JPH0613627B2 - Method for producing polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a propylene polymer / polyamide polymer composition having excellent strength, heat resistance, chemical resistance, moisture resistance, and external appearance as well as excellent heat aging resistance. It relates to a method of manufacturing.

[Conventional technology]

Modified olefin polymers grafted with olefin polymers, polyamides and unsaturated carboxylic acids or their derivatives
For melt-blending the components to obtain a composition having an excellent balance of strength, heat resistance, appearance, and moldability,
It has already been shown in Japanese Patent Publication No. 50-7636 and Japanese Patent Publication No. 45-30945. Utilizing such excellent properties, practical application is being considered in some applications, such as automobile parts, electric appliances, mechanical parts, and industrial parts, where strength and heat resistance are required, and some are in practical use. ing.

By the way, even a polymer composition having such many features still has a problem that the resistance to long-term thermal deterioration, that is, the heat aging resistance is not sufficient. Therefore, as a means for solving this problem, a method of blending a hindered phenol, an aromatic amine and a copper compound has been proposed, as in JP-A-59-27948. However, even if this method is applied to the one using a propylene polymer as the olefin polymer as in the present invention, the heat aging cannot be completely prevented and the deterioration may be promoted. I found out. It is considered that this is because copper in the copper compound blended as a stabilizer of the polyamide promotes thermal deterioration with respect to an unstable propylene polymer structurally containing a tertiary carbon. Estimated (so-called copper damage). From such an estimation, the present inventors have made repeated studies, considering that when a propylene polymer is used, it may be possible to suppress the deterioration of the propylene polymer due to copper by adding a copper damage inhibitor.

However, the present inventors using commercially available heat-resistant nylon as a polyamide, a composition obtained by melt-blending a propylene polymer, a modified propylene polymer and a copper damage inhibitor, still does not meet the expectations and the heat aging is insufficient. It turned out to be. Next, a copper compound was further added to the above system to attempt melt blending, but the heat aging resistance of the obtained composition was insufficient.

[Problems to be solved by the invention]

As a result of further studies in view of the current state of such research, the present inventors have surprisingly found that when a method of blending a copper compound to be blended as a stabilizer for a polyamide is devised, the heat resistance and the heat resistance are improved. It has been found that a composition having excellent aging properties can be obtained.

[Means for solving problems]

That is, the present invention comprises a propylene polymer (A), a polyamide (B), a modified propylene polymer (C) grafted with an unsaturated carboxylic acid or a derivative thereof, a copper compound (D) and a copper damage inhibitor (E). In the method for producing a polymer composition having excellent heat aging resistance by blending, a polyamide containing no copper compound is used as the polyamide (B), and the polyamide (B) component and the copper compound (D) are used.
It is a method for producing a polymer composition, which comprises blending each component in a state where only the components are not individually blended.

[Action]

In the present invention, the copper-damage-preventing agent should be added before the copper compound is contained in the polyamide, that is, (A), (B), (C), and (D) as the timing for adding the copper-damaging inhibitor when producing the composition.
When blending the component consisting of (E), a polyamide containing no copper compound is used as the polyamide (B), and the polyamide (A) and the copper compound (D) alone are not blended independently. It is important to blend each component in a state, and if this requirement is satisfied, any of the blending methods described later, for example, polyamide (B) and copper compound (D) and copper damage inhibitor (E) can be used. Even with the method of blending at the same time, a composition excellent in heat aging resistance can be obtained.

It should be noted that such a technique cannot be predicted from conventional conventional techniques.

That is, in the prior art, when the purpose of the present invention is to produce a composition having excellent heat aging resistance, a heat-resistant brand is naturally used as the polyamide to be used. However, commercially available polyamide heat-resistant brands have already been melt-blended and blended with a copper compound as a stabilizer. In reality, as described above, a heat-resistant polyamide containing a copper compound is used, or in order to further improve heat resistance, a copper compound is added again to the above system. That is, in the prior art, it is usual to use a polyamide in which a copper compound has been previously blended, and as described above, the one using such a polyamide is not effective in the present invention.

Here, the propylene polymer (A) is crystalline, and preferably has a density of 0.89 to 0.93 g / cm ³ and a metre flow rate (MFR: ASTM D1238, L) of 0.01 to.
It is 50 g / 10 min and is a homopolymer of propylene or a block or random copolymer of propylene with 20 mol% or less of α-olefin such as ethylene, 1-butene, 4-methyl-4-pentene.

The polyamide (B) used in the present invention is hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis. (Aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine and other aliphatic, alicyclic and aromatic diamines and adipic acid, suberic acid, sebacic acid,
Polyamides obtained by polycondensation with aliphatic, alicyclic, aromatic dicarboxylic acids such as cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid, aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanoic acid Examples thereof include polyamides obtained by condensation of ## STR3 ##, polyamides obtained from lactams such as .epsilon.-caprolactam and .omega.-laurolactam, copolymerized polyamides containing these components, and mixtures of these polyamides. Specific examples include nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11. Of these, nylon 6 and nylon 66 are preferable in terms of good rigidity and heat resistance. Although the molecular weight is not particularly limited, a polyamide having a relative viscosity ηr (measured in JIS K 6810, 98% sulfuric acid) of 1.0 or more is usually used. Among them, 2.0 or more is preferable because of its excellent mechanical strength. .

The modified propylene polymer (C) used in the present invention comprises 0.05 to 10 parts by weight, preferably 0.1 to 8 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof on the propylene polymer (A). It was done.

As the unsaturated carboxylic acid or its derivative, acrylic is used.
Acid, maleic acid, fumaric acid, tetrahydrophthalic acid,
Itaconic acid, citraconic acid, crotonic acid, isocrotone
Acid, nadic acid (Endocis-bicyclo [2,2,1]
(Unsaturated calcium, such as pto-5-ene-2,3-dicarboxylic acid)
Boronic acid, or a derivative thereof, such as acid halide, ami
, Imide, anhydride, ester, etc.
Contains maleenyl chloride, maleimide, maleic anhydride, no
Water citraconic acid, monomethyl maleate, di maleate
Examples include methyl and glycidyl maleate. this
Among them, unsaturated dicarboxylic acid or its anhydride is preferable.
And especially maleic acid and nadic acid Or these
Acid anhydrides are preferred.

The copper compound (D) is well known as a stabilizer for polyamides, and is an inorganic halogen copper such as cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide. , Sulfuric acid second
Copper, copper salts of inorganic acids such as cupric nitrate, copper phosphate, cupric acetate, cupric salicylate, cupric stearate, cupric oleate, cupric benzoate and other organic acids Examples thereof include copper salts, or inorganic copper and complex compounds such as xylenediamine, benzimidazole, and 2-mercaptobenzimidazole.

If the copper damage inhibitor (E) is well known, basically
May be, oxalic acid derivative, salicylic acid derivative
Body, hydrazide derivative, etc.
Name Eastman Inhitor OABH (Eastman Kodak
Company), Naugard XL-1 (Uniroyal Chemical Company), Mar
k CDA -1, Mark CDA -6, Mark ZS27 (End of ADEKA
・ Argus Chemical Co., Ltd., Chel -180, Inganox MD1024
(Above Chiba Geigy), Qunox (Mitsui Toatsu Huai
, Etc., and Japanese Patent Publication Nos. 37-14484 and 3
9-9072, Japanese Examined Sho 39-12454, Japanese Examined Sho 39-19541, Japanese Examined
40-12293, 40-18852, 42-4356, 42-4356
Japanese Patent Publication No. 42-4596, Japanese Publication No. 42-13247, Japanese Publication No. 43-6538
Issue, Japanese Examined Sho 43-18606, Examined Sho 47-27624, Examined Sho 48-3
6837, Japanese Patent Publication No. 49-15466, Japanese Patent Publication No. 52-22834, Japanese Patent Publication No.
54-43537, Japanese Patent Publication No. 54-90143, U.S. Patent No. 3357944,
US Patent 3367907, French Patent 1481105, French Patent 1
It may be the one exemplified in No. 495830.

In the present invention, the proportion of each component for producing a polymer composition having excellent heat resistance and heat aging resistance is 90 to 10 parts by weight, preferably 70 to 30 parts by weight of propylene polymer (A), and polyamide (B). 10-90 parts by weight, preferably 30-70 parts by weight, and (A) + (B) = 100 parts by weight, modified propylene polymer (C) 0.1-20 parts by weight, preferably 0.5-
Copper compound (D) 0.005 to 5 parts by weight, preferably 0.1 part by weight per (A) + (B) + (C) = 100 parts by weight.
The amount of the copper damage inhibitor (E) is 0.005 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 01 to 1 part by weight, and also (A) + (B) + (C) = 100 parts by weight. Propylene polymer (A)
Is less than 10 parts by weight, moisture resistance and chemical resistance are inferior, and conversely, when the polyamide (B) is less than 10 parts by weight, rigidity and heat resistance are inferior.
When the modified propylene polymer (C) is less than the above range, the compatibility between the propylene polymer and the polyamide is poor, and the appearance,
Heat resistance and chemical resistance decrease. When the copper compound (D) and the copper anti-doubler agent (E) are less than the above, the heat aging resistance is lowered.

In order to produce a polymer composition having excellent heat resistance and heat aging resistance by mixing the respective components in the above-mentioned blending ratio, the addition of the copper damage inhibitor (E) is effective when the copper compound which is the stabilizer of the polyamide is in the polyamide. Must be done before being included in. If a step of adding a copper compound to a polyamide and then adding a copper damage inhibitor does not exhibit heat aging resistance by any blending method, or even if it does, its effect is small and practical use Far from. Therefore, as a specific blending method for producing a heat-aging-resistant polymer composition, which is an object of the present invention, a propylene polymer, a polyamide containing no copper compound, a modified propylene polymer and a copper compound and copper are used. Method of blending harm inhibitors simultaneously, method of blending propylene polymer, copper compound and copper hazard inhibitor, modified propylene polymer if necessary, and then blending with polyamide containing no copper compound, containing no copper compound A method of blending a polyamide, a copper compound and a copper damage inhibitor, and then blending with a propylene polymer or a modified propylene polymer can be exemplified, and only the polyamide containing no copper compound and the copper compound can be uniquely blended. As long as it does not exist, a polymer composition having excellent heat aging resistance can be obtained by any method. Among these, and especially, the method is preferable because the effect is remarkable.

In order to blend (A) to (E), various known methods such as Hensiel mixer, V blender, ribbon blender, tumbler blender or the like are mixed or mixed and then granulated by an extruder, and then a single screw extruder, Bent type extruder, two-screw extruder, conical two-screw extruder, co-kneader, platey equator, mixing extruder,
Injection molding using a twin screw conical screw extruder, planetary screw extruder, gear type extruder, screwless extruder, etc.
It is molded into a desired shape by performing rotational molding or the like.

As one of the preferred embodiments of the present invention, an inorganic filler, that is, a powdery filler such as iron oxide, alumina, magnesium oxide, calcium oxide, zinc oxide, and other oxides, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, Hydrated metal oxides such as calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate and the like; carbonates such as calcium carbonate, magnesium carbonate and the like; talc, clay,
Silicates such as bentonite, attapulgite, etc .; Borates such as barium borate, zinc borate, etc., Phosphates such as aluminum phosphate, sodium tripolyphosphate etc .; Sulfates such as gypsum etc .; Sulfite; and mixtures of two or more thereof, or fibrous fillers such as glass fiber, potassium titanate fiber, metal-coated glass fiber, ceramics fiber, wollastonite, carbon fiber, metal carbide fiber, and hardened metal fiber. Etc., such as ultra-high elastic polyethylene fiber, other spherical materials such as glass beads, glass balloons, shirasu balloons, etc., glass powder, glass flakes, mica, etc. (A) + (B) = 100 parts by weight, preferably 5 or more. When added 150 parts by weight, more preferably 10 to 100 parts by weight, rigidity, heat resistance,
The tensile strength etc. are improved. Further, the surface of the inorganic filler may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropylethoxysilane, 2-glycidoxypropyltrimethoxysilane. Of these, fibrous materials, particularly glass fibers, are preferable because they have excellent reinforcing effects.

In addition, other polymers may be blended within the range not impairing the object of the present invention.

Further, various additives usually added to plastics such as heat resistance stabilizers, weather resistance stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, oils, pigments and dyes may be added.

In still another embodiment, when copper iodide is used as the copper compound, when it is added in the form of an aqueous solution of copper iodide dissolved in an aqueous potassium iodide solution, the dispersibility of the copper compound in the composition is improved. The appearance and the like are further improved.

[Examples] Hereinafter, the contents of the present invention will be described with reference to suitable examples, but the present invention is not limited to these examples unless otherwise specified.

Examples 1 to 6 and Comparative Examples 1 to 4 (A) Propylene polymer (Mitsui Petrochemical Polypropylene J70
0: Mitsui Petrochemical Industry Co., Ltd.) 50 parts by weight, (B) Copper compound-free nylon-6 (Amilan CM100
1: manufactured by Toray) 50 parts by weight, (C) maleic anhydride graft-modified propylene polymer
(Graft amount of maleic anhydride = 3.0 parts by weight, 135 ° C deca
Intrinsic viscosity [η] = 0.45dl / g) measured with phosphorus (A)
+ (B) = 1 part by weight with respect to 100 parts by weight, (D) the copper compound shown in Table 1 is (A) + (B) + (C)
= 100 parts by weight of the compounding amount (parts by weight) shown in Table 1, (E) the copper damage inhibitor shown in Table 1 (A) + (B) +
(C) = 100 parts by weight of compounding amount shown in Table 1 (weight
Parts) and were melt-mixed using an extruder and granulated. Obtained Pele
The press sheet with a thickness of 1mm is produced at
Then, a dumbbell-shaped test piece was produced by a punching method.

Next, the initial tensile strength of these test pieces and the tensile strength after standing in an oven at 150 ° C for 15 days were measured according to ASTM D.
It measured according to 638. The results are shown in Table 1.

Comparative Examples 5 to 7 Resin containing a copper compound as nylon-6 (Amilan cm
1026: manufactured by Toray, containing 30 ppm as copper ions)
The test was conducted in the same manner as in Example 1. The results are shown in Table 2.
You

As can be seen from the above Examples and Comparative Examples, the polymer composition obtained by the method of the present invention is excellent in heat resistance and heat aging resistance, but after the copper compound is present in the polyamide, copper damage is caused. Those containing an inhibitor have poor heat aging resistance.

〔The invention's effect〕

As described above, according to the method of the present invention, heat aging resistance, heat resistance, strength, chemical resistance, moisture resistance, appearance, and further, an inorganic salt, (used as a road deicing agent ) Resistance to automobile parts such as automobile radiator tanks and segmenters, electrical appliances,
It can be used for machine parts and industrial parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 23/26 LDA 7107-4J 51/06 LLD 7142-4J LLE 7142-4J 53/00 LLV 7142- 4J LLW 7142-4J LLY 7142-4J LLZ 7142-4J 77/00 KKQ 9286-4J KKU 9286-4J LQS 9286-4J // (C08K 13/02 3:10 5:00)

Claims (1)

[Claims] 1. A propylene polymer (A), a polyamide (B), a modified propylene polymer (C) grafted with an unsaturated carboxylic acid or a derivative thereof, a copper compound (D) and a copper damage inhibitor (E). In the method for producing a polymer composition having excellent heat aging resistance by blending, a polyamide containing no copper compound is used as the polyamide (B), and only the polyamide (B) and the copper compound (D) are unique. A method for producing a polymer composition, which comprises blending each component in a state of not being blended with