JPH0559221A - Quaternary ammonium salt composition and elastomer composition comprising said composition - Google Patents

Abstract

PURPOSE:To obtain a vulcanization system giving an elastomer having excellent storage stability and compression set in a high-temperature environment by melt blending a quaternary ammonium salt and a fatty acid (derivative) in specific weight proportions, followed by cooling. CONSTITUTION:1 pt.wt. quaternary ammonium salt (e.g. tetra-n-butylamonium chloride) and 0.2-10 pts.wt., in total, fatty acid (e.g. stearic acid) and fatty acid ester (derivative) are melt blended and cooled to produce a quaternary ammonium salt composition. This composition has no deliquescence. Therefore, blending this composition, used as a vulcanization system, with an epoxidized elastomer (e.g. epoxidized ethylene-vinyl acetate copolymer elastomer), isocyanuric acid, etc., gives an elastomer composition ensuring easy handling and having excellent scorch stability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to quaternary ammonium salt-containing compositions and elastomer compositions containing the compositions. According to the present invention, an elastomer that eliminates the problems caused by the deliquescent property of the quaternary ammonium salt, has excellent compression set, especially in a high temperature atmosphere, and has excellent scorch stability and storage stability. A composition can be obtained.

[0002]

2. Description of the Related Art Polyamine, diamine carbamate, ammonium organic carboxylate, dithiocarbamate, imidazoles and the like are generally used as a vulcanization system for an epoxy group-containing elastomer having an epoxy group as a crosslinking point. However, when these vulcanization systems are used, there is a defect that the scorch stability is poor when the compression set is excellent, and the compression set is poor when the scorch stability is excellent. Furthermore, these vulcanization systems require post-vulcanization for a long period of time in practical use.

Therefore, as a method for solving the above-mentioned drawbacks, a method of using a polyvalent carboxylic acid and a quaternary ammonium salt for an epoxy group-containing elastomer has been proposed (see JP-A-61-26620). .. However,
The quaternary ammonium salt has a deliquescent property and therefore has the following problems.

That is, when a solid quaternary ammonium salt is left in the air, it absorbs water within a short time (within 1 hour) and becomes a liquid. Although various additives are used in the rubber manufacturing process, liquid additives are extremely difficult to handle in industrial practice as compared with solid additives, and such liquid additives should be avoided. It is said that. Furthermore, when a quaternary ammonium salt is used, the necessary amount is being weighed, and the quaternary ammonium salt absorbs moisture in the air to change the weight, which makes accurate weighing difficult. There is also.

[0005]

In view of the above situation, the problem to be solved by the present invention is to eliminate the problems caused by the deliquescent property of the quaternary ammonium salt, and particularly to compress it under a high temperature atmosphere. It is intended to provide an elastomer composition which is excellent in permanent set property and is also excellent in scorch stability and storage stability.

[0006]

That is, the first aspect of the present invention is to provide a quaternary ammonium salt-containing composition obtained by melt-mixing the following components (A) and (B) and cooling them. It is related to. Component (A): 1 part by weight of quaternary ammonium salt (B) Component: Total amount of fatty acid, fatty acid ester and / or fatty acid ester derivative 0.2 to 10 parts by weight

The second aspect of the present invention relates to an elastomer composition comprising the following components (C) to (E). Component (C): Epoxy group-containing elastomer (D) Component: Two or more bonds represented by the following chemical formula (1) (in the formula, X and Y each independently represent an oxygen atom or a sulfur atom). Organic compound

[0008] Component (E): Quaternary ammonium salt-containing composition obtained in the first invention

The details will be described below. The first invention of the present invention relates to a quaternary ammonium salt-containing composition obtained by melt-mixing the following components (A) and (B) and cooling. Component (A): 1 part by weight of quaternary ammonium salt (B) Component: Total amount of fatty acid, fatty acid ester and / or fatty acid ester derivative 0.2 to 10 parts by weight

Specific examples of the quaternary ammonium salt as the component (A) include tetraethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide and tetra-n-.
Butyl ammonium iodide, lauryl pyridinium chloride, lauryl pyridinium bromide, decyl pyridinium chloride, etc. are mentioned.

As the component (B), fatty acids, fatty acid esters and / or fatty acid ester derivatives are used.
Of these, those having a melting point in the range of 40 to 150 ° C. are preferable. If the melting point is too low, it becomes liquid at room temperature and difficult to handle, while if the melting point is too high, it is difficult to melt-mix by heating to obtain the quaternary ammonium salt-containing composition of the present invention. become.

Specific examples of fatty acids include lauric acid, myristic acid, stearic acid, n-heneicosanoic acid and ceroplastic acid. Of these,
Stearic acid is preferable from the viewpoint that the melting point (freezing point) of the quaternary ammonium salt is close to that of the quaternary ammonium salt, and that when the mixture is melted and then cooled, it has good compatibility with the quaternary ammonium salt. As the fatty acid, dicarboxylic acid or other polycarboxylic acid may be used.

Specific examples of the fatty acid ester include methyl behenate, methyl lignocerate, methyl melicinate and the like. Specific examples of the fatty acid ester derivative include glycerin monostearate, glycerin monopalmitate, glycerin monolaurate, sorbitan palmitate, sorbitan stearate, propylene glycol monostearate, and the like, and preferably sorbitan stearate.

The ratio of the components (A) and (B) is (A)
The amount of the component (B) is 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 1 part by weight of the component. When the amount of component (B) is too small, the effect of preventing deliquescent is insufficient, while when the amount of component (B) is excessive, the effect of preventing deliquescent by using component (B) reaches a ceiling. However, it is not preferable from the economical point of view.

The temperature at which the components (A) and (B) are melt-mixed is not particularly limited as long as it is at or above the temperature at which the components (A) and (B) can be melt-mixed. The melt mixing is preferably performed in a dry nitrogen atmosphere in order to prevent water absorption during the same operation. The cooling may be carried out by leaving it at room temperature for cooling.

As described above, by using the quaternary ammonium salt as the quaternary ammonium salt-containing composition of the present invention, the above-mentioned problems caused by the deliquescent property of the quaternary ammonium salt are eliminated. It is. And by the second invention using the quaternary ammonium salt-containing composition of the present invention, while eliminating the problems caused by the deliquescent of the quaternary ammonium salt, in particular, compression set in a high temperature atmosphere It is possible to obtain an elastomer composition which is excellent in scorch stability and storage stability.

The second invention of the present invention is the following component (C):
It relates to an elastomer composition comprising the component (E). Component (C): Epoxy group-containing elastomer (D) Component: Organic compound having two or more bonds represented by the chemical formula (1) (E) Component: Quaternary ammonium salt-containing composition of the first invention

The epoxy group-containing elastomer as the component (C) is usually 0.1 to 10% by weight, preferably 0.5 to 3% by weight, of an epoxidized elastomer or an epoxy group-containing monomer as a crosslinking point. At least one monomer having a terminal vinyl or vinylidene group copolymerizable with
An elastomer obtained by copolymerizing 99.9% by weight with a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization.

Examples of the epoxy group-containing monomer used as a cross-linking point include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether and the like. Acrylate, glycidyl methacrylate and allyl glycidyl ether are preferred.

Examples of monomers having terminal vinyl and vinylidene groups copolymerizable with the epoxy group-containing monomer include
Acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and their methacrylates; vinyl acetate, vinyl propionate, vinyl acetate, etc. Esters; vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone; vinyl aromatic compounds such as styrene, α-methyl styrene, vinyl toluene; butadiene,
Conjugated dienes such as isoprene; ethylene, propylene,
Α-Mono-olefins such as 1-butene; vinyl monomers having hydroxyl groups such as β-hydroxyethyl acrylate and 4-hydroxylbutyl acrylate; vinyl and vinylidene having nitrile groups such as acrylonitrile, methacrylonitrile and β-cyanoethyl acrylate. Monomers and the like are included, and these monomers can be used alone or in combination of two or more.

Specific examples of the epoxy group-containing elastomer include epoxy group-containing acrylate copolymer elastomer, epoxy group-containing ethylene-vinyl acetate copolymer elastomer, epoxy group-containing ethylene-acrylate copolymer elastomer, epoxy group-containing ethylene. -Vinyl acetate-acrylate copolymer elastomer, epoxy group-containing ethylene-propylene copolymer elastomer, epoxy group-containing acrylate-acrylonitrile copolymer elastomer, epoxy group-containing butadiene-acrylonitrile copolymer elastomer, epoxy group-containing butadiene-styrene copolymer Examples thereof include polymer elastomers and epoxy group-containing butadiene-acrylonitrile-acrylate copolymer elastomers. , Or not particularly limited as long as the epoxy group obtained by epoxidizing an elastomer and crosslinking points.

The component (D) is an organic compound having two or more bonds represented by the chemical formula (1) and includes a heterocyclic compound, an aromatic compound and an aliphatic compound. Also,
The form containing two or more bonds represented by the chemical formula (1) includes a case where two or more bonds are independently present and a case where the bonds are continuously present as in the following chemical formula (3). Be done.

[0023] The bond represented by the chemical formula (1) may be present outside the ring as a substituent of the heterocyclic compound.

As the heterocyclic compound, parabanic acid, alloxan, alloxanthin, alloxan-5-oxime,
Valpituric acid, 5-hydroxyvalpituric acid, 5-benzalvalpituric acid, 5-aminovalpituric acid, 5-hydroxyiminovalpituric acid, 5,5-diethylvalpituric acid, 5-ethyl-5-phenyl Valpituric acid (valpital), 5- (1-methylbutyl) -5- (allyl)
Valpituric acid, 5,5-diallylvalpituric acid, isocyanuric acid, uric acid and the like, and compounds in which the oxygen atom of the carbonyl group is replaced by a sulfur atom, 2,4-dithiovalpituric acid, 2-thiovalpituric acid and the like. ..

Examples of the aromatic compounds include pyromellitic acid diimide, mellitic acid triimide, 1,4,5,8-naphthaldiimide and the corresponding thioimides. Examples of the aliphatic compound include triuret, 1-methyl triuret, 1,1-diethyl triuret, tetrauret and the like, and their corresponding thiouret.

These compounds can be added and mixed at the time of the polymerization reaction of the epoxy group-containing elastomer or at the time of the completion of the polymerization, or with the kneading machine usually used in the rubber industry, the compounding agent such as a reinforcing agent is added to the elastomer. They can be added and mixed together. The amount of these components (D) used is
A preferable range is selected from the viewpoints of vulcanization rate, mechanical properties of the vulcanized product, compression set and the like. (C) ingredient 10
The amount of the component (D) per 0 parts by weight is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight. If the amount is less than 0.1 part by weight, the crosslink density is low and it is difficult to obtain a practical vulcanized product. On the other hand, if the amount exceeds 10 parts by weight, the vulcanization rate is remarkably slow and it is difficult to obtain a vulcanizate that can be put to practical use.

The component (E) is the quaternary ammonium salt-containing composition of the first invention. Specific examples of the quaternary ammonium salt are as described in the first invention, but from the viewpoint of improving the compression set in a high temperature atmosphere, tetra-n-butylammonium chloride and Laurylpyridinium chloride is particularly preferred. The amount of the component (E) used is selected within the above ranges from the viewpoints of vulcanization rate, processing stability, storage stability, mechanical properties of the vulcanizate, compression set, etc. It is usually 0.1 in terms of the amount of quaternary ammonium salt per 100 parts by weight of component C).
10 to 10 parts by weight, preferably 0.1 to 5 parts by weight. If the amount is less than 0.1 parts by weight, the progress of vulcanization is not sufficient, while if the amount exceeds 100 parts by weight, the vulcanization rate becomes extremely high and the processing stability and storage stability are impaired. May be

The elastomer composition of the present invention may contain the following component (F) in addition to the components (C) to (E). Component (F): A compound having a bond represented by the following chemical formula (2) (wherein Z represents an oxygen atom or a sulfur atom).

[0029]

Specific examples of the component (F) include urea and N-
Methylurea, N-ethylurea, N, N-dimethylurea,
N, N-diethylurea, N, N'-diethylurea, N,
N'-ethylidene urea, N-acetyl urea, N-acetyl-N'-methyl urea, N, N'-dimethylol urea,
Aliphatic ureas such as tetramethylurea, carbamylurea, carbamoylcarbamic acid and their corresponding aliphatic thioureas; phenylurea, benzylurea, N-ethyl-N'-phenylurea, N, N'-diphenylurea ,
N, N-diphenylurea, N-acetyl-N-phenylurea, N-benzoylurea, tetraphenylurea, N,
Aromatic ureas such as N-dimethyl-N ', N'-dichlorophenylurea and their corresponding aromatic thioureas;
Ethylene urea, glycolyl urea, dimethyl parabanic acid,
Heterocyclic ureas such as benzimidazolone and 5-methyluracil and their corresponding heterocyclic thioureas are mentioned. In addition, these compounds can be used individually or in combination of 2 or more types.

In the present invention, the component (F) is not an essential component. The amount used is selected from the aspects of scorch stability, mechanical properties of vulcanizates, compression set, etc., and is usually 0.1 to 10 per 100 parts by weight of component (C).
Parts by weight, preferably 0.1 to 5 parts by weight. When the amount is less than 0.1 parts by weight, the effect of adjusting the vulcanization rate is insufficient, while when the amount exceeds 10 parts by weight, the vulcanization rate becomes extremely slow, which is not preferable in practice.

The elastomer composition of the present invention comprises, as the components (C) to (E) or the components (C) to (F), a reinforcing agent, a filler and a plasticizer usually used in the rubber industry. ,
It is prepared by mixing an antiaging agent, a stabilizer, a processing aid and the like with an ordinary kneader such as a roll or Banbury. The composition is molded into a shape according to the purpose,
The final product is passed through the vulcanization process. Vulcanization is usually 120
It is carried out at a temperature of not less than 0 ° C, preferably about 150 ° C to 220 ° C for 1 to 60 minutes. Furthermore, 150 to 200
By carrying out the secondary vulcanization at a temperature of about C for a relatively short time of 4 to 16 hours, the compression set in a high temperature atmosphere is greatly improved.

The vulcanized product of the elastomer composition obtained by the present invention is excellent in compression set in a high temperature atmosphere, and is also excellent in scorch stability and storage stability.
Since various properties such as mechanical properties and water resistance are excellent, by utilizing these properties, various sealing materials (gaskets, backings, O-rings, oil seals), various hoses, various belts, rolls, etc. It can be widely and effectively used for various purposes.

[0034]

EXAMPLES The present invention will be described with reference to Examples and Comparative Examples. Example 1 2 g of tetra-n-butylammonium chloride (hereinafter sometimes referred to as “TBA-Cl”) and 2 g of stearic acid were precisely weighed in a box in which nitrogen gas was passed, and a glass with a known tare weight was used. Mixed in container. afterwards,
Place the glass container on a hot plate at 200 ° C.
BA-Cl and stearic acid were melted, mixed with stirring, and then cooled at room temperature. The composition composed of TBA-Cl and stearic acid thus obtained was left in a constant temperature and humidity bath at a temperature of 30 ° C. and a relative humidity of 80%, and the weight change at a predetermined time of 1 hour to 168 hours was measured. The moisture absorption rate was calculated by the following formula. Absorption rate (%) = (total weight after standing-total weight before standing) / (weight of charged TBA-Cl) × 100 The results are shown in Table 1.

Example 2 Example 1 was repeated except that the amount of stearic acid was changed to 4 g. The results are shown in Table 1. Example 3 Instead of stearic acid, 2 g of Santite S (trade name, manufactured by Seiko Chemical Co., Ltd.), which is a higher fatty acid ester (wax)
Was performed in the same manner as in Example 1 except that The results are shown in Table 1. Example 4 The procedure of Example 3 was repeated except that 4 g of Suntite S was used. The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that TBA-Cl was used alone without melt mixing with stearic acid. The results are shown in Table 1. Comparative Example 2 The procedure of Example 1 was repeated, except that calcium stearate was used instead of stearic acid, and that calcium stearate and TBA-Cl were mechanically mixed without melt mixing. The results are shown in Table 1. Comparative Example 3 The procedure of Comparative Example 2 was repeated except that talc was used instead of calcium stearate. The results are shown in Table 1.

Examples 5 to 6, Comparative Examples 4 to 5 and Reference Example 1 The formulations shown in Table 2 were kneaded using an 8-inch roll to prepare formulations. Regarding the obtained compound, JIS K 630
The scorch time was measured according to 0. In addition, the compound (170 ℃ × 20 minutes press vulcanization + 185 ℃ × 4 hours
Vulcanization was performed under the conditions of secondary vulcanization in a gear oven), and the vulcanized product obtained was measured for vulcanized physical properties in accordance with JIS K6301. The results are shown in Table 2.

[0038]

[Table 1] ─────────────────────────────────── Component * 1 Weight ratio Water absorption rate (%) State * 2 ──────────────────── Standing time (Hr) 1 5 10 24 48 168 Example ───────────── ──────── 1 TBA-Cl / ST 1/1 1.5 5.6 7.7 9.5 12.0 25.0 Solid 2 TBA-Cl / ST 1/2 0.5 3.3 4.5 6.3 8.6 20.0 Solid 3 TBA-Cl / SUN 1/1 0.8 1.3 1.5 2.2 3.0 12.5 Solid 4 TBA-Cl / SUN 1/4 1.8 3.2 4.0 5.5 6.8 10.5 Solid Comparative Example 1 TBA-Cl / ST-Ca 1/1 14.7 19.8 24.3 27.1 38.3 45.2 Solid 2 TBA-Cl / talc 1 / 1 11.5 18.9 23.8 25.9 37.6 47.7 Solid 3 TBA-Cl / − 1/0 10.9 25.2 28.5 41.0 51.2 52.3 Liquid ─────────────────────────── ─────────

* 1 TBA-Cl: Tetra-n-butylammonium chloride ST: Stearic acid SUN: Santite S (higher fatty acid ester manufactured by Seiko Chemical Co., Ltd.) ST-Ca: Calcium stearate * 2 State after standing for 168 hours

[0040]

[Table 2] ─────────────────────────────────── Examples Examples Comparative examples Reference examples Blends (parts by weight) 5 6 4 5 1 Epoxy group-containing elastomer * 3 100 100 100 100 100 FEF black * 4 40 40 40 40 40 Stearic acid 1 1 1 1 1 No Guard 445 * 5 2 2 2 2 2 Isocyanuric acid 0.8 0.8 0.8 1.0 0.8 DPU * 6 2.3 2.3 2.3 2.3 2.3 Composition containing quaternary ammonium salt * 7 1.5 2.5---OTMAB * 8--1.5--DTMAC * 9---1.0 1.0 TBA-Cl * 10----0.5 Evaluation result ( Vulcanization properties) Tensile strength Kg / cm ² 172 168 180 172 167 Elongation% 400 380 420 400 360 Hardness JIS-A 62 64 65 63 65 Compression set 150 ℃ × 70Hr 24 22 40 44 23 185 ℃ × 70Hr 63 59 88 82 61 ───────────────────────────────────

* 3 Ethylene 39 wt%, Methyl acrylate 5
Epoxy group-containing elastomer consisting of 9 wt% and glycidyl methacrylate 2 wt% * 4 Seast SO * 5 Uniroyal Amine Antioxidant Product name * 6 Diphenylurea * 7 In Example 5, the quaternary ammonium salt of Example 1 was included. * 8 octadecyltrimethylammonium bromide * 9 n-dodecyltrimethylammonium chloride * 10 tetra-n-butylammonium chloride was used in Example 6 and the quaternary ammonium salt-containing composition in Example 4 respectively. ,
Used without melt mixing with stearic acid

In Examples 1 to 4, which are the quaternary ammonium salt-containing compositions of the present invention, the water absorption rate is small, that is, the problem due to the deliquescent property of the quaternary ammonium salt is sufficiently eliminated. I understand. On the other hand, in Comparative Examples 1 to 3 in which the quaternary ammonium salt was used as it was without the present invention, the water absorption rate was extremely large, and there was a problem due to deliquescent. Moreover, Examples 5 and 6 which are the elastomer compositions of the present invention are excellent in compression set in a high temperature atmosphere. On the other hand, Comparative Examples 4 and 5 which are conventional elastomer compositions not according to the present invention
Has poor compression set in a high temperature atmosphere.
The compression set of Examples 5 and 6 is about the same as that of Reference Example 1, and even when the quaternary ammonium salt is used as the quaternary ammonium salt-containing composition of the present invention, the quaternary ammonium salt is obtained. It can be seen that the improving effect on the compression set of the salt does not decrease at all.

[0043]

As described above, according to the present invention, the problems due to the deliquescent property of the quaternary ammonium salt are eliminated, and in particular, the compression set is excellent in a high temperature atmosphere and the scorch is stable. It was possible to provide an elastomer composition having excellent properties and storage stability.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08K 5/34 KBF 7167-4J

Claims (4)

[Claims] 1. A quaternary ammonium salt-containing composition obtained by melt-mixing the following components (A) and (B) and cooling. Component (A): 1 part by weight of quaternary ammonium salt (B) Component: Total amount of fatty acid, fatty acid ester and / or fatty acid ester derivative 0.2 to 10 parts by weight 2. The composition according to claim 1, wherein the quaternary ammonium salt is tetra-n-butylammonium chloride or laurylpyridinium chloride. 3. An elastomer composition comprising the following components (C) to (E). Component (C): Epoxy group-containing elastomer (D) Component: Two or more bonds represented by the following chemical formula (1) (in the formula, X and Y each independently represent an oxygen atom or a sulfur atom). Organic compound (E) component: The composition according to claim 1. 4. The components (C) to (E) according to claim 3,
And an elastomer composition comprising the following component (F). Component (F): A compound having a bond represented by the following chemical formula (2) (wherein Z represents an oxygen atom or a sulfur atom).