JP2001279191A - Rosin acid amide derivative, nucleating agent for crystalline thermoplastic resin and crystalline thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nucleating agent for crystalline thermoplastic resin which increases the rate of crystalli-zation of the crystalline thermoplastic resins and, in addition, can produce a molded product (a crystalline thermoplastic resin composition) having excellent mechanical properties, and a crystalline thermoplastic resin composition. SOLUTION: The nucleating agent for thermoplastic resins comprises a rosin acid amide derivative represented by the formula: X-Y-Z-D (wherein X is a rosin acid residue; Y is CONH; Z is a carboxyphenylene group or its metal salt; D is hydrogen atom or an organic group represented by Y-X), and the crystalline thermoplastic resin composition is obtained by incorporating (B) 0.001-30 pts.wt., nucleating agent into (A) 100 pts.wt., crystalline thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel rosinamide derivative, a nucleating agent for a crystalline thermoplastic resin containing the derivative, and a crystalline thermoplastic resin composition.

[0002]

2. Description of the Related Art Crystalline thermoplastic resins such as polyolefins, polyesters, polyamides, and polyacetals have excellent processability, chemical resistance, electrical properties, mechanical properties, and the like. Molded products, films,
It is processed into sheets, fibers, etc. and used for various purposes. However, these crystalline thermoplastic resins may not have sufficient rigidity, heat-resistant rigidity, transparency, etc. depending on the use.

It is known that, in order to improve the rigidity, heat resistance rigidity, and transparency of a molded body made of a crystalline thermoplastic resin, fine crystals should be rapidly generated during molding. Therefore, as a means for increasing the crystallization rate of a crystalline thermoplastic resin, a nucleating agent such as talc has been conventionally used. However, such a conventional crystal nucleating agent is not always sufficient to improve the crystallization rate, and also does not necessarily satisfy mechanical properties such as impact strength and optical properties such as gloss of the obtained molded article. Was.

In order to solve the above problems, the present applicant has proposed a crystal nucleating agent for a crystalline thermoplastic resin comprising a specific metal rosinate as Japanese Patent Application No. 6-127478.
The crystalline thermoplastic resin composition containing this crystal nucleating agent,
Although excellent in mechanical properties and optical properties, crystalline thermoplastic resin compositions are required to have further improved mechanical properties.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made under the above-mentioned circumstances, and is intended to increase the rate of crystallization of a crystalline thermoplastic resin and to provide a molded article having excellent mechanical properties. It is an object of the present invention to provide a nucleating agent for a crystalline thermoplastic resin and a composition for a crystalline thermoplastic resin which can produce (crystalline thermoplastic resin composition).

[0006]

Means for Solving the Problems The present inventor has conducted intensive studies in order to solve the above-mentioned object, and as a result, the following general formula (1)
It has been found that the above problem can be solved by using a novel rosinamide derivative represented by the formula (1) as a crystal nucleating agent for a crystalline thermoplastic resin, and the present invention has been completed.

That is, the present invention provides a compound represented by the following general formula (1): X
-YZD (wherein X is a rosin acid residue, Y is -CON
H- and Z represent a carboxyphenylene group or a metal salt thereof,
D represents a hydrogen atom or an organic group represented by YX), a rosinamide derivative; a crystal nucleating agent for a crystalline thermoplastic resin containing the rosinamide derivative; The present invention relates to a crystalline thermoplastic resin composition comprising 100 parts by weight of the resin (A) and 0.001 to 30 parts by weight of the nucleating agent (B).

[0008]

DETAILED DESCRIPTION OF THE INVENTION The rosinamide derivative of the present invention has a general formula (1): XYZD (wherein X is a rosin acid residue, Y is -CONH-, and Z is carboxyphenylene. A group or a metal salt thereof, and D represents a hydrogen atom or an organic group represented by YX), which is a novel compound not described in any literature.

The method for producing the rosin amide derivative represented by the general formula (1) is not particularly limited, but usually, the amino group-containing aromatic carboxylic acid represented by the general formula (2) and the general formula (3) ) And a rosin acid or a derivative thereof,
An amidation reaction is preferred.

The aromatic carboxylic acid containing an amino group represented by the general formula (2), which is one of the raw materials for producing the rosin acid amide derivative, includes, for example, o-aminobenzoic acid, m-aminobenzoic acid and p-aminobenzoic acid. Aminobenzoic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid Acids and the like can be exemplified.

Examples of the rosin acid represented by the general formula (3) or the rosin acid derivative, which is another raw material for producing the rosin acid amide derivative, include the following.

Specific examples of the rosin acids represented by the general formula (3) include, for example, pimaric acid, sandaracopimaric acid,
Examples include parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid. Among these rosin acids, at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid or dihydropimaric acid is preferable because of its excellent color tone stability and crystallinity. Particularly, dehydroabietic acid is preferred.

The rosin acid is usually present as a mixture in natural rosins such as gum rosin, tall oil rosin and wood rosin. Therefore, when a compound composed of a plurality of types of rosin acids such as natural rosin is used as the rosin acid, the amide compound represented by the general formula (1) is
It is obtained as a mixture of a plurality of amide compounds having different rosin acid residues. Further, as the rosin acid, various modified rosins such as disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, etc .; purified products of the natural rosin, purified rosin and the like can also be used. In addition, dehydroabietic acid is obtained by disproportionation or dehydrogenation of natural rosin, followed by purification.

The rosin acid derivatives represented by the general formula (3) include esters and halides of the rosin acid. In particular, rosin acid halides, particularly rosin acid chloride, are preferred in view of the high reactivity with the amino group-containing aromatic carboxylic acid of the general formula (2). In addition,
Methods for deriving rosin acid chloride from rosin acid include, for example, the phosgene method and the thionyl chloride method.
For example, in the case of the thionyl chloride method, equal amounts of rosin acid and thionyl chloride are charged and reacted under reflux of a solvent such as benzene anhydride. After completion of the reaction, the mixture is cooled, the aqueous layer is separated, and the organic solvent layer is washed to obtain rosin acid chloride.

As described above, the rosin acid amide derivative represented by the general formula (1) includes the amino group-containing aromatic carboxylic acid of the general formula (2) and the rosin acid of the general formula (3) or a derivative thereof. Are subjected to an amidation reaction. The conditions for the amidation reaction are not particularly limited, and general amidation conditions can be employed. However, it is better not to use an amine catalyst such as triethylamine in order to suppress the generation amount of by-products. When the rosin acid represented by the general formula (3) is used in the form of an acid halide in the amidation reaction, the reaction is carried out at room temperature in a solvent such as tetrahydrofuran or toluene, and then the reaction solution is concentrated.
After washing, the rosinamide derivative of the present invention can be obtained.

In order to produce a rosin acid amide derivative in which a carboxyl group derived from an amino group-containing aromatic carboxylic acid of the general formula (2) is a metal salt,
The following two methods can be adopted. First, the amino group-containing aromatic carboxylic acid of the general formula (2) is reacted with various metal compounds to prepare an amino group-containing aromatic carboxylic acid metal salt in advance, and the metal salt is converted to the general formula ( There is a method in which amidation reaction is performed with the rosin acid or its derivative represented by 3). Second, the amino group-containing aromatic carboxylic acid of the general formula (2) is amidated with the rosin acid or a derivative thereof represented by the general formula (3), and then the amide compound and various metal compounds are reacted with each other. There is a method to make it react. In the case where any of the above methods is employed as the salt formation reaction, a neutralization method or a double decomposition method can be employed. Examples of the metal compound include oxides and hydroxides of the following metals, and examples of the metal species include sodium, potassium, magnesium, calcium, zinc, and aluminum. Such a salt-forming reaction is carried out in the range of room temperature to about 160 ° C. by dissolving or dispersing the compound in the presence of an organic solvent such as tetrahydrofuran or toluene or water. After completion of the reaction, the product is separated by concentrating or filtering the reaction solution, followed by washing to obtain the desired rosinamide derivative having a metal carboxylate structure.

The rosinamide derivative thus obtained is used, for example, as a nucleating agent (B) to be mixed with the crystalline thermoplastic resin (A).

Examples of the crystalline thermoplastic resin (A) include polyolefin, polyamide, polyester and polyacetal.

Polyolefins include polyethylene,
Examples thereof include olefin homopolymers such as polypropylene, poly-1-butene, polymethylpentene, and polymethylbutene, and olefin copolymers such as propylene / ethylene random copolymer. Butene is particularly preferred. Such polyolefins may be used alone or in combination of two or more.

Examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12 and nylon-46, and aromatic polyamides prepared from aromatic dicarboxylic acids and aliphatic diamines. Nylon-6 is particularly preferred. Such polyamides may be used alone or in combination of two or more.

Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycaprolactone, and polyhydroxybutyrate, and polyethylene terephthalate is particularly preferred. Such a polyester may be used alone,
Two or more kinds may be used in combination.

Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like, with polyformaldehyde being particularly preferred. Such polyacetals may be used alone or in combination of two or more.

Among these crystalline thermoplastic resins (A), polyolefins, especially polypropylene, are preferred because of their great effect of improving mechanical properties and / or optical properties.

The crystalline thermoplastic resin composition comprising the crystalline thermoplastic resin (A) and the nucleating agent (B) comprises:
It is manufactured by melt-kneading at a temperature higher than the melting point of the crystalline thermoplastic resin (A) using an extruder, a kneader or the like.

The amount of the crystal nucleating agent (B) used is usually 0.001 to 100 parts by weight of the crystalline thermoplastic resin (A).
-30 parts by weight. The amount of the crystal nucleating agent (B) used is preferably 0.1% because the crystallization rate is greatly improved and the physical properties of the resin composition (molded article) are hardly affected.
005 parts by weight or more, more preferably 0.01 parts by weight or more. For the same reason, the amount of the crystal nucleating agent (B) used is preferably 5 parts by weight or less, more preferably 2 parts by weight or less.

In addition, the crystalline thermoplastic resin composition of the present invention may contain various compounding agents such as a crosslinking agent, a heat stabilizer, a weather stabilizer, a lubricant, a release agent, an inorganic filler, a pigment dispersant, a pigment or a dye. May be contained within a range that does not impair the object of the present invention.

The production conditions for the crystalline thermoplastic resin are as follows:
When the crystalline thermoplastic resin (A) is a polyolefin, the temperature during melt-kneading is usually in the range of 170 to 300 ° C, preferably 180 to 250 ° C, and the melt-kneading time is usually 0.2 to 20 minutes. , Preferably 0.5 to 10 minutes.

In the case of polyester, the temperature during melt-kneading is usually from 260 to 330 ° C., preferably from 270 to 330 ° C.
The temperature is within the range of 00 ° C., and the melt-kneading time is usually 0.2 to 20.
Minutes, preferably 0.5 to 10 minutes.

In the case of polyamide, the temperature during melt-kneading is usually 220 to 330 ° C., preferably 260 to 33 ° C.
0 ° C., and the melt-kneading time is usually 0.2 to 20.
Minutes, preferably 0.5 to 10 minutes.

In the case of polyacetal, the temperature during melt-kneading is usually 180 to 300 ° C., preferably 180 to 300 ° C.
250 ° C., and the melt-kneading time is usually 0.2 to 2
0 minutes, preferably 0.5 to 10 minutes.

The crystalline thermoplastic resin composition of the present invention thus obtained can be used for a wide range of applications from household goods to industrial goods,
For example, it is suitably used as a material for food containers, electric parts, electronic parts, automobile parts, mechanical mechanism parts, films, sheets, fibers and the like.

[0032]

According to the present invention, a novel rosinamide derivative is provided. Such an amide derivative is useful as a nucleating agent for a crystalline thermoplastic resin. The crystalline thermoplastic resin composition containing the amide derivative has a high crystallization rate during molding. In addition, the crystalline thermoplastic resin has excellent mechanical properties, especially excellent impact strength.

[0033]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The melting point of the obtained rosin acid amide derivative was determined by differential scanning calorimetry (DSC) at a heating rate of 10
Measured in ° C / min. IR is manufactured by Bio-Rad / FTS-
7. NMR was measured by Brooker / ARX-300.

Example 1 22.2 g (0.16 mol) of p-aminobenzoic acid and 256.6 g of tetrahydrofuran were added and dissolved in a reaction vessel equipped with a cooling pipe and a stirring device, and 26.1 g of dehydroabietic acid chloride was added thereto. (0.08 mol) in 130.5 g of tetrahydrofuran was added dropwise at room temperature over 1.5 hours with stirring. After stirring overnight,
The reaction solution was filtered to remove by-product p-aminobenzoic acid hydrochloride. About 40 g of the crude crystals obtained by distilling off tetrahydrofuran from the filtrate were 1200 g of methyl isobutyl ketone.
And washed with 10% hydrochloric acid and then with ion-exchanged water. After drying over magnesium sulfate, the reaction solution was concentrated to a total amount of 430 g and recrystallized. 27 g of crude crystals obtained
Is dissolved in 400 g of methyl isobutyl ketone and the total amount is 300
g and recrystallized. Drying at 100 ° C. under reduced pressure gave 13.6 g of rosinamide derivative A. The properties of the rosinamide derivative A are as follows.

Melting point: 261-269 ° C. IR (KBr, cm^-1): 3337cm^-1, 169
1cm^-1, 1653cm^-1, 1518cm^{-1 1} H-NMR (δ: DMSO-d₆): 0.80-1.
00 (3H, m), 1.16 (10H, t), 1.27
(3H, s), 1.38 to 2.05 (9H, m), 2.
24 to 2.28 (2H, m), 2.75 to 2.79 (3
H, m), 6.84 (1H, s), 6.98 (1H,
d), 7.20 (1H, d), 7.77 (2H, d),
7.87 (2H, d), 9.56 (1H, s), 12.
62 (1H, s)

Example 2 18.6 g (0.12 mol) of 3,5-diaminobenzoic acid and 372.6 g of dimethylformamide were added and dissolved in a reaction vessel equipped with a cooling tube and a stirring device. The solution was then added to dehydroabietic acid chloride 78.
A solution consisting of 3 g (0.24 mol) and 313.3 g of pyridine was added dropwise with stirring at room temperature over 1.5 hours. After stirring overnight, the reaction solution was filtered to remove by-product pyridine hydrochloride. Dimethylformamide and pyridine were distilled off from the filtrate to obtain crude crystals. About 14 crude crystals obtained
0 g was dissolved in 1000 g of methanol, 600 g of a saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was filtered to obtain crystals of sodium carboxylate. Dissolve sodium salt crystals in methyl isobutyl ketone, transfer to a separating funnel and add 10%
Hydrochloric acid was added to remove sodium to obtain carboxylic acid. After washing with water, the methyl isobutyl ketone layer was concentrated to obtain 14.7 g of crude crystals. The crude crystals were dissolved in 500 g of ethyl acetate, concentrated to a total amount of 80 g and recrystallized, and 7 g of the obtained crude crystals were dissolved in 140 g of ethyl acetate and concentrated to a total amount of 25 g for recrystallization. It was dried at 80 ° C. under reduced pressure to obtain 3.5 g of rosinamide derivative B. The properties of the rosinamide amide derivative B are as follows.

Melting point: 281-290 ° C. IR (KBr, cm^-1): 3363cm^-1, 170
3cm^-1, 1656cm^-1, 1539cm^{-1 1} H-NMR (δ: DMSO-d₆): 0.80-1.
00 (10H, m), 1.16 (22H, t), 1.2
5 (6H, s), 1.35 to 1.82 (26H, m),
2.26 (4H, d), 2.75 to 2.79 (6H,
m), 6.85 (2H, s), 6.98 (2H, d),
7.20 (2H, d), 7.92 (2H, d), 8.2
9 (1H, s), 9.49 (2H, s), 12.86
(1H, s)

Example 3 Rosinamide derivative A prepared in Example 1
4.2 g (0.01 mol) is dispersed in 40.0 g of ion-exchanged water, and 0.8 g of a 48% aqueous sodium hydroxide solution is dispersed.
(0.01 mol), and the mixture was stirred at 25 ° C. for 1 hour. A solution in which 1.1 g of magnesium chloride (0.01 mol) was dissolved in 10.0 g of ion-exchanged water was dropped into the reaction solution, and
The mixture was stirred at 0 ° C for 12 hours. The reaction solution was filtered, and the obtained filtrate was washed with water and dried to obtain 4.0 g of a white crystalline rosinamide derivative C. When the derivative C was observed by IR, the peak around 1700 cm ⁻¹ derived from the carboxylic acid found in the rosinamide derivative A moved to a lower wavenumber, and it was confirmed that the derivative C was a magnesium salt. .

Evaluation Example 1 Propylene block copolymer (melt flow rate measured at 230 ° C. under a load of 2.16 kg: 23 g /
10 minutes) 100 parts by weight of Irganox 1010TM
0.1 parts by weight (manufactured by Ciba Geigy) and 0.4 parts by weight of a crystal nucleating agent (rosin acid amide derivative A) were added, and the mixture was melt-kneaded at a resin temperature of 220 ° C. by a 20 mm single screw extruder to produce pellets.

Using the obtained propylene homopolymer pellets, various test pieces were prepared by injection molding at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., and compression molding at a melting temperature of 200 ° C. and a cooling temperature of 20 ° C. Using these test pieces, various physical properties were measured by the following test methods. Table 1 shows the results
Shown in

Evaluation Examples 2 and 3 In the same manner as in Evaluation Example 1, except that the type of the rosinamide derivative was changed as shown in Table 1 in place of the rosinamide derivative A as a crystal nucleating agent, Pellets were produced. Various test pieces were prepared in the same manner as in Example 1 using the obtained pellets. Using these test pieces, various physical properties were measured by the test methods described above. Table 1 shows the results.

Comparative Evaluation Example A pellet was produced in the same manner as in Example 1 except that the nucleating agent (rosin amide derivative A) was not used. Various test pieces were prepared in the same manner as in Example 1 using the obtained pellets. Using these test pieces, various physical properties were measured by the test methods described above. Table 1 shows the results.

The performance of the crystalline thermoplastic resin composition was evaluated by the following method.

Crystallization temperature (Tc): The obtained pellets were cooled from a molten state at a constant rate (10 ° C./min) by a differential scanning calorimeter (DSC) to obtain a crystallization exothermic peak temperature [crystallization temperature (Tc). )] Was measured to evaluate the crystallization rate. The higher the effect of increasing the crystallization temperature (Tc), the faster the crystallization speed.

Flexural modulus (FM): length 5 inches, width 1
Using an injection molded test piece having a size of 1/2 inch and a thickness of 1/8 inch, the flexural modulus was measured in accordance with ASTM D638. The greater the flexural modulus, the greater the rigidity.

Heat distortion temperature (HDT): The heat distortion temperature was measured according to ASTM D648 using an injection molded test piece having a length of 5 inches, a width of 1/8 inch and a thickness of 1/2 inch. The higher the heat distortion temperature, the greater the heat resistance.

Impact strength (IZ): Using a 2.5 inch long, 1/8 inch wide, 1/2 inch thick injection molded test piece, a notch was used, and the impact strength was measured according to ASTM D256. . The higher the impact strength, the better the impact resistance.

[0048]

[Table 1]

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Claims (6)

[Claims] 1. General formula (1): XYZD (wherein X is a rosin acid residue, Y is -CONH-, Z is a carboxyphenylene group or a metal salt thereof, D is a hydrogen atom or A rosin acid amide derivative represented by the formula: 2. An amino group-containing aromatic carboxylic acid represented by the general formula (2): H ₂ N—Z—E (where Z is a carboxyphenylene group, E is a hydrogen atom or NH ₂ ), and The rosin acid amide derivative according to claim 1, which is obtained by reacting a rosin acid or a derivative thereof represented by the formula (3): X-COOH (X represents a rosin acid residue). 3. The rosin acid residue (X) according to claim 1, wherein the rosin acid residue (X) is at least one rosin acid residue selected from the group consisting of dehydroabietic acid, dihydroabietic acid and dihydropimaric acid. Rosinamide derivatives. 4. A crystal nucleating agent for a crystalline thermoplastic resin comprising the rosinamide derivative according to claim 1. Description: 5. The nucleating agent (B) according to claim 5, in 100 parts by weight of the crystalline thermoplastic resin (A).
A crystalline thermoplastic resin composition containing parts by weight. 6. The crystalline thermoplastic resin (A) is at least one selected from polyolefins, polyesters, polyamides and polyacetals.
The crystalline thermoplastic resin composition as described in the above.