JPH0359073A - Nylon 46 resin composition for blow molding - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in blow moldability, heat resistance, and impact resistance by mixing a nylon 46 resin, an amorphous nylon, and a modified polyolefin containing functional groups so as to provide a melt viscosity and a degree of supercooling, when crystallized by lowering the temperature, respectively in a specified range. CONSTITUTION:30-98wt.% nylon 46 resin (A) consisting mainly of a polyamide obtained from tetramethylenediamine and adipic acid (functional derivative) and having a relative viscosity (at a concentration of 1g/dl in 96% sulfuric acid, at 25 deg.C) of 1.5 to 5.5 is mixed with 1-50wt.% amorphous nylon (B) having a glass transition temperature of 100 deg.C or higher and 1-50wt.% modified polyolefin (C) containing functional groups selected from carboxyl (metal carboxylate) groups, acid anhydride groups, ester groups, and epoxy groups to give the title composition having a melt viscosity satisfying the relation I and II (wherein eta is the melt viscosity at 300 deg.C and at a shear rate of 10sec<-1>, eta is that at 300 deg.C and at a shear rate of 100sec<-1>) and a degree of supercooling, when crystallized by lowering the temperature, satisfying the relation III [wherein T stands for the degree of supercooling (Tm-Tcc) defined by the difference between the melting temperature Tm of the crystal and the crystallization temperature Tcc when cooled at a temperature fall rate of 20 deg.C/min].

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a nylon 46 resin composition with improved blow moldability and impact resistance. Nylon 46 resin with improved viscosity and crystallization properties, excellent blow moldability, impact resistance, and heat resistance! It is about something.

(Prior Art) Nylon 46 resin composed of tetramethylene cyanide and adipic acid or a functional derivative thereof is already a well-known polyamide. For example, in Japanese Patent Publication No. 60-8248 and Japanese Patent Publication No. 60-28843, nylon 46
A method of manufacturing a resin is disclosed. This nylon 46 resin is also known to have excellent properties as an engineering plastic, particularly excellent heat resistance.

For example, its melting point is 295°C, and the 2
It is not only higher than 60°C, but also higher than 285°C for polyphenylene sulfide. In addition, the crystallinity and crystallization speed are high, and the heat distortion temperature (4.5Kg/c+
+1 load) is 285°C, the highest value among engineering plastics. Furthermore, it has excellent mechanical strength such as tensile strength and bending strength, sliding properties, and fatigue resistance.

However, the blow moldability of nylon 46 resin, especially for large molded products, is not necessarily excellent. First of all, once nylon 46 resin is melted at high temperatures, its melt viscosity is too low for blow molding, and the so-called drawdown is large, making it impossible to obtain a satisfactory molded product, or the blow molding itself becomes difficult. is extremely difficult. Another possible method is to increase the molecular weight of the nylon 46 resin in order to increase the melt viscosity.

For example, as disclosed in Japanese Patent Publication No. 60-28843, nylon 46 resin is made to have a high molecular weight by solid phase polymerization. However, even though the nylon 46 resin whose molecular weight has been increased by this method has a high initial molecular weight, once it is heated and melted, the molecular weight decreases significantly, and therefore the melt viscosity also decreases significantly, making it impossible to form a parison with preferable melt viscosity characteristics.

The second problem with blow molding of nylon 46 resin is that the crystallization rate is extremely fast, so the melt-extruded parison tends to solidify, making uniform blow molding difficult. Therefore, the surface of the molded product is likely to be rough, and the thickness of the molded product is likely to be uneven.

In extreme cases, blow molding may not be possible at all. However, few attempts have been made to date to suppress the crystallization rate of nylon 46 resin. A method of copolymerizing a small amount of ε-caprolactam is known, but this method is not preferred because it lowers the heat resistance represented by the melting point, which is the most important characteristic of nylon 46 resin.

Due to these circumstances, despite the fact that nylon 46 resin has various excellent properties as an engineering plastic, the blow molding method has hardly been applied due to the problems mentioned above. It is.

(Problems to be Solved by the Invention) In view of the above circumstances, the object of the present invention is to develop nylon 4 which has improved blow moldability and has excellent heat resistance and impact resistance.
6 to obtain a resin composition. Another object of the present invention is to use the nylon 46 resin composition with improved blow moldability to obtain a useful blow molded product that has excellent heat resistance and impact resistance and can be used in a wide range of fields. .

(Means for Solving the Problem) As a result of intensive research for this purpose, the inventors have found (A
) A resin composition consisting of nylon 46 resin, (B) amorphous nylon, and (C) modified polyolefin and having a specific melt viscosity and a specific degree of supercooling satisfies all the objects of the present invention, and moreover, The present invention was achieved by discovering the surprising effect that the excellent heat resistance of 46 citrus oil is not impaired at all.

That is, the present invention provides (8) nylon 46 resin, 30-9
8% by weight and (B) glass transition'/7: A is 100"C
1 to 50% by weight of the above amorphous nylon, and (C) at least one functional group selected from the group consisting of carboxylic acid groups, carboxylic acid metal bases, acid anhydride groups, ester groups, and epoxy groups. The modified polyolefin has a melt viscosity of 1 to 50% by weight at 300°C according to the formula (1).
The present invention relates to a nylon 46 resin composition for blow molding that satisfies (2) and has a degree of supercooling during crystallization upon cooling that satisfies formula [3].

s, ooo Boise≦ηJ'o'cp≦50,000 Boise (1) 4.000 Boise≦η5:, S≦40,0
00 poise (2) 40'C≦△T 2100℃
(3) Here, η represents the melt viscosity at a temperature of 300°C and a shear rate of 10 sec-'ocI, and η5;; represents the melt viscosity at a temperature of 300'C1
The melt viscosity at a shear rate of 100 sec-' is shown. Δ
T represents the degree of supercooling Tm-Tcc defined as the difference between the melting temperature Tm of the crystal and the cooling crystallization temperature Tcc when cooling is performed at a cooling rate of 20° C./min.

The nylon 46 resin used in the present invention is a polyamide whose main structural units are polyamides composed of tetramethylene diamine, adipic acid, and functional derivatives thereof. It may also be partially reconstituted with other copolymer components. The copolymerization component is not particularly limited, and known amide group-forming components can be used.

Representative examples of copolymerized components include 6-aminocaproic acid, 1
Amino acids such as 1-aminoundecanoic acid, 12-a≧nododecanoic acid, para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2.2. 4-/2, 4.4-) Limethylhexamethylene diamine, 5-methylnonamethylene diamine, metaxylylene diamine, paraxylylene diamine, 1,3-bis(aminomethyl)cyclohexane, l.

4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-)limethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl) )methane,
2,2-bis(4-aminocyclohexyl)propane,
Diamines such as bis(aminopropyl)piperazine and bis(aminoethyl)piperazine and adipic acid, superic acid, azelaic acid, sebacic acid, dodecanniic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-
Examples include dicarboxylic acids such as methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

Any method can be used for producing the nylon 46 resin used in the present invention. For example, the method disclosed in Japanese Patent Publication No. 60-28843, Japanese Patent Publication No. 60-8248, Japanese Patent Application Laid-open No. 58-83029, and Japanese Patent Application Laid-open No. 61-43631, that is, first, a preform with a small amount of cyclic terminal groups is used. After producing the polymer under specific conditions, it undergoes solid phase polymerization in a steam atmosphere to produce high-viscosity nylon 46 resin! Particularly preferred are those obtained by a method of producing FI or those obtained by a method of heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone.

The degree of polymerization of the nylon 46 resin used in the present invention is not particularly limited, but the relative viscosity is 1.5 to 5.5 when measured using 96% sulfuric acid at a concentration of 1 g/dIl at 25°C.
Furthermore, nylon 46 resin in the range of 2.0 to 4.5 is preferable. If the relative viscosity exceeds 5.5, it is not preferable because not only the fluidity of the composition deteriorates but also the variation in its mechanical and thermal properties becomes large. Relative viscosity is 1.5
Lower than! The disadvantage is that the mechanical strength of the Jltc product is low.

Amorphous nylon as used in the present invention refers to nylon that does not exhibit a heat of crystal fusion of 1 cal/g or more when measured using a differential thermal analyzer at a heating rate of 20° C./min.

The amorphous nylon used in the present invention has a glass transition temperature of 100° C. or higher in an absolutely dry state. The glass transition temperature can also be determined by measuring at a heating rate of 20"C/min using a differential thermal analyzer.For amorphous nylon with a glass transition temperature of less than 100°C, the resin composition may crystallize. It is not preferable because the suppressing effect is small.

Representative examples of the diamine constituting the amorphous nylon used in the present invention include hexamethylene cyagon, undecamethylene diamine, dodecamethylene diamine, 2,2.
4-/2, 4.4-1-limethylhexamethylenecyamine, 5-methylnonamethylenediamine, metaxylylenecyamine, paraxylylenecyamine, ■, 3-bis(aminomethyl)cyclohexane, 1,4 -bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 1-amino-3-aminomethyl-3,5,
5-trimethylcyclohexane, bis(3-methyl-4
-aminocyclohexyl)methane, 22-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, and the like.

Typical examples of dicarboxylic acids constituting the amorphous nylon used in the present invention include adipic acid, superric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid,
Examples include isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

Typical examples of the anoic acids and lactams constituting the amorphous nylon used in the present invention include 6-ξξcabronic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and lactam methylbenzoic acid. Lactams such as straw acid, ε-caprolactam, and ω-lauryllactam can be mentioned.

Specific examples of the most preferred amorphous nylon used in the present invention include polycondensates of 2.2.4-/2.4.4-)limethylhexamethylenecyamine/terephthalic acid and/or isophthalic acid, Polycondensates of methylenediamine terephthalic acid and isophthalic acid, polycondensates of hexamethylenediamine bis(4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid,
Hexamethylenediamine bis(3-methyl-4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid polycondensate, ε-caprolactam bis(4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid Polycondensate, ε-caprolactam bis(3-methyl-4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid polycondensate, ω-lauryllactam bis(4-aminocyclohexyl)methane terephthalate Polycondensates of acid and/or isophthalic acid, ω-lauryllactam
Examples include polycondensed metals of bis(3-methyl-4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid.

The modified polyolefin used in the present invention is a modified polyolefin having at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid metal base, an acid anhydride group, an ester group, and an epoxy group.

Specific examples of modified polyolefins used in the present invention include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer, ethylene/ethyl acrylate/acrylic acid copolymer, and ethylene/acrylic acid copolymer.
Representative examples include maleic anhydride copolymer, styrene/maleic anhydride copolymer, ethylene/propylene/maleic anhydride copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, etc. However, a modified polyolefin containing an olefinic monomer, a carboxylic acid group, or a carboxylic acid metal base (a modified polyolefin containing a carboxylic acid group is obtained by reacting a modified polyolefin containing a carboxylic acid group with an alkali such as NaOH or KOF). ), there are co-electrolytic polymers with vinyl monomers having acid anhydride groups, ester groups and epoxy groups.

Furthermore, ethylene-g-maleic anhydride copolymer (g represents a graft. The same applies hereinafter), ethylene-propylene-g-maleic anhydride copolymer, ethylene-propylene-g-acrylic acid copolymer, ethylene-g-acrylic acid copolymer, 1-butene-g
-Fumaru 1llj combination, ethylene/1-hexene-g-
Itaconic acid copolymer, ethylene/propylene/1,4-hexadiene-g-m water maleic acid copolymer, ethylene/
Propylene/dicyclopentadiene-g-fumaric acid copolymer, ethylene/propylene/5-ethylidene-2-norbornene-g-maleic anhydride copolymer, ethylene/
Vinyl monomers having carboxylic acid groups or acid anhydride groups in polyolefins, such as vinyl acetate-g-acrylic acid copolymer, styrene-butadiene-g-maleic anhydride copolymer, and derivatives thereof. Examples include modified polyolefins grafted with polymers.

Modified polyolefins can be produced by generally known methods. For example, it can be produced by the method disclosed in Japanese Patent Publication No. 59-8299 and Japanese Patent Publication No. 56-9925.

In the resin composition of the present invention, the amount of nylon 46 resin blended is 30 to 98% by weight. If the blended amount of nylon 46 resin is 30% by weight, it is not preferable because the thermal properties of the resin IjI compound acid are greatly reduced.

The blending amount of amorphous nylon in the resin 111I mold of the present invention is 1 to b.The resin 111I mold of the present invention exhibits the effect of increasing the melt viscosity and the effect of suppressing its crystallization rate.

However, if the amount is less than 1% by weight, the effect of suppressing crystallization is not significant. On the other hand, if the blending amount exceeds 50% by weight, the crystallinity of the resin composition will be significantly lowered, and the heat resistance will also be lowered, which is not preferable.

In the resin composition of the present invention, the amount of modified polyolefin blended is 1 to 50% by weight. The modified polyolefin functions to increase and adjust the melt viscosity of the resin and FItc material of the present invention. When the blending amount is less than 1% by weight, no significant increase in melt viscosity is observed in the resin composition, and drawdown in blow molding is large. On the other hand, the amount is 50! If it exceeds lit %, the heat resistance of the resin composition will decrease significantly.

In order for the resin composition of the present invention to have improved blow moldability, it is necessary to control its melt viscosity characteristics and crystallization characteristics. It is necessary to satisfy the formula.

The melt viscosity of the resin m-acid of the present invention can be measured by the method described as a reference test of JIS 7210, that is, by using a Koka type flow tester. In that case, the nozzle diameter is generally 0.5 mm and 1 m,
Generally, a nozzle length of 21 or 10 mm is used. The shear rate experienced by the molded body in the blown bottom shape is relatively low, on the order of 10 sec-' to 100 sec-'. Therefore, in the blown bottom type, 10se
The melt viscosity at a shear rate of c-' to 100 sec-' is important. In the resin composition of the present invention, formula (1)
Those having a melt viscosity that satisfies (2) and (2) exhibit the best blow moldability.

The melting temperature Tm of the crystal is defined as the temperature of the melting peak of the crystal when the resin composition is heated at a heating rate of 20° C./min using a differential thermal analyzer. In addition, the cooling crystallization temperature Tcc is
It is defined as the temperature of the crystallization peak when the resin composition is melted at 300°C and then cooled at a cooling rate of 20°C/min.

In the resin composition of the present invention, other polymers may be blended as necessary, as long as the properties thereof are not significantly impaired.

In this case, the blending amount is preferably 309% by weight or less. Such other polymers include polycarbonate,
Polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, nylon 6, nylon 66, nylon 11, nylon 12,
Nylon 610, polyphenylene oxide, polyphenylene sulfide, ABS, PMMA, polypropylene,
Examples include polyethylene, phenoxy resin, and liquid crystal polymer.

Furthermore, it is possible to add pigments, heat stabilizers, antioxidants, weathering agents, ζ reinforcing materials, etc. to the resin composition of the present invention, as long as they do not impair its moldability and physical properties. Reinforcements include glass fibers, metal fibers, potassium titanate whiskers, fibrous reinforcements such as carbon fibers, talc,
There are filler reinforcements such as calcium carbonate, mica, glass flakes, and metal flakes. Especially the diameter is 3~2
Glass fibers of 0 μm are preferred because they stabilize the melt viscosity of the resin composition and further improve its strength, elastic modulus, and heat resistance.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these. The measurement methods and raw materials used in Examples and Comparative Examples are as follows.

Temporal dilatation measuring device: Koka type flow tester (manufactured by Uozu Seisakusho, CF
T-500A) Nozzle: Diameter 0.5mm+, Length 2I Temperature: 30
0° C. Shear rate: The shear rate was varied over a wide range by changing the load.

Melt viscosity: The shear rate and melt viscosity were plotted to determine the melt viscosity at shear rates of 10 sec-' and 100 sec-'.

10" degree/ldl meter: PerkinElmer, DSC-2C
Type Differential Thermal Analyzer Conditions: Temperature rising and cooling rate 20°C/min ASTM D256. With notch, test piece thickness 3.21
I11 Juku (Gen 4-hen ASTM D648. Load 4.6 Kg/c4 blow molding) Inner volume 1 liter, average wall thickness approx. 1
．． A 5m+m container was filled with water, the mouth was tightly sealed, and the bottom was turned downward, and the container was repeatedly dropped from a height of 2.5m onto a horizontal concrete floor to determine the number of drops until the container broke. . This test was conducted on five containers molded under certain conditions, and evaluated based on the average number of times the container was dropped until it broke.

Heat resistance is determined by the degree of deformation of the container after it is placed in a hot air constant temperature bath at 270°C for 1 hour using the same container as in 1. was evaluated.

Shiriou Beni Nylon 46: Manufactured by Unitika, F5000 Relative viscosity 3.
5 Amorphous nylon PA-1: Reference example 1, glass transition temperature 150°C Toroga ξ
DoT: manufactured by Dynamite Nobel, glass transition temperature 14
8℃ 2,2,4-/2,4.4-) Limethylhexamethylenediamine/terephthalic acid polycondensate X-2t: manufactured by Mitsubishi Kasei Corporation, glass transition temperature 125℃, hexamethylenediamine/terephthalic acid/isophthalic acid Acid polycondensate TR55: manufactured by EMS, glass transition temperature 152°C 1ω-
Polycondensate-modified polyolefin taffer MC206 of lauryl lactam bis(3-methyl-4-anocyclohexyl)methane isophthalic acid: manufactured by Mitsui Petrochemicals, ethylene α
-Olefin/maleic anhydride copolymer Bondine AX8390: manufactured by Sumitomo Chemical Co., Ltd., ethylene/ethyl acrylate/maleic anhydride copolymer Keirin 1650: manufactured by Mitsui Polyke Shukal Co., Ltd., ethylene/ethyl acrylate/maleic anhydride copolymer
Zn salt reference example 1 of methacrylic acid copolymer: Amorphous nylon (PA-1) isophthalic acid 4
5 mol% of raw materials, 5 mol% of terephthalic acid, 45 mol% of hexamethylene cyanide, 5 mol% of bis(4-antano-3-methylcyclohexyl)methane were placed in a reaction tank together with 8 g of pure water. The air in the reactor was purged several times with nitrogen. Raise the temperature to 90″C for approx.
After reacting for an hour, the reaction temperature was gradually increased to 28''C over 10 hours while stirring the tank under pressure (18 bar).
raised to.

Then, the pressure was released and the pressure was lowered to atmospheric pressure, followed by polymerization at the same temperature for 6 hours. After the reaction was completed, the polymer was discharged from the reaction tank and cut to obtain pellets.

This copolymerized nylon showed no melting point, and its glass transition temperature was 150°C. This amorphous nylon is PA-1
shall be.

Examples 1 to 4, Comparative Example 1.2 After mixing the respective raw materials in a tumbler in the blending ratio shown in Table 1, vacuum drying was performed at 90°C for 16 hours. Then, using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., P CM2S), it was melt-kneaded at 300''C and cut to obtain pellets of the nylon 46 resin composition. J100S) at 300"C to obtain a test piece. The test piece was subjected to various physical property measurements. In addition, using the obtained pellets, the internal volume was 1
Little, average yen * 1.511 II 11 containers for 300
It was molded by direct blowing at a cylinder temperature of 'C and subjected to measurement.

Examples 1 to 4 were able to be blow molded without any problems.

In Comparative Example 1, the drawdown was large, and continuous and stable blow molding could not be performed, and only containers with large wall thickness fluctuations were obtained. In Comparative Example 2, the drawdown was relatively small, but the parisons solidified quickly, and many had rough surfaces or incomplete air blowing.

Table 1 lists the performance evaluation of the resin composition using test pieces and blow molded products. As specifically shown in Table 1, the nylon 46 resin composition of the present invention has both improved blow moldability and excellent heat resistance and impact resistance.

Examples 5 to IO Pellets of a nylon 46 resin composition having the composition listed in Table 2 were obtained in exactly the same manner as in Examples I to 4, and test pieces and blow molded products were molded using the pellets. The results of those performance evaluations are listed in Table 2. All have excellent blow moldability, heat resistance, and impact resistance.

(Effect of the invention) The nylon 46 resin composition of the present invention has (A) nylon 4
6 resin, (B) amorphous nylon, and (C) modified polyolefin, and has a specific melt viscosity and a specific degree of supercooling, the blow moldability of nylon 46 is significantly improved, and moreover, the blow moldability of nylon 46 is significantly improved. The excellent heat resistance of 46 resin is not impaired at all.

Furthermore, it has the surprising effect of significantly improving impact resistance.

Claims (1)

[Claims] (1) (A) Nylon 46 resin, 30-98% by weight and (
B) an amorphous nylon having a glass transition temperature of 100°C or higher, 1 to 50% by weight, and (C) selected from the group consisting of carboxylic acid groups, carboxylic acid metal bases, acid anhydride groups, ester groups, and epoxy groups. 1 to 50% by weight of a modified polyolefin having at least one functional group;
The melt viscosity at °C satisfies formulas (1) and (2),
A nylon 46 resin composition for blow molding, in which the degree of supercooling during temperature-lowering crystallization satisfies formula (3). 5,000 poise≦▲There are mathematical formulas, chemical formulas, tables, etc.▼
≦50,000 poise (1) 4,000 poise ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼≦40,000 poise (2
)40℃≦∆T≦100℃ (3) Here, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is the temperature 300℃
℃, shows the melt viscosity at a shear rate of 10 sec^-^1, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ indicates the temperature of 300℃
, shows the melt viscosity at a shear rate of 100 sec^-^1. ΔT represents the degree of supercooling Tm−Tcc defined as the difference between the melting temperature Tm of the crystal and the cooling crystallization temperature Tcc when cooling is performed at a cooling rate of 20° C./min.