JPH045662B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a radically curable unsaturated alkyd having a novel structure useful for various uses such as paints, adhesives, molding materials, and FRP, and a method for producing the same.

[Conventional technology]

Currently, unsaturated polyester resins and vinyl ester resins are widely used as radical-curable resins that can be cured at room temperature.

However, as the uses of resins become more diverse, the performance required of the resins becomes more detailed and sophisticated, and it is often felt that existing resins are insufficient to meet these demands. For example, in the case of gel coat, which is commonly used as a coloring and surface protection layer for FRP, there is a movement to improve water resistance, alkali resistance, and corrosion resistance against specific chemicals without increasing costs.

Vinyl ester resins have extremely excellent water and chemical resistance, so naturally they can be used for this purpose, and in fact, their boiling resistance itself is extremely good, so they are generally used as gel coats. However, the workability required for gel coats, namely sprayability, thixotropy imparting properties,
There is a need for further improvement in various aspects such as the absence of color separation, and although efforts are being made to improve in line with these expectations, desired results have not been obtained at this stage.

On the other hand, for unsaturated polyester resin, the bisphenol type polyester shown by the following formula Styrene solutions have become the mainstream gel coat for bathtubs because of their good workability. However, it has the drawback that its hot water resistance is inferior to that of vinyl ester resins, and it does not meet high demands.

[Problem that the invention seeks to solve]

As a result of intensive research to improve the various drawbacks of these existing resins, the present inventors discovered that an unsaturated alkyd with a new structure represented by the general formula below has excellent water resistance and
The present inventors have discovered that this resin has chemical resistance that is at least equal to or better than these existing resins, and is also superior in terms of workability, leading to the completion of the present invention.

[Means for solving problems]

That is, the present invention is based on the general formula [However, R ₁ and R ₂ each represent hydrogen or a methyl group, n is 0 to 2, and m is 2 to 2.
An integer of 20] is a curable unsaturated alkyd.

Furthermore, the present invention relates to the general formula The epoxy resin represented by is reacted with paracumylphenol in an amount that eliminates the epoxy groups in the epoxy resin to form a reaction product [] is produced, and then the hydroxyl group in the reaction product [] is esterified with an α-β unsaturated polybasic acid or its anhydride. The object of the present invention is to provide a method for producing a curable unsaturated alkyd represented by the formula (where R ₁ , R ₂ , n and m are the same as above).

[Function] The unsaturated alkyd of the present invention has a novel structure represented by the above general formula, is bulky because it has a paracumylphenoxymethylene group in the side chain, and has a large number of double bonds per molecular weight. It is presumed that this will have a favorable effect on the boiling resistance and heat distortion temperature of the resin. In addition, since the main chain of the unsaturated alkyd of the present invention is composed of repeating units in which bisphenol diglycidyl ether and α-β unsaturated polybasic acid are ester-bonded, it can be dissolved in styrene solution like bisphenol type polyester. It is thought that this product will have excellent workability when used as a tool. Repeat unit is 2~
20 (equivalent to about 1,000 to 10,000 when converted to molecular weight), and if the repeating unit is smaller than 2, the curability of the resin will be poor, and if it is larger than 20, it will be difficult to carry out the present invention.

The unsaturated alkyd according to the present invention can be used in paints, adhesives, molding material,
It can be used for various purposes such as FRP.

The method for synthesizing the unsaturated alkyd of the present invention is to react bisphenol diglycidyl ether type epoxy resin with paracumylphenol, and then convert the hydroxyl groups in the reaction product [] into α-β
Examples include a method of esterification with an unsaturated polybasic acid or its anhydride. The flow is shown below using a typical example.

The epoxy resin used in the present invention is of the phenyl glycidyl ether type, commonly referred to as the so-called bisphenol type.

For example, the type shown by the following general formula synthesized from bisphenol A and epichlorohydrin, It is preferable that n be in the range of 0 to 2, and there is no need to increase the number of repeating units.

Furthermore, a methylene-bisphenyl glycidyl ether type epoxy resin commonly referred to as a bisphenol F type epoxy resin can also be used.

The reaction ratio of the epoxy resin and paracumylphenol is suitably 1 equivalent or less of phenolic hydroxyl group or more than 0.5 equivalent per 1 equivalent of epoxy group.

If it is less than 0.5 equivalent, it is not preferable because it tends to gel when esterified with an unsaturated polybasic acid or its acid anhydride.

During the reaction, tertiary amines that are generally used as curing accelerators for epoxy resins, such as benzyldimethylamine and tris(dimethylamino), are used.
The use of phenol, quaternary ammonium salt, etc. is highly effective in promoting the reaction.

Examples of the α-β unsaturated polybasic acid or its acid anhydride used in the present invention include maleic anhydride, maleic acid, and fumaric acid. At that time, it can also be modified with a small amount of saturated polybasic acid.

Esterification is carried out in the usual manner, i.e. in an inert gas stream.
It is carried out at a temperature of about 180 to 220 degrees Celsius.

The unsaturated alkyd obtained by esterification can be dissolved in copolymerizable monomers such as styrene, vinyltoluene, diallyl phthalate, diallyl terephthalate, methacrylic acid esters, etc., and can be provided for various uses.

At this time, in order to prevent gelation, it is necessary to add a small amount (0.01 to 0.5 phr) of commonly used polymerization inhibitors such as polyhydric phenols and quinones.

It goes without saying that fillers, reinforcing materials, colorants, mold release agents, polymers, etc. can be used in combination, depending on the needs of the application.

[Examples] Next, examples will be shown below to help understand the present invention.

Note that the parts used are parts by weight.

Example 1 A separable flask equipped with a stirrer, thermometer, gas inlet tube, and fractionation condenser was charged with epoxy resin. Add 360 g of n≒0 (DER332 from Asahi Dow), 424 g of paracumylphenol (ratio of epoxy group to phenolic hydroxyl group is 1:0.97), and 2 g of trimethylbenzylammonium chloride, and heat at 120°C.
Since it rapidly generates heat when the temperature exceeds 160°C, it was cooled as necessary to maintain the temperature below 160°C.

After about 3 hours, as a result of infrared analysis (see Figure 1), free epoxy groups were no longer observed, so 116 g of fumaric acid was added and esterification proceeded at 200 to 210°C in a nitrogen gas stream. Ta.

Stopped at acid value 19.2 (estimated average molecular weight approximately 5500),
Add 0.1g of hydroquinone and inject into a metal vat.
Solidified. An unsaturated alkyd (A) with a yellowish brown color and a melting point of about 110°C was obtained (see Figure 2).

Grind 100 parts of unsaturated alkyd (A) and add styrene.
100 was heated and dissolved at 60-70°C.

The obtained polyester resin (B) had a Gardner color number of 2 to 3 and a viscosity of 4.7 poise.

100 parts of unsaturated polyester (B), 2 parts of methyl ethyl ketone peroxide, 1 part of cobalt naphthenate
The system containing 0.1 part of dimethylaniline and 0.1 part of dimethylaniline gelled in 36 minutes and then slowly generated heat, reaching a maximum temperature of 131°C. The heat distortion temperature was 98°C.

After testing a 100 mm x 25 mm x 3 mm cast plate with a 10% caustic soda solution at 90°C for 1000 hours, the bending strength retention rate was 93 (%), which was excellent with no change in appearance.

Example 2 A bisphenol F type epoxy resin was added to the same equipment as in Example 1. 350g of n≒0 (Epicote 807 from Yuka Ciel Co., Ltd.),
Paracumylphenol 382g (ratio of epoxy group to hydroxyl group is 1:0.9), benzyldimethylamine 2
When the temperature is raised to 110°C, it rapidly generates heat, so the temperature is cooled to below 160°C, and then kept at 150 to 160°C for 3 hours. As a result of infrared analysis, the temperature is increased. It was determined that the epoxy group had disappeared.

Next, 98 g of maleic anhydride was added, esterification was carried out at 200 to 210° C. in a nitrogen gas stream, and the mixture was stopped at an acid value of 20.9. 0.1 g of hydroquinone was added, and the mixture was poured into a metal vat and solidified.

An unsaturated alkyd (C) with a yellowish brown color and a melting point of about 110°C was obtained. (Estimated average molecular weight: approximately 5000) 100 parts of unsaturated alkyd (C) was ground and dissolved in 100 parts of vinyltoluene at 60 to 70°C.

An unsaturated polyester resin (D) having a Gardner color number of 2 to 3 and a viscosity of 3.9 poise was obtained.

100 parts of unsaturated polyester resin (D), 2 parts of methyl ethyl ketone peroxide, 1 part of cobalt naphthenate, and 0.1 part of dimethylaniline are added.
It gelatinized in 23 minutes and slowly generated heat, reaching a maximum exothermic temperature of 133°C.

The heat distortion temperature was 96°C.

[Brief explanation of drawings]

FIG. 1 shows an infrared spectrum of the reaction product of the epoxy resin obtained in Example 1 and paracumylphenol. FIG. 2 shows an infrared spectrum of the unsaturated alkyd of the present invention obtained by the reaction of the above reaction product with fumaric acid.

Claims (1)

[Claims] 1. A curable unsaturated alkyd substantially represented by the following general formula: [However, R ₁ and R ₂ each represent hydrogen or a methyl group, n is 0 to 2, and m is 2 to 2.
is an integer of 20]. 2 General formula The epoxy resin represented by is reacted with paracumylphenol in an amount that eliminates the epoxy groups in the epoxy resin to form a reaction product [] is produced, and then the hydroxyl group in the reaction product [] is esterified with an α-β unsaturated polybasic acid or its anhydride. A method for producing a curable unsaturated alkyd represented by [However, R ₁ , R ₂ , n and m are the same as above].