin of component (a). Not only can it be applied to obtain a transparent cured product by blending, but of course it can also be used to accelerate the curing of an unsaturated polyester resin that optionally contains a colorant, a filler, a reinforcing material, a release agent and the like. Is.

[0026]

In the present invention, even when a large amount of the acetoacetoxy compound of the unsaturated alcohol as the component (c) is used in combination, the unsaturated polyester resin has an excellent curing-accelerating action as a curing-accelerating aid at room temperature or near room temperature. And the reason why the physical properties of the cured product are not impaired is not clear, but the unsaturated group of the component (c) is copolymerized with styrene which is a copolymerizable monomer during the curing of the unsaturated polyester resin. It is presumed that this is because it does not remain in the cured product as it is as one component of the cured product, unlike the conventional curing accelerators such as keto-enol tautomers.

[0027]

EXAMPLES In order to facilitate understanding of the present invention, examples will be shown below.

Example 1Synthesis of unsaturated polyester resin (A)  Equipped with stirrer, fractional condenser, thermometer, gas inlet pipe
Add 1 liter of separable flask and propylene glycol.
160 g, phthalic anhydride 148 g, maleic anhydride 98
g, and an acid value of 3 at 195 to 205 ° C in a nitrogen gas stream.
After the esterification proceeds to 8.1, the temperature is lowered to 130 ° C.
Gelatin, hydroquinone 0.04g, then styrene 246
g was added to obtain an unsaturated polyester resin (A). Get
Hazen color number of the unsaturated polyester resin (A) is 1
00 and the viscosity was 5.9 poise.

With respect to 100 parts by weight of this unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt octylate (8% Co) and US Eastman
Acetoacetoxyethylmethacrylate (abbreviated as AAEM) manufactured by Chemical Co. was blended as shown in Table 1 and the curability was measured.

As can be seen from the results shown in Table 1, the addition of AAEM showed a remarkable excellent hardening promoting action.

[0031]

[Table 1]

Embodiment 2Synthesis of unsaturated polyester resin (B) for gel coat  Equipped with stirrer, fractional condenser, gas inlet pipe, thermometer
In a 1 l separable flask, add 1,4-cyclohexa
Dimethanol 150g, 2,2-diethylpropanedi
Charge all 1,3 140g, isophthalic acid 166g
Esterification at 190-200 ℃ in nitrogen gas stream
After adjusting the acid value to 24.1, add 98 g of maleic anhydride,
Furthermore, the acid value was esterified to 29.2. Then set the temperature to 1
Lowered to 30 ℃, hydroquinone 0.07g, styrene 4
15 g was added to obtain an unsaturated polyester resin (B).
Hazen color number of the resulting unsaturated polyester resin (B)
Was 70 and the viscosity was 11.4 poise.

[0033]Creating a gel coat  To 100 parts by weight of unsaturated polyester resin (B),
4 parts by weight of # 200, 15 parts by weight of styrene, silicone
Add 10 ppm defoamer and knead with three rolls
It was a transparent gel coat for stones. Divide the transparent gel coat for 2 minutes,
As (I), 0.2 phr of cobalt octylate was added.
As (II) to 0.05 phr of cobalt octylate
Acetoacetoxypropyl meta manufactured by Nippon Emulsifier Co., Ltd.
Acrylate (about 95% purity, 3-4% unreacted hydroxy)
It contains cypropylmethacrylate and a little less than about 1% acetic acid.
Adjust each with 3 phr of AAPM)
Was. Hardener E manufactured by Kayaku Akzo Co., Ltd. for (I) and (II)
Any one with S added in 1.5 phr
Gelled at room temperature in 30-40 minutes.

On the glass plate coated with the release agent, 0.6 to
Immediately after the blending, each of the blends (I) and (II) was spray-coated so that the thickness was 0.7 m / m.

After gelling, the gel coat was cured in a constant temperature bath at 60 ° C. for 20 minutes, and a 1.5 m / m thick glass mat FRP colored white on one side was placed in a gap of 1 cm. ) Rigolac # 380 manufactured by
0 parts by weight and glass frit M manufactured by Nippon Fellow Co., Ltd.
A system was prepared in which 200 parts by weight of -10B and 1.5 parts by weight of Perkadox # 16 manufactured by Kayaku Akzo Co., Ltd. were mixed.

After curing at 50 ° C. for 14 hours and at 80 ° C. for 3 hours, the mold was removed, and a gel coat layer was formed on one side and white FRP was formed on the back side.
A layered bath test piece was obtained. The system containing 0.2 phr of cobalt octylate (I) was colored a pale dark reddish purple, while the system containing (II) AAPM was very slightly purple and white. It was transparent and beautiful.

When the gel-coated surfaces of both test pieces were immersed in boiling water for testing, the results shown in Table 2 were obtained, and a remarkable difference in yellowing resistance was observed.

[0038]

[Table 2]

[0039]

The unsaturated polyester resin composition of the present invention uses an acetoacetoxy compound of an unsaturated alcohol having an unsaturated group and a keto-enol type tautomeric structure in one molecule as a curing accelerator. As a result, the unsaturated polyester resin can be completely cured in a short time without yellowing at room temperature or a temperature close to it, and there is no deterioration in the physical properties of the cured molded product. Therefore, FRP, paint, lining, It is extremely useful in the field of room temperature curing such as casting.

Claims (1)

(57) [Claims] 1. An ester of (a) an α, β-unsaturated polybasic acid or an acid anhydride thereof and a polybasic acid component containing a saturated or unsaturated polybasic acid or an acid anhydride thereof and a polyhydric alcohol. Unsaturated alkyd obtained by the polymerization of an unsaturated polyester resin dissolved in a copolymerizable monomer,
An unsaturated polyester resin composition comprising (b) an organic acid salt of cobalt and (c) an acetoacetoxy compound of an unsaturated alcohol having an unsaturated group and a keto-enol type tautomeric structure in one molecule. Stuff.