JPH0597945A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the subject resin containing a specific unsaturated polyester resin, a specific Co organic acid salt and an unsaturated alcohol acetoacetoxy compound, preventing the discoloration when cured, perfectly cured in a short time and free from lowering in physical properties. CONSTITUTION:The objective composition contains (A) an unsaturated polyester resin comprising an unsaturated alkyd dissolved in a copolymerizable monomer, the unsaturated alkyd being obtained by esterifying (i) a polybasic acid component containing an alpha,beta-unsaturated polybasic acid (anhydride) and an (saturated) polybasic acid (anhydride) with (ii) a polyhydric alcohol, (B) an organic acid salt of Co, (C) the acetoacetoxy compound of an unsaturated alcohol having an unsaturated group and a keto-enol tautomeric structure.

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 the unsaturated polyester resin is also heavily used for applications such as paints, decorative boards, various castings and buttons.

As a recent trend, unsaturated polyester resins are used especially for household appliances, for example, artificial marble bathtubs,
Significant expansion to areas 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 when 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 initially white and beautiful turned discolored 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 have been made in the past to reduce the amount of organic acid salt of cobalt, and a typical example thereof is a keto-enol tautomer such as acetylacetone (the following formula).

[0005]

[Chemical 1] Is known to be used in combination with an organic acid salt of cobalt as a curing accelerator. In a similar example, it is known to use diacetone, an acetylcyclopentanone, and an acetoacetoxy compound of a secondary amine together as a curing accelerator.

Each of these keto-enol type tautomers is extremely useful and has been successful in reducing the amount of organic acid salt of cobalt used. However, since these keto-enol tautomers remain in the cured product as they are, the amount used is usually 0.2 to 1.0 phr, except when the amount used is small. Then, for example, the boiling resistance is deteriorated or discoloration with time is observed.
In particular, when it is necessary to cure with a thin film such as a gel coat, when the organic acid salt of cobalt is 0.1 phr or less and the keto-enol tautomer is 0.3 phr or more, it becomes remarkable. 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 overcomes the drawbacks of coloring and yellowing that 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]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems. As a result, acetoacetoxyethyl methacrylate represented by the following formula is given as an example.

[0009]

[Chemical 2] 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 unsaturated polyester resin is significantly accelerated 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 curing of the unsaturated polyester resin is significantly promoted. It was possible to complete the present invention by knowing that the above can be solved.

That is, the present invention comprises (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 polyvalent acid. 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
It relates to an unsaturated polyester resin composition characterized by containing an acetoacetoxy compound of an unsaturated alcohol having an unsaturated group and 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 its acid anhydride with a saturated or unsaturated polybasic acid or its acid anhydride. It is obtained by dissolving an unsaturated alkyd obtained by esterifying a component and a polyhydric alcohol in a copolymerizable monomer, and the composition thereof 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,
Endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, het acid, succinic acid, adipic acid, sebacic acid and the like can be mentioned.

The polyhydric alcohol 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, phenyl glycidyl ether, etc. can be treated similarly to glycols.

The copolymerizable monomer for dissolving the unsaturated alkyd to give the unsaturated polyester resin serves both as a solvent and a crosslinking agent, and typical examples thereof include styrene. , Vinyltoluene, chlorostyrene, methyl methacrylate and methacrylic acid esters.

The amount of the copolymerizable monomer used is usually 20 to 200 relative 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 as 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 with respect to 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 the reaction of unsaturated alcohol and diketene.

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

[0020]

[Chemical 3]

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. Although it is also possible to use those types in which caprolactone is added to these unsaturated alcohols, the addition amount is inevitably large due to the high molecular weight, and a modifier for 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. Representative 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, for example, fields such as FRP, paint, lining and casting. In addition, the unsaturated polyester resin composition of the present invention is based on the unsaturated polyester resin of the component (a), an organic acid salt of cobalt of the component (b) and an acetoacetoxy compound of the unsaturated alcohol of the component (c). Not only can it be applied to obtain a transparent cured product by blending, but it can also be used for accelerating the curing of an unsaturated polyester resin that further contains a colorant, a filler, a reinforcing material, a release agent, etc., if necessary. 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 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 a copolymerizable monomer such as styrene 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 a 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
In a 1 l separable flask, add 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, lower the temperature to 130 ° C.
Gelatin, hydroquinone 0.04g, then styrene 246
g was added to obtain an unsaturated polyester resin (A). Got
Hazen color number of the unsaturated polyester resin (A) is 1
00 and the viscosity was 5.9 poise.

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

The results, as shown in Table 1, show that the addition of AAEM has a very excellent hardening promoting action.

[0031]

[Table 1]

Example 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
140g of all 1,3 and 166g of isophthalic acid were charged.
Esterification at 190-200 ℃ in nitrogen gas stream
After adjusting the acid value to 24.1, 98 g of maleic anhydride was added,
Furthermore, esterification was performed up to an acid value of 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 10ppm antifoaming agent, knead with three rolls,
It was a transparent gel coat for stones. 2 minutes clear gel coat,
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)
It was Hardener E manufactured by Kayaku Akzo Co., Ltd. for (I) and (II)
Add S by 1.5 phr each.
Gelled at room temperature in 30-40 minutes.

On a glass plate coated with a release agent, 0.6 to
Immediately after the blending, each of the blends of (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, and Showa High Polymer Co., Ltd. 10) Rigolac # 380 manufactured by
0 parts by weight and glass frit M made 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 the gel coat layer was formed on one side and white FRP was formed on the back side.
A layered bathtub test piece was obtained. The system containing 0.2 phr of cobalt octylate (I) was colored a reddish-purple color with a slight darkness, while the system containing AAPM of (II) was 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)

[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. The 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. object.