JPH0670109B2 - Composition having curing promoting action - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a reinforced plastic having glass fiber as a reinforcing material (hereinafter abbreviated as FRP) as a housing relation such as a bathtub and a septic tank, a fishing boat, a yacht, a boat, etc. A composition that accelerates the curing of radical curable resins, which has been put to practical use in a wide range of applications such as ships, plants such as pipes and tanks, and non-FRP paints, linings, castings, decorative boards, laminated boards, etc. Regarding things.

[Conventional technology]

Radical curable resins such as unsaturated polyester resins and vinyl ester resins are well known and widely used as means for curing them by using a radical generator and a curing accelerator together.

In recent years, there has been a strong demand for reducing the color tone of cured products as much as possible to improve their appearance regardless of whether they are FRP or non-FRP.

For example, when manufacturing a marble-thick wall-thick casting bath, an organic acid salt of cobalt is used as a hardening accelerator in order to carry out hardening at room temperature or low temperature. Yellowing occurs, and the appearance tends to be seriously damaged. On the contrary, if the amount is small, there is a drawback that the curing does not proceed at room temperature.

The same phenomenon applies to light-colored paints and decorative boards.

[Problems to be Solved by the Invention]

If you try to cure the radical curable resin at room temperature or a temperature close to it, it is inevitable to use the organic acid salt of cobalt, but even if you try to take one trouble of yellowing, to avoid this It is essential that there is only a way to reduce the amount of cobalt salt, and that the curing time is not extended and the physical properties of the molded product are not deteriorated. In this case, it is general to mix the resin with an acceleration aid in advance, but the addition of the acceleration aid tends to significantly impair the storage stability of the mixed resin and does not deteriorate the curability. In addition, there has been a strong demand for improving storage stability.

However, no satisfactory solution to this requirement has yet been found.

The present invention eliminates the above-mentioned drawbacks of conventional curing agent systems, prevents discoloration that occurs when the radical-curable resin is cured at room temperature or a temperature close thereto, and has excellent storage properties. It is intended to provide a composition which has stability, is completely cured in a short time, and does not deteriorate the physical properties of a cured product at all, and has a curing-accelerating action for a radical-curable resin.

[Means for Solving the Problems]

In order to solve the above-mentioned problems, the present inventors have studied a combination of several types of acceleration aids and stability, and as a result, acetylacetone, which has been conventionally used as an acceleration aid, is mixed with a radical curable resin. It is known that the stability will be significantly impaired, but if a copper compound soluble in an organic solvent (hereinafter referred to as a copper salt) is used as a stabilizer to restore the stability, acetylacetone It was found that the ability to accelerate curing was severely hindered. On the contrary, when an acetoacetonate amine compound containing an N-acetoacetyl group bonded to a nitrogen atom in a secondary amino group (hereinafter simply referred to as an acetoacetonate compound) is used as a accelerating aid in combination with a copper salt, Contrary to the above-mentioned acetylacetone, it was found that not only the effect of the acetoacetonate amine compound as a promoter aid is accelerated, but also the stabilizing effect of the copper salt is maintained as it is, and the present invention can be completed. did it.

[Action]

The reason why the composition of the present invention in which the acetoacetonate amine compound and the copper salt are used in combination exhibits excellent curing acceleration action and stability as a room temperature curing acceleration aid for radical curable resins such as polyester resin and vinyl ester resin. Although it is not clear, it is presumed that the presence of the N-acetoacetyl group bonded to the nitrogen atom largely contributes.

The acetoacetonate amine compound used in the present invention is 2
It can be easily synthesized by N-acetoacetylating a primary amine with a ketene dimer. The reaction is exothermic and is carried out with cooling if necessary. Examples of the secondary amine include a heterocyclic compound and an aromatic secondary amine compound, but it is not necessary to particularly limit the production thereof.

The acetoacetonate amine compound obtained from the secondary amine of the heterocyclic compound preferably used in the present invention is represented by the following general formula [I].

Examples of the secondary amine of the heterocyclic compound that can be used include:
Morpholine, piperidine, N-methylpiperazine, piperazine, pyrrole, ethyleneimine, pyrrolidine, azetidine, 2-pyrroline, pyrazole, pyrazoline, pyrazolidine, anabasine, 4-methylimidazole and other imidazoles, indoles, carbazoles, indazole The kind is mentioned.

In particular, those using morpholine as a raw material are preferable because the cured resin has a good hue.

An acetoacetonate amine compound obtained from an aromatic secondary amine that can be used in the present invention is represented by the following general formula [II] as a model.

[R is an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group, an acetoacetoxyalkyl group, and R'is 1 to 8 carbon atoms.
Examples of the aromatic secondary amine preferably used in the present invention include monomethylaniline, monoethylaniline, monobutylaniline, monoethanolaniline, paramethyl N-methylaniline and benzylaniline. Can be mentioned. Other aromatic secondary amines such as other monomethylnaphthylamines can also be used.

Aromatic secondary amines, especially those with alcoholic hydroxyl groups, can be powerful and useful accelerating aids because the hydroxyl groups are also acetoacetoxylated.

The acetoacetonate amine compound obtained from the aliphatic secondary amine that can be used in the present invention is represented by the following general formula [III].

[R ₁ and R ₂ represent an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group or an acetoacetoxyalkyl group] Examples of the aliphatic secondary amine preferably used in the present invention include dimethylamine, Examples include diethylamine, diisopropylamine, dibutylamine, diethanolamine, N-methylaminoethanol.

In particular, an aliphatic secondary amine having a hydroxyl group is preferable because the hydroxyl group is also acetoacetoxylated, and thus, it is a very useful accelerator aid.

The copper salt used in the present invention needs to be soluble in an organic solvent, and by its nature, an organic acid salt of copper, for example, copper naphthenate or copper octylate best meets the purpose of the present invention.

The amount of the acetoacetonate amine compound used per 100 parts by weight of the radical curable resin (hereinafter referred to as “part”) is 0.01
It is from 5 parts to 5 parts, preferably from 0.05 part to 0.5 parts.

The mixing ratio of the copper salt to 100 parts of the acetoacetonate amine compound is 0.01 to 1 part as copper.
Even if the blending ratio is more than 1 part, the tendency that the effect is increased in proportion to the blending amount is diminished, and if it is less than 0.01 part, the effect of using the copper salt together is small. Suitably, the compounding ratio of the copper salt is preferably in the range of 0.1 to 10 ppm with respect to the radical effect resin.

Radical curable resins that are the subject of the present invention are unsaturated polyester resins and oligoacrylates represented by vinyl ester resins.

The unsaturated polyester resin contains an α-β unsaturated polybasic acid as an essential component, and is obtained by esterifying with a polyhydric alcohol with or without any saturated or unsaturated polybasic acid. It is obtained by dissolving saturated alkyd in a copolymerizable vinyl monomer, and its composition does not need to be particularly limited.

Oligoacrylates are classified into the following types.

i) vinyl ester resin, ii) urethane to acrylate, iii) polyester to acrylate, but vinyl ester resin is mostly used in practical use.

The vinyl ester resin is usually obtained by reacting an epoxy resin with (meth) acrylic acid, and styrene is used as a monomer in a room temperature curing system used in the field of corrosion resistance.

The type of epoxy resin is not specified, but the bisphenol type and novolac type occupy most practically.

The urethane-acrylate is obtained by reacting an unsaturated alcohol having a (meth) acryloyl group with a diisocyanate in the presence or absence of any polyhydric alcohol, polyether or polyester.

Polyester to acrylate are (meth) acrylic acid,
It is synthesized by direct esterification of a saturated or unsaturated polybasic acid or its acid anhydride with a polyhydric alcohol.

As the organic peroxide used as a curing agent for the radical curable resin, those generally used are sufficient, and are used in the range of 0.5 part or more and 3 parts or less. Further, an organic acid salt of cobalt is required as a curing accelerator, and examples thereof include cobalt salts such as naphthenic acid and octylic acid, and these are used in an amount of 0.01 part or more and 2 parts or less. It is possible to freely use other metal, for example, an organic acid salt such as manganese or vanadine.

The composition having a curing promoting action according to the present invention is a curing agent,
It can be used together with a curing accelerator in the field of room temperature curing of radical curable resins, such as FRP, paints, linings, and casting.

Also, reinforcing materials, fillers, coloring agents, release agents, polymers,
It goes without saying that the above can be used together if necessary.

〔Example〕

Next, in order to help understanding of the present invention, examples will be shown below.

After performing Reference Example 1 N-acetoacetyl charged morpholine 609g synthesis autoclave acetyl morpholine, nitrogen substitution (3.0 kg / cm ² was subjected under reduced pressure to 0.2kg / cm ²⁾ 3 times, 617 g of ketene dimer to a closed dropping funnel After charging, the internal pressure in the funnel was adjusted to about 5 kg / cm ² with nitrogen gas, and the mixture was added dropwise to morpholine in the autoclave over about 2 hours.

Since the exotherm was observed by dropping the ketene dimer, the reaction was carried out while cooling so that the reaction temperature was 60 ± 3 ° C.

After the dropping of the ketene dimer was completed, the temperature was maintained at 60 ° C. for 30 minutes, then the temperature was returned to room temperature, and the contents were injected into a closed air and solidified.

A pale yellow, melted 53 ° C. crystal was obtained, and as a result of elemental analysis, it was determined to be a compound of the following formula. The yield was 98.7 (%).

N-acetoacetylmorpholine (hereinafter abbreviated as accelerating aid A) Reference Example 2 Synthesis of N-methylacetoacetanilide Charge autoclave with 642 g of monomethylaniline,
Nitrogen substitution returned to normal pressure was repeated three times to 0.2 kg / cm ² from the pressure 3.0 kg / cm ^2, were charged ketene dimer 529g to the dropping funnel, a pressure of about 5 kg / cm ² was added with nitrogen gas filling, autoclave Was added dropwise.

Since heat was generated with the dropping, cooling was performed so that the temperature did not rise above 50 ° C.

After dropping for 2 hours, the mixture was aged for 30 minutes while maintaining the temperature at 45 to 50 ° C.

It was poured into a nitrogen sealed container and solidified. N-methylacetoacetanilide (the following formula), which were pale yellow needle-like crystals, was obtained with a yield of 99 (%).

N-methylacetoacetanilide will be referred to as a accelerating aid (B) hereinafter.

Reference Example 3 Synthesis of N-methylamino N-acetoacetoxyethylacetoacetamide N-methylaminoethanol 375g, styrene 375g, copper naphthenate 1ppm (relative to styrene) were charged into an autoclave, and nitrogen substitution (3.0kg / cm was applied to this). (Reduced pressure to 0.2 kg / cm ² ) 3 times, and then put in a closed dropping funnel with ketene dimer.
Charge 1024g, and use nitrogen gas to increase the internal pressure of the funnel to about 5kg / cm ^2.
Then, it was added dropwise to N-methylaminoethanol in the autoclave over about 2 hours.

The reaction temperature was kept at 50 ° C. or lower because heat was generated at the same time as the dropping.

50 ~ after completion of dropping the ketene dimer (it takes about 2 hours)
After holding at 60 ° C. for 30 minutes, the pressure was returned to normal pressure, and the contents were put in a closed container and cooled.

Light yellowish brown liquid, the following formula A styrene solution of a compound of N-methyl N-acetoacetoxyethylacetoacetamide was obtained. Infrared analysis and NM
From the result of R analysis, the structure of the above formula was deduced.

The yield was 99 (%), which was quantitative. This was designated as a promotion aid (C).

Example 1 Bisphenol A propylene oxide adduct, 2,
360 g of 2'bis [para (hydroxy-n-propoxy) phenyl] propa and 116 g of fumaric acid were weighed in a 1 l separable flask equipped with a stirrer, a fractionating condenser, a gas inlet tube, and a thermometer, and nitrogen gas was added. Esterification at 210-220 ℃ in airflow to synthesize unsaturated alkyd with acid value 28.1, 0.15g
Was added to a metal vat and solidified.

Next, 400 parts of the crushed unsaturated alkyd was added to styrene 400
Was added to the above parts under stirring to prepare a bisphenol type unsaturated polyester resin [I] as a uniform solution.

Its Hazen color number was 450 and its viscosity was 5.4 poise. Methyl ethyl ketone peroxide 1 to 100 parts of resin [I]
Part, a system in which 0.1 part of cobalt octylate was added, and Reference Example 1
Each of the acceleration aids (A) to (C) produced in Examples 3 to 3, acetylacetone (D) as a comparative example, and a predetermined amount of copper naphthenate were mixed, and a curability test was performed. The results are shown in Table 1.

It is clear that, while acetylacetone significantly reduces the curing acceleration ability by the combined use of copper, morpholine to acetylacetonate conversely increases the curing acceleration ability by the combined use of copper.

The stability of the system without the addition of methyl ethyl ketone peraxide at 60 ° C. seems to be seen in Table 1, and the effect of copper naphthenate was recognized.

Example 2 A curability test was conducted in the same manner as in Example 1 except that acetylacetonate of pyrrolidine (N-acetoacetylpyrrolidine) was used in place of the morpholine to acetylacetonate of Example 1. The results are shown in Table 2.

Example 3 Synthesis of vinyl ester resin [II] In a 1 l separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 550 g of Epicoat ^# 1001 of Yuka Shell Co., Ltd. as an epoxy resin, 86 g of methacrylic acid, and 0.5 of hydroquinone were used. g, trimethylbenzylammonium chloride 2g, and reacted for 3 hours with vigorous stirring at 130-135 ° C, the acid value became 9.4, so the initial content of styrene was 300g, and then the content was poured into a 2l beaker. Further, 250 g was added to obtain vinyl ester resin [II].

The Gardner color number was 5, and the viscosity was 5.4 poise.

The same system as in Reference Examples 1 to 3 was added to 100 parts of vinyl ester resin [II], 1.5 parts of peroxide (328 of Kayaku Nouri Co., Ltd.) and 0.3 part of cobalt naphthenate as a promoter. N-acetoacetylpiperidine (E) produced by the method,
N-acetoacetoxyethylacetanilide (F) and
The curability of the system with N-methyl-N-acetoacetoxyethylacetoacetamide (G), copper naphthenate, was tested. The results were as seen in Table 3.

The storage stability at 60 ° C is 3 days for the addition of 0.3 phr of N-acetoacetylpiperidine, and 7 days for the addition of copper naphthenate.
A clear difference was observed by day.

〔The invention's effect〕

The composition having a curing-accelerating effect of the present invention has excellent storage stability by using the N-acetoacetyl group-containing compound and a copper salt together, and the radical-curable resin is yellowed at room temperature or a temperature close thereto. It can be completely cured in a short time without any change, and the physical properties of the cured molded product are not deteriorated at all, so it is extremely useful in the field of room temperature curing such as FRP, paint, lining, and casting.

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Hiromitsu Abe 3100 Uemiyata Minamishitaura-cho, Miura City, Kanagawa Prefecture (72) Inventor Yakichi Igarashi 782-4 Shinko-ji Town, Machida City, Tokyo

Claims (4)

[Claims] 1. A acetoacetonate amine compound containing (A) an N-acetoacetyl group bonded to a nitrogen atom in a secondary amino group, and (B) an organic solvent-soluble copper compound. A composition having a curing-accelerating action on a radical-curable resin. 2. As an acetoacetonate amine compound containing an N-acetoacetyl group, N-acetoacetylmorpholine, N-acetoacetylpiperidine, N-acetoacetylpyrrolidine, N-methylacetoacetanilide, N-acetoacetoxy. Ethyl acetoacetanilide, N, N-dimethylacetoacetamide or N-methyl N-acetoacetoxyethylacetoacetamide is used for curing acceleration action of the radical-curable resin according to claim 1. A composition having. 3. Accelerating the curing of the radical-curable resin according to claim 1 or 2, wherein copper naphthenate or copper octylate is used as the copper compound soluble in an organic solvent. A composition having an action. 4. A vinyl ester resin obtained by reacting an unsaturated polyester resin or an epoxy resin with (meth) acrylic acid as a radical-curable resin. A composition having a curing-accelerating action on the radical-curable resin according to item 3.