JPH03106965A - Nylon 66 resin composition for blow molding - Google Patents

Abstract

PURPOSE:To prepare a nylon 66 resin compsn. excellent in the blow molding properties, impact strength, and heat resistance by compounding nylon 66 resin, a specific amorphous nylon, and a specific modified polyolefin, thereby causing the resulting compsn. to have specified melt viscosity and degree of supercooling in crystallization by temp. fall. CONSTITUTION:A nylon 66 resin compsn. which comprises 30-98wt.% nylon 66 resin, 1-50wt.% amorphous nylon having a glass transition point of 100 deg.C or higher (e.g. a polycondensation product of 2,2,4-/2,4,4- trimethylhexamethylenediamine with terephthalic acid), and 1-50wt.% modified polyolefin having at least one functional group selected from among carboxyl, metal carboxylate, acid anhydride, ester, and epoxy groups (e.g. ethylene/alpha-olefin/maleic anhydride copolymer) and which has a melt viscosity (280 deg.C) and the degree of supercooling in crystallization by temp. fall both satisfying values defined by specific formulas.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a nylon 66 resin composite material with improved blowability and impact resistance. This invention relates to a nylon 66 resin composition that has improved both viscosity and crystallization properties, and has excellent blowability, impact resistance, and heat resistance.

(Prior art) Nylon 66 has excellent mechanical properties. In particular, it has good toughness and fatigue resistance, as well as good heat resistance and chemical resistance, so it is used in many fields such as fibers, films, plastics, and molded products. However, the blowability of nylon 66 cannot necessarily be said to be excellent. Among these, problems have been pointed out in the past regarding the blow moldability of large-sized articles.

Firstly, once nylon 66 is melted at high temperatures, its melt viscosity is too low for blowing and forming, and the drawdown of the so-called balisong is large, making it impossible to obtain satisfactory forming products. However, the blow molding itself is extremely difficult. Therefore, various proposals have been made for the purpose of increasing the melt viscosity of nylon 66. For example, a polyfunctional epoxy compound is used as nylon 66.
Method of adding and mixing and heating and melting (Special Publication No. 4B-7509
Japanese Patent Publication No. 50-2790, Japanese Patent Publication No. 502791, Japanese Patent Publication No. 502791, Japanese Patent Publication No. 50-2790, Japanese Patent Publication No. 502791, Japanese Patent Publication No. 50-2790, Japanese Patent Publication No. 502791, Japanese Patent Publication No. 502791, 50-3193 and Japanese Patent Publication No. 50-104297, etc.), methods of blending ethylene ionomer resins and ethylene/vinyl acetate copolymers with branched nylon 66, methods of blending ethylene ionomers or carboxy-modified nitrile rubber with nylon 66, Methods of blending are known. However, although these methods increased the melt viscosity of nylon 66 during blowing, the effect of improving blowability was not necessarily sufficient. A method of copolymerizing a lactam with a small amount of ε 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 66 resin.

Due to these circumstances, despite the fact that nylon 66 resin has various excellent properties as an engineering plastic, the blowing method has hardly been applied due to the problems mentioned above. It is.

(Problem to be solved by the invention) In view of the above circumstances. The purpose of the present invention is to improve the blowability. Nylon 6 has excellent heat resistance and impact resistance.
The goal is to obtain a 6-resin combination.

Another object of the present invention is 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 by using such a nylon 66 resin composition with improved blow-formability. It is in.

(Means for solving the problem) Is this the result of the inventor's intensive research for this purpose? A resin composition consisting of A) nylon 66 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. However, the present invention was achieved by discovering the surprising effect that the excellent heat resistance of nylon 66 resin is not impaired at all.

That is, the present invention is based on (^) nylon 66 resin 30-9
8% by weight, (B) 1 to 50% by weight of amorphous nylon having a glass transition temperature of 100°C or higher, and (C) 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 selected from the group consisting of. The melt viscosity at 280'C satisfies formulas (I) and (It). A nylon 66 resin assembly for blowing and molding, and the degree of supercooling during temperature-lowering crystallization satisfies the formula (In).

5,000 poise≦ηyut≦50,000 poise [I
〕Composition. 5,000 poise≦η2■:≦40,000
Boise (IF) 50℃ ≦∆C ≦110℃
(I[r) where η is at a temperature of 280°C and a shear rate of 10
It shows the melt viscosity at sec-', and η≦2 is the temperature 2
It shows the melt viscosity at 80°C and a shear rate of 100 sec-', and η100280 is the crystal melting temperature TIl1,
Cooling crystallization temperature T when cooling at a cooling rate of 20°C/min
The present invention relates to a resin composition whose supercooling degree Tm-Tccf is defined as the difference between cc and Tccf.

The melt viscosity of the resin composition of the present invention is determined by JIS K721.
It can be measured using the method described as a reference test for No. 0, that is, using a Koka type flow tester. In that case, the nozzle diameter is generally 0.5mm and 1mm, and the nozzle length is generally 21nII+ or 10m.
m is used. The shear rate to which the molded object is subjected in blow molding is relatively low. 10sec-' to 1
00 sec-'. Therefore, in blow molding, +10 sec-' to 100 sec-
'Melt viscosity at shear rate is important.

Among the resin compositions of the present invention, those having a melt viscosity satisfying formulas (I) and (n) exhibit the best blowability. The melting temperature Tm of the crystal is . It is defined as the temperature of the melting peak of crystals when a resin composition is heated at a heating rate of 20° C./min using a differential thermal analyzer. Further, the cooling crystallization temperature Tcc is . It is defined as the temperature of the cooling crystallization peak when the resin composition is melted at 280°C and then cooled at a cooling rate of 20°C/min.

The nylon 66 resin used in the present invention has polyamide as a main structural unit consisting of hexamethylene diamine, adipic acid, and their functional derivatives, but the adipic acid component or hexamethylene diamine or A part of the copolymer may be replaced with another copolymer. The copolymerization component is not particularly limited, and known amide group-forming components can be used.

A typical example of a copolymerized component is 6-anocabronic acid.
11-Aminoundecanoic acid. Amino acids such as 12-anododecanoic acid and para-ξ-nomethylbenzoic acid, ε-cabrolactam. Lactams such as ω-lauryllactam, tetramethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2.2.4 -/2,4.4-
}Limethylhexamethylenediamine. 5-Methylnonamethylene diane ξ, metakynolene diane, baraxy9 diane ξ, 1,3^
^Bis(aξnomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane.
1-amino-3-aξnomethyl-3.5.5-1-limethylcyclohexane, bis(4-aξnocyclohexyl)methane, bis(3-methyl-4-a5nocyclohexyl)methane, 2 .Diamines such as 2-bis(4-anocyclohexyl)propane, bis(ξnopropyl)piperazine, bis(agonoethyl)piverazine, suberic acid, azelaic acid. Sebacic acid, dodecanniic acid, terephthalic acid, isophthalic acid. 2-chloroterephthalic acid, 2
-Methyl terephthalic acid. 5-methylisophthalic acid, 5-
Examples include dicarboxylic acids such as sodium sulfoisophthalic acid, hexahydrideterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

Any method can be used for producing the nylon 66 resin used in the present invention. For example, melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, and combinations of these methods are applied.
Melt polymerization is the most common.

There is no particular restriction on the degree of polymerization of the nylon 66 resin used in the present invention, but the relative viscosity is 96% sulfuric acid and the concentration is lg7dl. 1.5-5.5 when measured at 25°C
More preferably, nylon 66 resin is in the range of 2.0 to 4.5. If the relative viscosity exceeds 5.5, it is not preferable because not only the fluidity of the composition deteriorates, but also the dispersion of its mechanical and thermal properties becomes large. Relative viscosity is 1.5
If it is lower than , there will be a disadvantage that the mechanical strength of the first precept will be low. If the amount of nylon 66 resin blended is less than 30% by weight, the heat resistance of the resin composition will be greatly reduced, which is not preferable.

In the present invention, amorphous nylon 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 is. It 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. Amorphous nylon having a glass transition temperature of less than 100° C. is not preferred because it has little effect on suppressing crystallization of the resin composite.

Typical examples of diamines that can be used in the amorphous nylon used in the present invention are: Tetramethylene diamine, hexamethylene diamine. undecamethylene diamine, dodecamethylene diamine, 2.2.4 −/2,4.4− }
Limethylhexamethylene diamine, 5-diamine, monomethyl nonamethylene diamine, metaxylene diamine. Barraxylene diamine, 1,3-bis(A^ξnomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, Bis(4-Aξnocyclohexyl)methane, 1-Amino-3-Aξnomethyl-3. 5.
5-trimethylcyclohex, san. Bis(3-methyl-
4-aminosichexyl)methane, 2,2-bis(4
-aminocyclohexyl)propane, bis(aminopropyl)biverazine, bis(aminoethyl)piperazine, etc.

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

Typical examples of the amino acids and lactams that make up the amorphous nylon used in the present invention are: Examples include 75 amino acids such as 6-aminocaproic acid, 11-aξnoundecanoic acid, 12-aminododecanoic acid, and vararaaξnomethylbenzoic acid, and lactams such as ε-monocubic lactam and ω-lauryl lactam.

A specific example of the most suitable amorphous nylon used in the present invention is a polycondensate of 2,2.4-/2,4.4-}limethylhexamethylenedia terephthalic acid and/or isophthalic acid. , polycondensate of hexamethylene diamine terephthalic acid and isophthalic acid, hexamethylene diamine bis(4-anocyclohexyl)methane
Polycondensates of terephthalic acid and/or isophthalic acid,
Polycondensate of hexamethylenedia ξ bis(3-methyl-4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid, ε monolactam bis(4-aminocyclohexyl)methane terephthalic acid and/or or polycondensate of isophthalic acid, ε-monocarboxylic lactam bis(3-methyl-4-aminocyclohexyl)
Polycondensates of methane-terephthalic acid and/or isophthalic acid, ω-lauryllactam-bis(4-anocyclohexyl)polycondensates of methane-terephthalic acid and/or isophthalic acid. ω-Lauryl lactam bis(3
Examples include polycondensates of monomethyl-4-aminocyclohexyl)methane terephthalic acid and/or isophthalic acid.

Amorphous nylon exhibits the effect of increasing the melt viscosity and suppressing the crystallization rate in the resin composition of the present invention. 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 decrease significantly.
At the same time, heat resistance also decreases, which is not preferable.

The modified polyolefin used in the present invention includes carboxylic acid groups, carboxylic acid metal bases, and acid anhydride groups. It is a modified polyolefin having at least one functional group selected from the group consisting of 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.・Maleic anhydride copolymer, styrene/maleic anhydride copolymer. Ethylene/propylene/maleic anhydride copolymer, ethylene/glycidyl methacrylate copolymer.
Olefinic monomers, carboxylic acid groups, carboxylic acid metal bases, such as ethylene/vinyl acetate/glycidyl methacrylate copolymers (modified polyolefins containing carboxylic acid metal bases) It can be obtained by reacting with an alkali such as NaOH or KOI.
Acid anhydride group. There are copolymers with vinyl monomers having 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-albutene-g -Fumaric acid copolymer, ethylene/1-hexene-
Itaconic acid copolymer, ethylene/propylene/1.4-
Hexadiene-g-mono-maleic anhydride copolymer, ethylene/propylene/dicyclopentadiene-g-fumaric acid copolymer, ethylene/propylene/5-ethylidene-2-
Polyolefins containing carboxylic acids, such as norbornene-g-maleic anhydride copolymer, ethylene-vinyl acetate-g-acrylic acid copolymer, styrene-butadiene-g-maleic acid copolymer, and derivatives thereof, Examples include modified polyolefins grafted with vinyl monomers having groups or acid anhydride groups.

Modified polyolefins can be produced by generally known methods. For example, it can be manufactured by the method disclosed in Japanese Patent Publications No. 59-8299 and Japanese Patent Publication No. 56-9925. The modified polyolefin functions to upper limit and adjust the melt viscosity of the resin composition 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 during blow-forming is large.

On the other hand, if the blending amount exceeds 50% by weight, the heat resistance of the resin composition will be greatly reduced.

In the resin composition of the present invention. The blending amount of nylon 66 resin is 30 to 98% by weight.

In the resin-composed sacrament of the present invention. The content of the modified polyolefin is 1 to 50% by weight.

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 30% by weight or less. Other such polymers include polycarbonate,
Polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, nylon 6, nylon 46, nylon 11, nylon 12,
Nylon 610, polyphenylene oxide, polyphenylene sulfide, ABS, PMMA, polypropylene.
Examples include polyethylene, phenoxy resin, and liquid crystal polymer.

Furthermore, the resin composition of the present invention may be used as long as its moldability and physical properties are not impaired. Pigments, heat stabilizers, antioxidants. Weathering agent. Flame retardants. Plasticizer. It is possible to add a mold release agent, reinforcing material, etc.

Reinforcing materials include glass fiber, metal fiber, and potassium titanate whiskers. Fibrous reinforcing materials such as carbon fiber, aramid fiber, etc., talc. There are filler-based reinforcements such as calcium carbonate, mercury, glass flakes, and metal flakes. Glass fibers having a diameter of 3 to 2 .mu.m are particularly preferred because they stabilize the melt viscosity of the resin composition and further improve its strength, elastic modulus, and heat resistance.

(Example) The measurement methods and raw materials used in Examples and Comparative Examples are as follows.

Fruit failure grade measuring device: Koka type flow tester (manufactured by Shimadzu Corporation, CF
T-500A) Nozzle: Diameter 0.5mm, length 2rnrn Temperature: 28
0° C. Shear rate: The shear rate was adjusted 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-'.

Measuring device conditions: Birkin Elmer, DSC-2 C-type differential thermal analyzer: Temperature rising and cooling rate 20'C/min 1l1C' temperature ASTM D256, with notch, test piece thickness 3 .2m
＋＊Never-changing speed ASTM D648. Load: 4.6 Kg/ctl Mountain volume: 1 liter of internal volume obtained by blowing 1° of 0, average wall thickness: approximately 1
．． Fill a 5m-long container with water, seal the mouth, and drop it repeatedly from a height of 2.5m onto a horizontal concrete floor with the bottom facing downwards to determine the number of drops until the container breaks. Ta. This test was conducted on five containers molded under certain conditions, and evaluated based on the average number of times the containers were dropped until they 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 250'C for 1 hour, using the same container containing A, holding the container horizontally by supporting the mouth of the container while empty. The gender was evaluated.

Nylon 66 for use: manufactured by ICI, AI25. Relative viscosity 3.0 Amorphous nylon PA-1: Reference example, glass transition temperature 150''C Trogamid T: Dynamite Nobel, glass transition temperature 14
8℃. 2.2.4 -/2,4.4-Trimethylhexamethylenediamine/terephthalic acid polycondensate X-21: manufactured by Mitsubishi Kasei Corporation, glass transition temperature 125°C Hexamethylenediamine/terephthalic acid/isophthalic acid polycondensate Manufactured by TR55nEMS, glass transition temperature 152°C, polycondensate-modified polyolefin tamer MC206 of ω-lauryllactam/bis(3-methyl-4-aminocyclohexyl)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 Surlyn 1650: manufactured by Mitsui Polychemical Co., Ltd. ethylene·
Reference example of Zn salt of methacrylic acid copolymer: 45 mol% of amorphous nylon isophthalic acid, 5 mol% of terephthalic acid, 45 mol% of hexamethylene diamine, bis(4-ano3
-Methylcyclohexyl)methane 10 kg of a raw material containing 5 mol% of methane was charged into a reaction tank together with 8 kg of pure water, and the air in the reaction tank was purged several times with nitrogen. After raising the temperature to 90"C and reacting for about 5 hours, the reaction temperature was gradually raised to 280C over IO hours while stirring the tank under pressure (18 bar).

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 vessel 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.

Example 1 - Composition. 5. Comparative Example 1.2 After mixing each raw material in a tumbler at 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., PCM45),
The mixture was melt-kneaded at 0° C. and cut into pellets of nylon 66 resin composition. This pellet was molded at 280''C using an injection molding machine (JIOOS manufactured by Nippon Steel Corporation) to obtain a test piece.The test piece was subjected to various physical property measurements.

In addition, using the obtained pellets, a blowing machine (65 mm blowing machine made by Nippon Steel Corporation) was used to obtain an internal volume of 1 liter.
Average wall thickness 1. A 5+++ m container was shaped by direct blowing at a cylinder temperature of 280° C. and subjected to measurements. In Examples 1 to 4, blowing commands were made without any problems. In Comparative Example 1, the drawdown was large and continuous, stable blowing was not possible, resulting in a container with large wall thickness fluctuations. In Comparative Example 2, the drawdown was relatively small, but the parisons solidified quickly, and many had rough surfaces and incomplete air blowing.

Table 1 lists the performance evaluation of the resin-composed sacraments using test beads and blown-in articles. As specifically shown in Table 1. The nylon 66 resin composition of the present invention has both improved blowability and excellent heat resistance and impact resistance.

Examples 5 to 10 Pellets of a nylon 66 resin composition were obtained in exactly the same manner as in Examples 1 to 4 with the assembly strength listed in Table 2, and test beads and blow molded products were molded using the pellets. The results of those performance evaluations are listed in Table 2. All have excellent blowability, heat resistance, and impact resistance.

(Effect of the invention) The nylon 66 resin composition of the present invention has (A) nylon 6
6 resin, and (B) amorphous nylon. (C) It is composed of a modified polyolefin and has a specific melt viscosity and a specific degree of supercooling, which significantly improves the blowability of nylon 66, while completely impairing the excellent heat resistance of nylon 66 resin. Never.

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

Claims (1)

[Claims] (1) (A) 30-98% by weight of nylon 66 resin, (
B) 1 to 50% by weight of amorphous nylon having a glass transition temperature of 100°C or higher, and (C) selected from the group consisting of carboxylic acid groups, carboxylic acid metal bases, acid anhydride groups, ester groups, and epoxy groups. 280% by weight of a modified polyolefin having at least one functional group.
A nylon 66 resin composition for blow molding, whose melt viscosity at °C satisfies formulas [I] and [II], and whose degree of supercooling during cooling crystallization satisfies formula [III]. 5,000 poise≦η^1^0_2_8_0≦50,0
00 poise [I] 4,000 poise ≦η^1^0^0
_2_8_0≦40,000 poise [II] 50℃≦ΔT
≦110℃ [III] Here, η^1^0_2_8_0 indicates the melt viscosity at a temperature of 280℃ and a shear rate of 10sec^-^1, and η^1
^0^0_2_8_0 is a temperature of 280℃ and a shear rate of 100
The melt viscosity at sec^-^1 is shown. ΔT is the degree of supercooling Tm defined as the difference between the melting temperature Tm of the crystal and the cooling crystallization temperature Tcc when cooling at a cooling rate of 20°C/min.
- represents Tcc.