JPH02191633A - Composition having curing accelerating action - Google Patents

Abstract

PURPOSE:To obtain a composition, consisting of a specific acetoacetonatoamine compound and copper compound soluble in organic solvents, excellent in storage stability, capable of curing radical curing type resins at about ambient temperature in a short time without yellowing and suitable as FRP, coatings, etc. CONSTITUTION:The objective composition consisting of (A) an N- acetoacetonatoamine compound (preferably N-acetoacetylmorpholine, N- acetoacetylpiperdine, N-acetoacetylpyrrolidine, N-methylacetoacetanilide, N- acetoacetoxyethylacetoacetanilide, N,N-dimethylacetoacetamide or N-methyl-N- acetoacetoxyethylacetoacetamide) containing N-acetoacetyl group bound to nitrogen atom in secondary amino group and (B) a copper compound (preferably copper naphthenate or copper octylate) soluble in organic solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a bathtub as a reinforced plastic (hereinafter abbreviated as FRP) using glass fiber as a reinforcing material.

It has been put to practical use in a wide range of applications, including housing-related products such as septic tanks, fishing boats, boats, and other vessels, plant-related products such as vibrators and tanks, and non-FRP products such as paint 1 linings, cast 5 decorative boards, and laminates. , relates to a composition that enhances the effect of accelerating the curing of radical curable resins.

[Conventional technology]

For radical curable resins such as unsaturated polyester resins and vinyl ester resins, the method of curing them by using a radical generator and hard cutting in combination is well known and widely used.

In recent years, there has been a strong desire to make the color of cured molded products as light as possible to improve their appearance, regardless of whether they are FRP or non-FRP.

For example, when manufacturing a thick-walled cast bathtub with an astronomical stone look, cobalt organic acid salts are used as hardening accelerators in order to harden at room temperature to low temperatures. There is a tendency for yellowing to occur inside the product, seriously detracting from its appearance. On the other hand, if the amount is small, curing will not proceed at room temperature.

A similar phenomenon is true for light-colored paints and decorative boards.

[Problem to be solved by the invention]

When trying to cure radical-curing resins at room temperature or a temperature close to this temperature, the use of cobalt a-organic acid salts is unavoidable, but in order to avoid the trouble of yellowing, The only option is to use a reduced amount of cobalt salt, and it is essential that there be no prolongation of the curing time or deterioration of the physical properties of the molded product. In this case, it is common to mix an accelerator with the resin in advance, but adding an accelerator tends to significantly impair the storage stability of the mixed resin. Therefore, there was a strong need to improve storage stability.

However, at present, a satisfactory solution to this requirement has not yet been found.

The present invention overcomes the above-mentioned drawbacks of conventional curing agent systems.[2] It also prevents discoloration that occurs during curing of radical curing resins at or near room temperature. To provide a composition that has storage stability, is completely cured in a short time, and has no deterioration in the physical properties of the cured molded product, and has an effect of accelerating the curing of a radical-curable resin.

[Means for Solving the Three Problems] In order to solve the three problems mentioned above, the present inventors investigated combinations of several types of accelerators and stabilizers, and found that It is known that when acetylacetone is mixed with a radical-curing resin, its stability is significantly impaired, but in order to restore its stability, a copper compound (soluble in organic solvents) is used as a stabilizer. It has been found that the combined use of copper salts (hereinafter referred to as copper salts) severely inhibits the ability of acetylacetone to accelerate curing. On the other hand, when an acetoacetonate amine compound (hereinafter simply referred to as an acetoacetonate compound) containing an N-acetoacetyl group bonded to a nitrogen atom in a secondary amino group is used as a promoter in combination with a copper salt, It was discovered that, contrary to the above-mentioned acetylacetone, the effect of the acetoacetonate amine compound as a promoter is not only accelerated, but also the stabilizing effect of the copper salt is maintained, and the present invention has been completed. did it.

[Function] The composition using the acetoacetonate amine compound of the present invention in combination with a copper salt has excellent curing accelerating action and stability as a room temperature curing accelerator for radical curing resins such as polyester resins and vinyl ester resins. Although the reason for this property is not clear, it is presumed that the presence of the N-acetoacetyl group bonded to the nitrogen atom contributes greatly.

The acetoacetonate amine compound used in the present invention is 2
It can be easily synthesized by N-acetoacetylation of a class amine with a ketene dimer. The reaction is exothermic and is carried out with cooling if necessary. Examples of the secondary amine include heterocyclic compounds, aromatic, and aliphatic secondary amine compounds, but there is no need to particularly limit the structure 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 (1).

Examples of secondary amines of heterocyclic compounds that can be used include:
Morpholine, piperidine, N-methylbiperazine, piperazine, virol, ethyleneimine, pyrrolidine 8azetidine, 2-viroline.

Pyrazole, pyrazoline, pyrazolidine, anabasine,
Imidazoles including 4-medylimidazole,
indoles, carbazoles.

Examples include indazoles.

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

The acetoacetonate amine compound obtained from an aromatic secondary amine that can be used in the present invention is represented by the following general formula (U).

(Left below) [R is an alkyl group having 1 to 8 carbon atoms, hydroxyalkyl style, acetoacetoxyalkyl group, R' is an alkyl group having 1 to 8 carbon atoms
[Representing an alkyl group] Examples of aromatic secondary amines suitably used in the present invention include monomethylaniline, monoethylaniline, monobutylaniline, monoethanolaniline, 5-methyl N-methylaniline, and benzylaniline. Can be mentioned. Other aromatic secondary amines such as monomethylnaphthylamines can also be used.

In particular, aromatic secondary amines having alcoholic hydroxyl groups can be very useful accelerators because the hydroxyl groups are also acetoacetoxylated.

An acetoacetonate amine compound obtained from an aliphatic secondary amine that can be used in the present invention is represented by the following general formula (III).

[R and R2 represent an alkyl group having 1 to 8 carbon atoms, a hydroxyunoalkyl group, or an acetoacetoxyalkyl group] Examples of aliphatic secondary amines preferably used in the present invention include dimethylamine, diethylamine, etc. , diisopropylamine, dibutylamine.

jetanolamine, N-methylaminoethanol)
I can get hit.

Particularly, aliphatic secondary amines that convert hydroxyl groups into acetoacetoxylates are suitable because they also serve as very useful accelerators.

The copper salt used in the present invention must be soluble in an organic solvent, and organic acid salts with typical properties, such as copper naphthenate and copper octylate, are most suitable for the purpose of the present invention.

The amount of acetoacetonate amine compound used per 100 parts by weight (hereinafter referred to as parts) of radical curable resin is 0.
,01 parts to 5 parts, preferably 0.05 parts to 0.0 parts.
No more than 5 copies.

Further, the blending ratio of the copper salt to 100 parts of the acetoacetonate amine compound is in the range of 0.01 to 1 part as copper. Even if the blending ratio is greater than 1 part, the tendency for the effect to increase in proportion to the blending amount is reduced, and 0, 0
If the amount is less than 1 part, the effect of the combined use of copper salt will be small. Preferably, the blending ratio of the copper salt is Q, I to 1 with respect to the radical curing resin.
．． A range of Qppa is desirable.

The radical curable resins to which the present invention is applied are unsaturated polyester resins and oligoacrylates typified by vinyl ester resins.

Unsaturated polyester resin contains an α-β unsaturated polybasic acid as an essential component, and can be obtained by esterifying it with a polyhydric alcohol, with or without any saturated or unsaturated polybasic acid. It is obtained by dissolving a saturated alkyd in a copolymerizable vinyl monomer, and there is no need to place any particular restrictions on its composition.

Oligoacrylates can be divided into the following types:

1) Vinyl ester resin, 11) Urethane acrylate, 1ii) Polyester acrylate. However, from a practical standpoint, vinyl ester resin is mostly used.

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

Although the type of epoxy resin is not specified, bisphenol type and novolak type account for most in practical use.

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

Generally used organic peroxides used as curing agents for radical-curable resins are sufficient, and 0.5
It is used in the range of 1 part or more and 3 parts or less.

In addition, as a curing accelerator, an organic acid salt of cobalt is required, and examples thereof include cobalt salts such as naphthenic acid and octylic acid, and these include cobalt salts such as naphthenic acid and octylic acid. O is used in an amount of 1 part or more and 22 parts or less. AA of other metals such as manganese, vanadine, etc.
The concomitant use of lytic acid salts can be freely carried out.

The composition having a curing accelerating effect according to the present invention includes 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.

In addition, reinforcing materials, fillers, colorants, mold release agents, polymers,
Of course, a hat can be used in combination as needed.

〔Example〕

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

Reference Example I Synthesis of N-acetoacetylmorpholine 609 g of morpholine was charged into an autoclave and replaced with nitrogen (applying 3.0 kg/e- and reducing the pressure to 0.2 kg/c-)
After doing this three times, put 617g of ketene dimer into a closed dropping funnel, and reduce the internal pressure inside the funnel to about 5B with nitrogen gas.
/ ej to morpholine in the autoclave about 2
It dripped over time.

Since heat generation was observed due to the dropwise addition of the ketene dimer, the reaction was carried out while cooling to a reaction temperature of BO±3°C.

After dropping the ketene dimer, the temperature was maintained at 60° C. for 30 minutes, and then the temperature was returned to room temperature and the contents were poured into a sealed container and solidified.

A pale yellow crystal with a melting point of 53° C. 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 (
%)Met.

N-acetoacetylmorpholine (hereinafter abbreviated as accelerator A) Reference example 2 Synthesis of N-methylacetoacetanilide 842 g of monomethylaniline was charged into an autoclave, and nitrogen substitution was performed from a pressure of 8.0 kg/cd to 0.2 kg/cj. After repeating 3 times, return to normal pressure and add ketene dimer 52 to the dropping funnel.
9 g was charged, and a pressure of about 5 kg/c was applied by filling with nitrogen gas, and the mixture was dropped into an autoclave.

Since heat was generated during dropping, the solution was cooled to prevent the temperature from rising above 50°C.

After dropping for 2 hours, the temperature was maintained at 45-50℃ for 3 hours.
Aged for 0 minutes.

It was poured into a nitrogen-filled container and solidified. N-methylacetoacetanilide (the following formula), which is a pale yellow needle-like crystal, was obtained in a yield of 99 (%).

The contents were placed in a sealed container and cooled.

A pale yellowish brown liquid with the following formula: %formula% Hereinafter, this will be referred to as the accelerator (B).

Reference example 3 375g of N-methylaminoethanol in an autoclave
, 375g of styrene and 1pp of copper naphthenate fat (relative to styrene) were charged, and after nitrogen substitution (applying 3.0kg/cm and reducing the pressure to 0.2kg/J) three times, a sealed layer (0-) was added. 1,024 g of ketene dimer was added to the autoclave, and the internal pressure in the funnel was increased to about 5 kg/cd using nitrogen gas, and about 2 g was added to N-methylaminoethanol in the autoclave.
It dripped over time.

Since heat is generated when dropping, l, iJ, the reaction temperature is 50°C.
I kept it below.

After the completion of dropping the ketene dimer (requires about 2 hours), 50
After maintaining the temperature at ~60°C for 30 minutes, the pressure was returned to normal pressure to obtain a styrene solution of the compound N-methyl N-acetoacetoxyethyl acetoacetamide. Infrared analysis and N
From the results of MR analysis, the structure of the above formula was deduced.

The yield was 99 (%) and quantitative. This is promoted by an aid (
C).

Example l Bisphenol A propylene oxide adduct, 2
．． 2' Bis [rose (hydroxy-〇-propoxy)
phenyl]propane, 3θog, fumaric acid flag,
Stirrer 1 fractionation condenser, gas inlet pipe.

It was weighed into a 1 g separable flask equipped with a thermometer and esterified at 20 to 220°C in a nitrogen gas stream to synthesize an unsaturated alkyd with an acid value of 28.1.
Hydroquinone was added, poured into a metal vat, and solidified.

Next, 400 parts of the pulverized unsaturated alkyd was added to 400 parts of styrene with stirring to produce a bisphenol type unsaturated polyester resin [11] as a homogeneous solution.

Its Hazen color number was 450, and its viscosity was 5.4 voids. To a system in which 1 part of methyl ethyl ketone peroxide and 0.1 part of cobalt octylate were added to 100 parts of resin CI3, accelerators (A) to (C) produced in Reference Examples 1 to 3, and acetylacetone (D) as a comparative example were added. A predetermined amount of copper naphthenate and copper naphthenate were blended and a hardenability test was conducted. The results are shown in Table 1.

It is clear that acetylacetone's ability to accelerate hardening is significantly reduced when used in combination with copper, while morpholine acetylacetonate conversely increases its ability to accelerate hardening when used in combination with copper.

60℃ without adding methyl ethyl ketone peroxide
As shown in Table 1, the stability of copper naphthenate was found to be effective.

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

Table 2 Example 3 Into a six-component vinyl ester resin (II) separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 550 g of epoxy resin Epicoat "+" and ooi of oily shell ■ and methacrylic acid were added. 88
g z 0.5 g of hydroquinone, 2 g of )limethylbenzyl ammonium chloride, 130-1
After reacting at 35°C for 3 hours with vigorous stirring, the acid value was 9.4, so styrene was initially added to 300g, then 2
The contents were poured into a beaker and an additional 250 g was added to obtain vinyl ester resin CU].

Guard Qi color number 5. The viscosity was 5.4 voids.

Reference Example 1: To 100 parts of vinyl ester resin (n), 1.5 parts of peroxide (Kayaku Nouri Oki 328) and 0.3 parts of cobalt naphthenate were added as a promoter.
N-acetoacetylpiperidine (B), N-acetoacetoxyethylacetanilide (F), N-methyl-N-acetoacetoxyethylacetoacetamide (C), and copper naphthenate produced in the same manner as in step 3. The curability of the system was tested. The results were as seen in Table 3.

(The following is a blank space) Regarding the storage stability at 00° C., a clear difference was observed between 3 days for the addition of 0.3 phr of N-acetoacetylpiperidine and 7 days for the addition of copper naphthenate.

〔Effect of the invention〕

The composition having a curing accelerating effect of the present invention has excellent storage stability by using an N-7 cetoacetyl group-containing compound and a copper salt in combination, and allows the radical curing resin to turn yellow at room temperature or a temperature close to it. FRP, PJ! It is extremely useful in the field of room temperature curing such as materials, linings, and casting.

Patent applicant: Showa Kobunshi Co., Ltd. same Nippon Emulsifier Co., Ltd. teenager Reason Man

Claims (4)

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