JPS5840569B2 - Netsukou Kaseiji Yushiso Seibu Tsuno Koukahouhou - Google Patents

Description

Detailed Description of the Invention The present invention relates to a thermosetting resin composition (hereinafter simply referred to as epoxy ester resin) comprising a reaction product of a bisphenol type epoxy resin and an unsaturated basic acid and a polymerizable unsaturated monomer. It is called.

) at a temperature in the range of 0 to 60°C.

Epoxy ester resin is a thermosetting resin composition that has emerged as a high-performance resin to replace unsaturated polyester resin.

In other words, cured unsaturated polyester resins have a low tensile elongation rate, resulting in poor impact resistance and residual internal strain due to curing shrinkage.Additionally, the resin is reinforced with glass fibers to create composite materials (hereinafter referred to simply as FRP). It is called.

), epoxy ester resins have disadvantages such as being susceptible to peeling and cracking due to physical shock or thermal shock during handling such as transportation or assembly, or during use. The cured product has high corrosion resistance that is equal to or higher than that of unsaturated polyester resin, and extremely high tensile elongation performance. Epoxy ester resin can be adjusted to an extremely low viscosity at room temperature, and is free from organic peroxides and metals. It hardens in a short time through a radical reaction by adding soap, etc., and can be reinforced with fiber materials such as glass fiber.It can be used in the same way as conventional unsaturated polyester resins, and is extremely easy to work with. It is a resin with excellent productivity.

For this reason, epoxy ester resins have not only come to be actively used in fields such as bathtubs, corrosion-resistant pipes, and corrosion-resistant tanks, where conventional corrosion-resistant unsaturated polyester resins were used, but also in areas where unsaturated polyester resins have been used. It is widely used in a variety of fields, such as materials that come into contact with highly concentrated alkaline or oxidizing atmospheres, where the corrosion resistance was inadequate, such as in the cover of electrolytic cells for sodium chloride. .

There are many ways in which epoxy ester resins are used, depending on the field of application, the shape of the molded product, production volume, etc., such as the hand lay-up method in which it is molded and cured at room temperature, the spray-up method, and the flyment winding method in which it is heated and cured after molding. The current situation is that

In addition, the curing method used at that time can be almost the same as that used for unsaturated polyester resin.
For example, in the high temperature curing method, it is common to add and heat benzoyl peroxide, tert-butyl perbenzoate, etc., and in the room temperature curing method, ketone peroxide, typified by methyl ethyl ketone peroxide, cyclohexanone peroxide, etc. A representative method is to add a metal soap containing cobalt or vanadium as a radical generation promoter to oxide, and further use a tertiary amine such as dimethylaniline or a keto-enol type tautomer compound such as methyl acetoacetate. It can be mentioned as follows.

However, it is worth noting that when curing at room temperature, conventional unsaturated polyester resins can be completely cured by the method described above, whereas epoxy ester resins cannot be cured simply by applying the method described above. Even after a long period of time, the resin is not completely cured, and in order to fully cure and exhibit the original performance of the resin, treatment at a temperature of 60° C. or higher (hereinafter simply referred to as after-cure) is required.

), and this tendency becomes stronger as the usable life of the resin liquid, which is made by adding a curing agent or an accelerator to an epoxy ester resin, becomes longer.

This property of epoxy ester resins is a major obstacle when actually using the resins for curing at room temperature.

This is because epoxy ester resin is mainly used in the field of large molded products such as tanks, ducts, pipes, etc., and the usable life of the resin liquid containing hardeners and accelerators is generally longer than 20 minutes. This is because it is technically difficult to after-cure such large molded products, and it is also a heavy economic burden.

Against this background, sometimes the after-cure is insufficient or omitted, making it impossible to bring out the original physical properties of the epoxy ester resin, which can significantly shorten the service life of the molded product. The current situation is that this has led to cases of deterioration.

Therefore, the present inventors believe that if the epoxy ester resin can be completely cured at room temperature without any after-cure, it will not only be advantageous in terms of medicine, but also in terms of design and
As a result of intensive research, we believe that the epoxy ester resin can be used regardless of the size of the molded product and is extremely advantageous from the perspective of application development. It was discovered that the bisphenol type epoxy resin, which is a component of the epoxy ester resin, has an epoxy equivalent of 170 to 225 and 40.
The inventors have found that the curing system is particularly effective when the mixture is a mixture of 0 to 600 epoxy resins in a specific ratio, leading to the present invention.

Accordingly, it is an object of the present invention to provide a method for substantially completely curing epoxy ester resins at relatively low temperatures in the range of 0 to 600 G without the need for after-curing.

Other objectives will become apparent from the description below.

The present invention cures a thermosetting resin composition comprising a reaction product of a bisphenol type epoxy resin and an unsaturated basic acid and a polymerizable unsaturated monomer at a temperature in the range of 0 to 6°C. (where R1 and R4 represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a phenyl group, or an alkyl-substituted phenyl group).

R2 represents an alkyl group having 4 to 10 carbon atoms.

R3 represents an alkylene group having 6 to 20 carbon atoms.

), an organic acid salt of cobalt (B), and acetoacetate (Q).

The bisphenol type epoxy resin in the present invention has the general formula (wherein R5 represents -H or -CH3 and independently represents -H1-Br- or Ci).

n is O or an integer of 1 to 15. ), the value of n in the above formula does not need to be pure in terms of molecular weight, and the main component is a molecule with a molecular weight represented by the value of n-nl, -2t nl-1, nl +
It is usually a mixture of several types of molecules having different molecular weights, such as 12 nl +2.

In actual use, for example, ``Araldite'', ``Epicoat'', ``Dowepoxy'', and ``Sumiepoxy'' are manufactured by Ciba of Switzerland, Shell and Dow of the United States, Sumitomo Chemical and Dainippon Ink of Japan, etc. Epoxy resins generally referred to as bisphenol-type or bisphenol-epichlorohydrin-type epoxies, which are commercially available under trade names such as "Epiclon" and "Epiclon", can be used.

Typical examples of unsaturated basic acids are acrylic acid and methacrylic acid, but half esters of dicarboxylic acids with hydroxyalkyl acrylates or hydroxyalkyl methacrylates can also be used.

Examples of the polymerizable unsaturated monomer include styrene, vinyltoluene, α-methylstyrene, halogenated styrene,
Representative examples thereof include aromatic vinyl compounds such as divinylbenzene, and esters of acrylic acid or methacrylic acid such as methyl acrylate, methyl methacrylate, ethylene glycol diacrylate, and propylene glycol dimethacrylate.

The amount used is within the range of 10 to 70% by weight, preferably 20 to 60% by weight of the epoxy ester resin.

If the amount used is less than 10 weight φ, the viscosity of the resulting epoxy ester resin will become too high to be practical, while if it is more than 70 weight φ, the tensile elongation rate will decrease, which is both undesirable.

A thermosetting resin composition comprising a reaction product of a bisphenol type epoxy resin and an unsaturated basic acid and a polymerizable unsaturated monomer, that is, an epoxy ester resin, can be produced by a conventionally known method.

A typical method is to use an unsaturated basic acid at a ratio of 0.8 to 1.2 moles per mole of epoxy group, and use a reaction catalyst such as lithium chloride, triethylamine, dimethylpendelamine hydrochloride, etc., or hydroquinone. , a method of reacting at a temperature of 80 to 160°C in the presence of a polymerization inhibitor such as tert-butylcatechol, and then adding a polymerizable unsaturated monomer; Examples include a method of reacting in the presence of a sexually unsaturated monomer.

However, the present invention is not limited by this method of producing an epoxy ester resin.

The present invention can be effectively used for the epoxy ester resin obtained in this way, but in particular, the bisphenol type epoxy resin used in preparing the epoxy ester resin is a bisphenol type epoxy resin having an epoxy equivalent of 170 to 225 ( Hereinafter, it will simply be referred to as epoxy resin rlJ.

) and a bisphenol type epoxy resin with an epoxy weight of 9400 to 600 (hereinafter simply referred to as epoxy resin rlJ).

), and the effects of the present invention are most effectively exhibited when the mixing ratio of epoxy resin "I"/epoxy resin rl [J is 2/8 to 4/6 in terms of number of moles.

The cause is not clear, but it is speculated that epoxy resin
Epoxy ester resins prepared using only IJ inevitably have a high temperature of the unsaturated basic acid ester introduced therein, and once curing has progressed to a certain extent, the resin as a whole becomes crosslinked to a considerable degree and becomes flexible. The residual unsaturated basic acid ester and polymerizable unsaturated monomer are confined therein, so their movement is restricted and the progress of curing is prevented. The prepared epoxy ester resin does not lose its flexibility even after curing progresses beyond a certain point because the concentration of the unsaturated base acid ester that is inevitably introduced is small, but the unsaturated base acid that is to be reacted does not lose its flexibility. Since the amount of basic acid ester is small, it is difficult to exhibit the effects of the present invention.

In comparison, epoxy resin rlJ and epoxy resin "
The epoxy ester resin prepared using the epoxy resin prepared by mixing the above-mentioned amount of esters in the above-mentioned range has a moderate concentration of unsaturated basic acid ester and moderate flexibility, so it does not have any residual residue even after it has been cured to a certain extent. Saturated - Unsaturation that remains because the concentration of basic acid ester is high and flexibility is not lost -
Since the movement of the basic acid ester and the polymerizable unsaturated monomer is not restricted, it is considered that the effects of the present invention can be exhibited most effectively.

Note that it goes without saying that the present invention is not limited solely by this reason.

The alkyl peroxy ester used in the present invention is a compound represented by the above general formula, and representative examples include tert-butyl peroxybenzoate, tert-butyl peroxy acetate, tert-butyl peroxyofftate, and t-butyl peroxybenzoate. Butyl peroxyisobutyrate, tert-butyl peroxy bivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5-di(peroxy-2- ethylhexanoyl)hexane, 2,5-dimethyl-2゜5-di(peroxybenzoyl)hexane, 2゜5-dimethyl-2,
5-di(peroxybenzoyl)hexyne-3,1,1
, 3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di-tert-butyl peroxy adipate, among others, tert-rib nano 2 liver oxybenzoate, tert-butyl peroxy-2-ethyl. Hexanoate is particularly effective.

The amount of the alkyl peroxyester used is in the range of 0.4 to 4.0 parts by weight, preferably 0.7 to 3.0 parts by weight, per 100 parts by weight of the epoxy ester resin, and the amount used is 0.4 to 4.0 parts by weight, preferably 0.7 to 3.0 parts by weight. If the amount used is small, less than 4 parts by weight, the time required for curing will be extremely long and it will be difficult to completely cure; even if the amount used is increased to more than 4.0 parts by weight, the amount will increase It has no effect, is not practical, and is not desirable.

The organic acid salt of cobalt is a cobalt salt of an organic acid having 2 to 18 carbon atoms, and among them, cobalt octenoate and cobalt naphthenate are most preferred from the viewpoint of compatibility with the resin.

The amount used is 0.005 to 0.3 parts by weight per 100 parts by weight of epoxy ester resin in terms of the amount of cobalt used.
Preferably, the amount is in the range of 0.01 to 0.25 parts by weight; if the amount used is less than 0.005 parts by weight, the time required for curing would be extremely long, which would be impractical. Further, even if the amount is increased to a proportion exceeding 0.3 parts by weight, the effect of the increased amount is small and is not practical, and both are not preferred.

Acetoacetic acid ester is an ester of acetoacetic acid and a monohydric alcohol having 1 to 15 carbon atoms, a polyhydric alcohol having two or more hydric alcohols, or an oxyalcohol.

In the case of esters with polyhydric alcohols or oxyalcohols, it is not necessary that all the hydroxyl groups of the alcohol be acetoacetate esters, and it is sufficient that at least one hydroxyl group of the alcohol be acetoacetate esters. be.

Typical examples of such acetoacetates include methyl acetoacetate, ethyl acetoacetate, propylacetoacetate, butylacetoacetate, heptyl acetoacetate, hexylacetoacetate, benzylacetoacetate, ethylene glycol monoacetoacetate or diacetoacetate, propylene glycol Examples include monoacetoacetate or diacetoacetate, diethylene glycol monoacetoacetate or diacetoacetate, methyl cellosolve acetoacetate, ethyl cellosolve acetoacetate, glycerin monoacetoacetate, diacetoacetate, or triacetoacetate.

Among these, methyl acetoacetate, ethyl acetoacetate, propylacetoacetate, ethylene glycol diacetoacetate, propylene glycol diacetoacetate, etc. are particularly effective.

The amount of acetoacetate used is in the range of 0.01 to 4.0 parts by weight, preferably 0.05 to 3.0 parts by weight, per 100 parts by weight of the epoxy ester resin. If the amount is less than 0.01 parts by weight, complete curing will not occur, and if the amount is increased to 4.0 parts by weight or more, not only will the effect of the increase be small, but the corrosion resistance of the cured product of the epoxy ester resin composition will decrease. Let it be, both are undesirable.

Further, the usefulness of this acetoacetate can be confirmed by curing the epoxy ester resin composition in the same manner as in the present invention except that acetylacetone having a functional group group relatively similar to that of the ester is used instead of acetoacetate. This can be easily understood if you consider that even if left at room temperature for a long time, it will not completely harden and that after-curing is required for complete hardening.

The present invention is characterized by using an alkyl peroxy ester represented by the above general formula, an organic acid salt of cobalt, and an acetoacetate. It can be substantially completely cured at temperatures in the range of 0 to 60°C.

In addition, it can be expected to have effects such as not requiring after-cure.

EXAMPLES Hereinafter, the effectiveness of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the scope of these Examples.

In addition, parts in the examples mean parts by weight unless otherwise specified.

Example 1 A bisphenol-type epoxy resin with an epoxy equivalent of 473 (6-Araldite 607 manufactured by Chill Co., Ltd.
1) Bisphenol type epoxy resin with 615 parts and epoxy equivalent of 185 (6Araldite "GY-260" manufactured by Chill Co., Ltd.)
) 130 parts, methacrylic acid 176 parts, hydroquinone O
1.1 parts of triethylamine and 3.2 parts of triethylamine were charged and reacted at 110'C for 5 hours while introducing air, and the reaction was terminated when the acid value reached 7. 650 parts of styrene monomer was added to produce an epoxy ester resin (hereinafter simply referred to as resin-rlJ).

) was obtained. Resin-rlJ was a clear, pale yellow liquid with a viscosity of 5.2 poise at 25°C.

Resin - 2 parts of tert-butyl peroxybenzoate (manufactured by NOF Corporation, "Perbutyl 2") per 100 parts of 1J,
Cobalt octenoate (cobalt content, 8% by weight) 0.
After adding 6 parts and 1 part of methylacetoacetate, 2
It was injected between two glass plates at a temperature of 5°C and kept at a temperature of 25°C for 2 days to cure.

A casting board with a thickness of 3 mounds (hereinafter referred to as casting board-rlJ).

) was obtained. The physical properties of the cast plate-rlJ were as shown in Table 1.

Examples 2-4 Epoxy equivalent weight 47 was added to the same flask used in Example 1.
946 parts of bisphenol type epoxy resin ("Araldite" Φ6071 manufactured by Chill Co., Ltd.), 176 parts of methacrylic acid, 0.1 part of hydroquinone, and 3.3 parts of triethylamine.
A reaction product was obtained in the same manner as in Example 1 by charging 2 parts.

748 parts of styrene monomer was added to the system containing this reaction product to create an epoxy ester resin (hereinafter simply referred to as Resin-111).
It's called J.

) was obtained. An alkyl peroxy ester, an organic acid salt of cobalt, and acetoacetate as shown in Table 1 were added to Resin-rlIJ, and a cast plate was obtained in the same manner as in Example 1.

The physical properties of each cast plate were as shown in Table 1.

Examples 5 to 6 In Example 2, instead of the bisphenol epoxy resin with an epoxy equivalent of 473, a bisphenol epoxy resin with an epoxy equivalent of 185 (6Araldite manufactured by Chill Co., Ltd.) was used.
A reaction product was obtained in the same manner except that 370 parts of GY-260) was used.

364 parts of styrene monomer was added to the system containing this reaction product to create an epoxy ester resin (hereinafter simply referred to as resin - "■").
It is called.

) was obtained. A cast plate was obtained in the same manner as in Example 1 by adding an alkyl peroxy ester, an organic acid salt of cobalt, and acetoacetate as shown in Table 1 to resin-rl[J.

The physical properties of each cast plate were as shown in Table 1.

Examples 7-8 Resin “■” and Resin Il” in the proportions shown in Table 1
Then, an alkyl peroxy ester, an organic acid salt of cobalt, and acetoacetate were added, and a cast plate was obtained in the same manner as in Example 1.

The physical properties of each cast plate were as shown in Table 1.

Comparative Example 1 2 parts of methyl ethyl ketone peroxide (manufactured by NOF Corporation, "Permec N"), 0.3 parts of cobalt octoate (co content 8%) and 0.4 parts of dimethylaniline were added to 100 parts of resin "■". In addition, a cast plate with a thickness of 3.0 mm was obtained in the same manner as in Example 1.

The physical properties of the cast plate were as shown in Table 2.

Comparative Examples 2 to 5 Cast plates were obtained in the same manner as in Comparative Example 1, except that the resins and resin mixtures shown in Table 2 were used.

The physical properties of the cast plate were as shown in Table 2.

Comparative Example 6 Resin - "1" 10 To 0 parts of oxybenzoate (Co content 8φ), 2.0 parts of tert-butylpar, 0.6 parts of cobalt octenoate and 71.0 parts of acetylacetate were added, and the same as in Example 1 was added. Similarly, the thickness is 3. A casting board of Q ynm was obtained.

When the physical properties of this cast plate were measured, the bending strength was 75%.
The tensile strength was 74% and the Percoll hardness was 71%.

Claims (1)

[Claims] 1. A thermosetting resin composition comprising a reaction product of a bisphenol-type epoxy resin and an unsaturated basic acid and a polymerizable unsaturated monomer is cured at a temperature in the range of 0 to 60°C. In formula (wherein, R1 and R4 represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a phenyl group, or an alkyl-substituted phenyl group. R2 represents a group having 4 to 10 carbon atoms). represents an alkyl group. R3 represents an alkylene group having 6 to 20 carbon atoms. A method for curing a thermosetting resin composition.