JPH01284552A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin composition having low water absorptivity and improved in moldability, tensile strength, tensile elongation, etc., by mixing a polyamide resin with an acid-modified polyolefin, a PP resin and a specified compound. CONSTITUTION:100 pts.wt. in total of 100 pts. wt. polyamide resin (A), 0.5-100 pts.wt. acid-modified polyolefin (B) formed by grafting 0.1-5.0 pts.wt., alpha,beta-unsaturated carboxylic acid (derivative) onto 100 pts.wt. polyolefin and 5-150 pts.wt. PP resin (C) of an MFR of 1-50g/10min is mixed with 0.01-3 pts.wt. at least one compound (D) selected from among a silicate mineral (e.g., talc), a polymer of a degree of polymerization of at least two, having repeating units of formula I (wherein n is 2-4), e.g., polyethylene terephthalate, an alkali metal-containing organic phosphorus compound of formula II [wherein M' is Na or K, X and Y are each formula III or IV (wherein R<1-2> are each H or a 1-6 C alkyl)] and an alkaline earth metal-containing organic phosphorus compound of formula V (wherein R<2> is Mg or Ca, and Z is X).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyamide resin composition, and more specifically, it combines the excellent properties of polyamide and polypropylene, and has excellent water absorbency as well as moldability. Characteristics (low warpage,
The present invention relates to a polyamide resin composition having excellent properties (low deformation, high cycle performance, etc.) and various physical properties (tensile strength, tensile elongation, etc.).

[Prior art and problems to be solved by the invention] In general, polyamide resins are widely used as synthetic fibers due to their excellent physical and chemical properties.
In recent years, it has come to be used as a molding material. This is because polyamide resin is contained within thermoplastic resin and has high mechanical strength.

This is because it has excellent abrasion resistance, chemical resistance, heat resistance, and relatively hard electrical properties, and has sufficient performance as an engineering plastic.

However, on the other hand, it has undesirable performance such as dimensional changes due to water absorption and a decrease in mechanical strength due to the amide group (-CONH-), which makes it less marketable as a molding material. Limited.

On the other hand, polypropylene is cheap and breathable? Although it exhibits almost no R property, it has drawbacks such as being soft and having poor physical properties at high temperatures.

Therefore, in order to improve the respective disadvantages of polyamide resin and polypropylene resin, it is natural to think of using these resins together, but it is possible to use a resin mixture obtained by mixing polyamide resin and polypropylene resin in the usual way, or a mixture of them. A resin composition obtained simply by melting and kneading has poor compatibility and cannot provide a composition with the desired excellent properties.

Therefore, we have traditionally developed resin compositions that combine the excellent properties of polyamide resin, polypropylene resin, and pyrene resin, that is, the excellent abrasion resistance of polyamide resin,
Electrical properties, heat resistance 1 mechanical strength.

-3= Oil resistance and low water absorption of polypropylene resin,
Various proposals have been made for the purpose of obtaining a resin composition that has hot water resistance, metal halide resistance, and low-temperature impact resistance (Japanese Patent Publication No. 42-12546, Japanese Patent Publication No. 50-7636, etc.) ).

In the case of these so-called polymer alloy compositions, considerable improvements have been made in terms of low water absorption performance, but at present little consideration has been given to molding properties and other physical properties. In other words, in the case of these polymer alloy compositions, since a reaction is involved as a compatibilization method, there is a problem that the molding shrinkage rate increases. Additionally, since polypropylene resins have lower melting points than polyamide resins, these polymer alloy compositions tend to take longer to solidify than polyamide resins. Therefore, molded products tend to warp and deform, and the molding cycle becomes longer, which is a major problem.

The present inventors have conducted extensive research with the aim of improving the above-mentioned molding properties and other physical properties as well as having excellent low water absorption.

[Means to solve the problem]

As a result, it has been found that when using polyamide resin and polypropylene resin together, the objective can be achieved by blending acid-modified polyolefin, silicate mineral, polyethylene terephthalate, polybutylene lentilephrate, or a specific organic phosphorus compound.

The present invention was completed based on this knowledge. That is, the present invention includes (A) 100 parts by weight of polyamide resin.

(B) 0.5 to 100 parts by weight of acid-modified polyolefin.

(C) 5 to 150 parts by weight of polypropylene resin and (D((1) silicate mineral.

(2) General formula [where n is 2 or 4]. ] A polymer having a degree of polymerization of 2 or more and having a repeating unit represented by the following.

(3) General formula (where M+ represents sodium or potassium,
, Y (here, R' and R2 are each hydrogen or carbon number 1)
~6 alkyl group. ) is shown. An alkali metal-containing organic phosphorus compound represented by the formula (4) (wherein, M2 represents magnesium or calcium, and Z is (here, R' and R2 are the same as above). ] At least one compound selected from the group consisting of alkaline earth metal-containing organophosphorus compounds represented by 0.01 parts by weight per 100 parts by weight of the above (A), (B), and (C). The present invention provides a polyamide resin composition characterized in that the weight of the polyamide resin composition is 3 parts by weight.

The component (A) in the composition of the present invention is nylon 6,
Nylon 11. Polylactums such as nylon 12; nylon 66, nylon 610. Nylon 612. Polyamide neck obtained from dicarboxylic acid such as nylon 46 and diamine; nylon 6/66, nylon 6/610. Nylon 6/612° Nylon 6/12. Nylon 6/6
Copolymerized polyamides such as 6/610; nylon 6/6T
(T: terephthalic acid component); Aromatic polyamide I"ff obtained from aromatic dicarboxylic acid such as isophthalic acid and mexylenediamine, or semi-aromatic obtained from aromatic dicarboxylic acid such as isophthalic acid and alicyclic diamine Group polyamides, and further include polyesteramide, polyetheramide, and polyesteretheramide.Incidentally, as the polyamide resin which is the component (A), these polyamides may be used alone, or two types may be used. The above can also be used together.

Note that the polyamide resin that can be used in the present invention is not limited by the type, concentration, molecular weight, etc. of the terminal group of these polyamides as long as it is selected from the above-mentioned polyamides, and various resins can be used. However, highly carboxylic acid terminated polyamides are particularly preferred. In addition, monomers remaining or generated during polymerization of polyamide,
It is also possible to use polyamide in which low molecular weight substances such as oligomers are mixed.

Next, component (B) of the composition of the present invention is an acid-modified polyolefin, and although there are various types, in the present invention, it can be roughly classified into the following two types. That is, (1) a grafted acid-modified polyolefin obtained by grafting α2β-unsaturated carboxylic acid or a derivative thereof to a polyolefin in the presence of a radical generator, and (2) a monomer of an olefin (especially α-olefin),
It is a ternary acid-modified polyolefin obtained by copolymerizing α, β-unsaturated carboxylic acid or its derivative, and methacrylic acid ester or acrylic acid ester.

Among these, for the graft acid-modified polyolefin mentioned above, various polyolefins can be used as the base, but preferably low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, and polybutene. -1, polymethylpentene-1, copolymer of ethylene and α-olefin (ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-butene-1 copolymer, etc.), ethylene and copolymers with vinyl compounds (ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer) , ethylene-(meth)acrylic acid (ester)-α, β-unsaturated carboxylic acid (derivative) terpolymer, ethylene-vinyl chloride copolymer, etc.), or mixtures thereof.

Further, as the α,β-unsaturated carboxylic acid or its derivative used for graft modification, acrylic acid is used.

Maleic acid, fumaric acid, itaconic acid, 3.6-nindomethylene-1,2,3.6-titrahydrosis-phthalic acid or their anhydrides and esters, alkylaminomethacrylates such as 2-dimethylaminoethyl methacrylate, and glycidyl Examples include methacrylate, and among these, acrylic acid, maleic acid, maleic anhydride, and 3,6-nindomethylene-L2,3,6-titrahydrosis-phthalic anhydride are preferred. In addition, these may be used individually or in mixture of 2 or more types.

Further, as radical generators used for graft modification, dicumyl peroxide; hensyl peroxide; di-L-butyl peroxide; 2,5-dimethyl-
2,5-di(t-butylperoxy)hexane; 2.5
Organic peroxides such as -dimethyl-2,5-di(t-butylperoxy)hexene-3; lauroyl peroxide; and t-butyl peroxyhenzoate are preferably used.

In producing the grafted acid-modified polyolefin of (1) above, the above-mentioned polyolefin is suspended or dissolved in a suitable solvent, and the above-mentioned α is added to the above-mentioned polyolefin.

A method of adding a β-unsaturated carboxylic acid or its derivative and a radical generator and stirring with heating, or a method of pre-mixing the polyolefin and α,β-unsaturated carboxylic acid or its derivative and a radical generator and using an extruder or Banbury mixer. -, a method of melt-kneading using a kneader, etc., and the latter method is particularly preferably employed. The amount of each compound used in this case is not particularly limited as long as it can be selected appropriately depending on various situations, but usually α, β-unsaturated carboxylic acid or its derivative is used per 100 parts by weight of polyolefin. A rough guideline is 0.1 to 5.0 parts by weight and 0.1 to 5.0 parts by weight of the radical generator.

On the other hand, regarding the above ternary acid-modified polyolefin,
Various olefin monomers can be used, but ethylene and propylene are preferred.

These include butene-1, methylpentene-1, etc., and ethylene is particularly preferred. Further, the α,β-unsaturated carboxylic acid or its derivative is the same as described above.

This ternary acid-modified polyolefin can be produced using a conventional polymerization method. The amount of each compound used at this time is not particularly limited, as long as it can be selected appropriately depending on the various circumstances.
Usually, the composition of the present invention may contain 1 to 5 parts by weight of α,β-unsaturated carboxylic acid or its derivative and 8 to 25 parts by weight of methacrylic ester or acrylic ester per 100 parts by weight of olefin. Component (B) is an acid-modified polyolefin, especially the above-mentioned grafted acid-modified polyolefin and/or
Alternatively, (3) a ternary acid-modified polyolefin is preferably used, and the blending amount thereof is 0.5 to 100 parts by weight per 100 parts by weight of the polyamide resin as component (A). If the amount of acid-modified polyolefin (B) is less than 0.5 parts by weight, the compatibility between the polyamide as the component (A) and the polypropylene resin as the component (C) cannot be improved. The desired physical properties cannot be imparted to the composition. On the other hand, even if the amount of the acid-modified polyolefin (B) exceeds 100 parts by weight, there will be no effect corresponding to the amount, but rather there is a risk that the various physical properties of the resulting composition will be deteriorated.

Next, component (C) of the composition of the present invention is a polypropylene resin, which includes not only a propylene homopolymer but also a propylene copolymer.

Examples of propylene copolymers include propylene-ethylene copolymers, propylene-butene-1 copolymers, and block copolymers and random copolymers thereof. As this component (C), a propylene homopolymer or a propylene copolymer may be used alone, or two or more types may be used in combination.

The molecular weight of this propylene homopolymer and propylene copolymer is not particularly limited, but generally MFR is 1 to 1.
50 g/10 minutes is preferably used. Also, the amount of component (C) to be blended should be 5 to 150 parts by weight based on 100 parts by weight of the polyamide (A) component. It is preferably selected within the range of 10 to 140 parts by weight. If the amount of component (C) is less than 5 parts by weight, the excellent properties inherent to polypropylene (low water absorption, etc.) cannot be sufficiently imparted to the resulting composition.

If the amount exceeds 150 parts by weight, the resulting composition will not be satisfactory in physical properties such as heat resistance and mechanical strength.

Among the physical properties required for the composition of the present invention, when reducing water absorption is important, the total blending amount of (B) acid-modified polyolefin and (C) polypropylene resin should be changed to the blending amount of (A) polyamide resin. It is effective to increase the amount of polyamide resin (A) to (B) when heat resistance is particularly expected for the composition of the present invention.
It is preferable that the amount is greater than the total amount of components (C).

Furthermore, in the composition of the present invention, the above (A).

It is necessary to blend not only components (B) and (C) but also one or more compounds selected from the above (1) to (4) as component (D). Here, component (1) is a silicate mineral, more specifically, it contains 5iOz as an essential component, and also contains MgCh and AfzOh.

It is a hydrous or anhydrous salt containing one or more of each component such as CaO, Fed, Fe2O3, Na2O, etc.

Specifically, talc, clay, silica, silica/alumina, mica, allophane, pyrophyllite, kaolinite, montmorillonite, vermiculite, wollastonite, kaolin, etc. can be mentioned.

In addition, the component (2) is represented by the general formula % [wherein n is 2 or 4]. ] A polymer having a degree of polymerization of 2 or more and having a repeating unit represented by the following formula, specifically, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). However, these do not necessarily have to be polymers, and may be low molecular weight oligomers.

Furthermore, component (3) and component (4) are both organic phosphorus compounds, and each has the general formula (α) described above.

It is represented by the general formula (β). All of these have been conventionally used as nucleating agents for polyamide resins, and various types can be mentioned, but in the present invention, commercially available ones may be used.

In the composition of the present invention, the above (1) is used as the component (D).
) to (4) may be used alone or in combination of two or more, and the blending amount of component (D) is the same as that of (A) above.
, (total of 100 parts by weight of BL (C) component = 16
- from 0.01 to 3 parts by weight, preferably from 0.1 to 2 parts by weight. Here, the blending amount of component (D) is 0
．． If the amount is less than 0.01 parts by weight, it will be difficult to improve the warpage of the molded product obtained from the composition, and it will also be impossible to shorten the molding cycle. On the other hand, if it exceeds 3 parts by weight, the fluidity of the composition will decrease and the impact resistance will also decrease.

When producing the polyamide resin composition of the present invention (
The resin components A), (B), and (C) and at least one of the additives (components (1) to (4)) that are component (D) can be melt-kneaded in various states. for example,
(B) acid-modified polyolefin, (C) polypropylene resin and (D) additives may be added to (A) polyamide resin which is still in a molten state after completion of the polymerization reaction and then melt-kneaded, or it may be in the form of powder or pellets. The above components (B), (C) and (D) may be added to the polyamide resin (A) and melt-kneaded. Furthermore, in order to maximize the effect of the additive that is component (D), it is necessary to add at least one of the additives listed in (1) to (4) above to the polyamide resin (A) and then melt-knead it. , (B), and (C) are preferably added and melt-kneaded.

The temperature when melting and kneading each component may be selected as appropriate, but is usually 180°C to 350°C, preferably 200°C.
-300°C. If the temperature is too low, each component will be insufficiently melted, making complete melt-kneading difficult, and if the temperature is too high, there is a risk that a decomposition reaction will proceed, which is not very preferable.

The above-mentioned melt-kneading operation may be performed using a known melt-kneading device such as a single-screw or twin-screw extruder.

The composition of the present invention includes (A) and (B) as described above.

The main components are components (C) and (D), but depending on the purpose, dyes, pigments, fillers, and nucleating agents may be added.

Appropriate amounts of fibrous substances, plasticizers, lubricants, mold release agents, coupling agents, blowing agents, heat resistant agents, weather resistant agents, flame retardants, etc. can also be added.

The composition of the present invention can also be used in pipes and tubes.

It can be processed into rods, injection molded products, etc., and can also be subjected to post-processing such as plating.

[Example] Next, the present invention will be described in more detail based on Examples and Comparative Examples.

The various physical properties of the polyamide resin compositions obtained on each side below were measured based on the following test methods.

Test W11 sum lambda skin test piece was prepared by molding the composition using a screw in-line injection molding machine. The cylinder temperature at this time is (
A) 280°C when using nylon 66 as the polyamide resin, 265° when using nylon 6/66
When C and nylon 6 were used, the temperature was 250°C. Moreover, the mold temperature was 60°C.

Kaikyorutan 1M Supervision (1) Water Absorption Characteristics (1-1) Measurement of Water Absorption Rate Using a tensile test specimen specified in ASTM-D-63'8, immerse it in boiling water at 100°C for 24 hours. The weight was calculated according to the following formula from the absolute dry weight after molding and the weight after water absorption.

(1-2) Measurement of dimensional change rate □ upon water absorption From the longitudinal dimension of the above water-absorbed tensile test piece and the longitudinal dimension of the test piece at the time of absolute drying (absolutely dry) □ after molding, Calculated according to the formula.

(2) Tensile strength and elongation measurement □ Measured in accordance with ASTM-D''63EH.

(3) Heat distortion temperature □ Based on ASTM-D-134s, bending stress 46 kg
Measured using f/CTM. (4) Molding shrinkage rate A No. 1 test piece specified in ASTM-D-638 was molded and placed at a temperature of 23°C for 24 minutes in an absolutely dry state, and then the longitudinal dimension was measured. Then, in the next generation, the molding shrinkage rate was determined.

1'20 x 12,0" The distance from the plane was measured to determine the warpage condition.

(6) High cycle test 45 on a disc with a medullary diameter and a thickness of 3 mm, and an outer diameter of 7 mm.

Inner diameter 2.5mm, length j5. Shape 9 molded products made by integrating cylinders of mm in diameter were molded with different cooling times, and judgment was made based on whether the shape of the pin holes inside was good or not.

In addition, (A) polyamide resin used on each side,
(B), acid-modified polyolefin, (C) polypropylene resin, and (D) additives are as follows.

A Bo1 Amide L ■Nylon 66 Relative viscosity: 2.85 Amino end group concentration: 5. OX, 10-5 equivalent/g
■Nylon 6/66 Copolymerization ratio: Nylon 6/Nylon 66 = 10/90
Relative viscosity: 2.90 Amino end group concentration: 4.5X10-' equivalent 7bis Nylon 6 Relative viscosity: 3.10 Amino end group concentration: 4.5X10-'equivalent/g-RoΣm'h-born n- L/Sununo ■ Grafted acid-modified polypropylene (type ■) 23 (1
A grafted acid-modified polypropylene obtained by adding 0.35% by weight of maleic anhydride to tactical polypropylene having an MFR of 1.0 g/10 min.

■Ternary acid-modified polyethylene (type■) Ethylene 100
A ternary acid-modified polyethylene obtained by copolymerizing 7 parts by weight of methyl methacrylate and 1 part by weight of maleic anhydride.

Cbo 1 Propylene 1 ■ Propylene homopolymer JIS K 6758 MFR of 18 g/10 min Propylene homopolymer (manufactured by Showa Denko ■, Shore 1: +7-
MA 610H).

■Propylene block copolymer A propylene ethylene block copolymer with an MFR of JIS K 6758 of 16 g/10 minutes (manufactured by Showa Denko ■, Showaromer-MK511).

"Warm (1) Talc (average particle size 2μ, manufactured by Hayashi Kasei Co., Ltd. 5000
S ) (2J PET powder (molecular weight 20,000) (
3) Organophosphorus compound or ~) II (t-Bu OP 0Na (4) as organic phosphorus compound (t-Bu represents a tertiary butyl group) 23 - Examples 1 to 11 and Comparative Examples 1 to 5 (A) polyamide resin, (B) acid-modified polyolefin, (C) polypropylene resin, and (D) various additives were mixed in advance for 5 minutes using a Henschel mixer in the amounts (wt%) shown in Table 1. Dry blended.

Each of the obtained mixtures was kneaded using a vented co-directional twin-screw extruder (inner diameter 30 mm) to create pellets. In addition, for nylon 66-based mixtures, the temperature is 280°C, nylon 6/
The mixture was heated to 265°C for the 66-based mixture, and 250°C for the nylon 6-based mixture.

Samples for measuring physical properties were prepared from each pellet using an injection molding machine, and each physical property was measured. The results are shown in Table 2.

(The following is a blank space) [Effects of the Invention] According to the present invention, it combines the excellent properties of polyamide and polypropylene, and in addition to its original low water absorption,
Molding properties (low warpage, low deformation.

A polyamide resin composition with improved molding cycle (equivalent to that of polyamide resin) and various physical properties (tensile strength, tensile elongation (impact resistance), heat deformation resistance) can be obtained.

Therefore, the polyamide resin composition of the present invention is expected to be widely and effectively used as an engineering resin, specifically as a material for automobile parts 3 pump housings, electric or electronic parts, and connectors thereof.

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Claims (1)

Scope of Claims: (A) 100 parts by weight of polyamide resin, (B) 0.5 to 100 parts by weight of acid-modified polyolefin, (C) 5 to 150 parts by weight of polypropylene resin, and (D) (1) silicate mineral. , (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n is 2 or 4. ] A polymer with a degree of polymerization of 2 or higher and having a repeating unit represented by (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, M^1 represents sodium or potassium,
X and Y each have a ▲ mathematical formula, chemical formula, table, etc. ▼ or ▲ a mathematical formula, chemical formula, table, etc. ▼ (Here, R^1 and R^2 are each hydrogen or an alkyl group having 1 to 6 carbon atoms. ). ] Alkali metal-containing organophosphorus compounds represented by (4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, M^2 represents magnesium or calcium, Z represents ▲ Numerical formula, chemical formula, table, etc. There is ▼ or ▲ there is a mathematical formula, chemical formula, table, etc. ▼ (Here, R^1 and R^2 are the same as above.) Indicates. ] at least one compound selected from the group consisting of alkaline earth metal-containing organic phosphorus compounds represented by 0.01 to 3 parts by weight per 100 parts by weight of the above (A), (B), and (C). A polyamide resin composition characterized in that it contains parts by weight.