JPS59149940A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having improved impact resistance without detriment to various characteristics such as rigidity, surface gloss, heat resistance, etc. inherent to polypropylene, by blending polypropylene, a polyamide and a specified modified ethylene/alpha-olefin copolymer. CONSTITUTION:0.01-5pts.wt. unsaturated carboxylic acid (derivative) such as maleic anhydride is grafted onto 100pts.wt. ethylene/alpha-olefin copolymer having a crystallinity index of 0-50% as measured by X-rays and an ethylene content of 40-93mol% to obtain a modified ethylene/alpha-olefin copolymer, which is then used as a dispersant for a polyamide to be incorporated in polypropylene. 40- 98pts.wt. propylene polymer ( I ), 60-2pts.wt. polyamide (II) such as nylon 6 having a relative viscosity of 0.5 or above and 1-50pts.wt. said modified etnylene/alpha- olefin copolymer (III) are blended together such that the combined quantity of component I and II is 100pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a propylene polymer composition having excellent rigidity, impact resistance, water resistance, surface gloss and heat resistance.

Crystalline polypropylene has excellent rigidity, surface gloss, heat resistance, etc., but has the drawback of poor impact resistance. Conventionally, as a method for improving impact resistance, a method of mixing polypropylene with a rubbery substance such as polyisobutylene, polybutadiene, a non-quality ethylene-propylene copolymer, or polyethylene has been widely used. However, on the other hand, these modified materials are softer than polypropylene and have a lower softening point, so they have the disadvantage of reducing the inherent characteristics of polypropylene, such as rigidity, surface hardness, heat resistance, oil resistance, etc. .

On the other hand, attempts have been made to improve the dyeability, heat resistance, and heat setting properties of polyolefins by adding and mixing polyamides and the like to polyolefins such as polypropylene. However, mechanical strength such as impact resistance of polyolefin and polypropylene is extremely reduced. Various methods have been used to improve the compatibility between polyolefin and polyamide, such as adding an ionomer to a mixture of polyolefin and polyamide (Japanese Patent Publication No. 652.9/1989), and adding an ionomer to a mixture of polyolefin and polyamide. A method of using a modified polyolefin into which at least one of acid, ester, amide, acid anhydride, and epoxide groups has been introduced as a polyolefin (Japanese Patent Publication No. 45-30945), or when blending crystalline polypropylene and polyamide. A method of intervening maleic anhydride-modified polypropylene (Kobunshi Kagaku, -λ2, 265 (1972)) and the like have been proposed. However, although these methods improved the compatibility between polypropylene and polyamide, the impact resistance was not sufficiently improved or effective.

In view of the current situation, the present inventor conducted various studies with the aim of improving impact resistance without impairing the original characteristics of crystalline polypropylene, such as rigidity, surface gloss, heat resistance, water resistance, etc. Result 1: It was found that the above object could be achieved by adding a graft modified product of a specific ethylene/α-olefin copolymer with a low saturated carboxylic acid or its derivative to polypropylene and polyamide, and the present invention was completed.
I ended up doing it.

That is, the present invention provides X based on 4'0 to 98 parts by weight of propylene polymer (A), 6'0 to 2 parts by weight of boriamy (B), and (A) + (B) = 100 parts by weight.
Linear crystallinity 0 to 50% and ethylene content 4
0 to 96 mol% of ethylene/α-olefin copolymer (modified ethylene obtained by graft-modifying 0.01 to 5 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof to 100 parts by weight)・Provides a propylene polymer composition with excellent rigidity, impact resistance, water resistance, surface gloss, heat resistance, etc., characterized by comprising 1 to 50 parts by weight of an α-olefin copolymer (D). It is.

The propylene polymer (A) used in the present invention is crystalline and preferably has a density of 0.89 to 0.93.
g/(7)3, melt flow rate (MFR:AS
TMD 1238, L) from 0.01 to 50 g/
10 min. Propylene homopolymer or propylene and a small amount of ethylene, 1-butene,
It is a block or random lli combination with α-olefins such as 4-methyl-1-pentene and 1-hexene.

The polyamide (B) used in the present invention includes hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2.4- or 2,4.4-trimethylhexamethylene diamine, 1,3- or 1,4-bis Aliphatic, alicyclic, aromatic diamines such as (aminomethyl)cyclohexane, bis(p'-aminocyclohexylmethane), m- or p-kylysylenediamine, adipic acid, speric acid, sebacic acid, cyclohexanedicarboxylic acid acids, aliphatic and alicyclic acids such as terephthalic acid and isophthalic acid,
Polyamides obtained by polycondensation with dicarboxylic acids such as aromatics, polyamides obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanoic acid, and lactams such as ε-prolactam and ω-laurolactam. Examples include polyamides obtained from polyamides, copolyamides composed of these components, and mixtures of these polyamides. Specifically, nylon 6, nylon 66, nylon 610, nylon 9S nylon 11, nylon 121 nylon 6/66, nylon 66/610
, nylon 6/11, etc. Among these,
Preferred are nylon 6 and nylon 66, which have excellent melting point, rigidity, etc., and have a large modifying effect on propylene copolymers (N).Moreover, the molecular weight is not particularly limited, but usually the relative viscosity ηr (J Engineering S K6810, in 98% sulfuric acid ) is 0
．． Polyamides with a polyamide of 5 or more are used, and among them, polyamides with a polyamide of 2,0 or more are preferred.

The modified ethylene/α-olefin copolymer (D) used in the present invention has a crystallinity determined by XPJ of 0 to 50%, preferably 0 to 60%, and an ethylene content of 40 to 96 mol%, preferably 70 to 60%. To 100 parts by weight of 90 mol% ethylene/α-olefin copolymer (C),
0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof.
It is a copolymer graft-modified by 1 to 1.0 parts by weight. Even if a copolymer graft-modified with an ethylene/α-olefin copolymer (C) with a crystallinity of 50% and an ethylene content of more than 93 mol% is used, the impact resistance of the propylene polymer composition remains the same. Almost no improvement. On the other hand, even if a copolymer obtained by modifying an ethylene/α-olefin copolymer having an ethylene content of less than 40 mol % is used, the impact resistance of the propylene polymer composition is not improved. In addition, the ethylene/α-olefin copolymer (0) is usually melt flow ray (MFR: ASTM D 125B, L)
is 0.05 to 50 g/10 m1n, and even 0.05 to 50 g/10 m1n.
Preferably, the amount is in the range of 5 to 20 g/10 m1n.

When a copolymer having an MFR outside the above range is used, a modified ethylene/α-olefin copolymer obtained from the copolymer and the propylene polymer (A) and polyamide (B)
The difference in melt viscosity between the two tends to increase, the dispersion effect is not sufficient, and the effect of improving impact resistance is not sufficient.

The α-olefin component units constituting the ethylene-α-olefin copolymer (C) are α-olefins having 6 or more carbon atoms, especially those having a carbon content of 6 to 1 day, such as propylene, 1-butene, 1 Examples include -hexene, 4-methyl-1-pentene, and 1-decennato, and one or a mixture of two or more thereof. The ethylene-α
The -olefin copolymer is usually a copolymer of an ethylene component and an α-olefin, but it may contain a diene component in a trace amount, for example, 0.5 mol % or less, depending on the case.

Examples of unsaturated carboxylic acids or derivatives thereof include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid,
Itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid 0 (endocys-bicyclo(2,2,1
) hept-5-ene-2,5=dicarboxylic acid), or derivatives thereof, such as acid halides,
Examples include amide 1 imide, anhydride, ester, etc., and specific examples include maleyl chloride, maleimide A maleic anhydride, citraconic anhydride, monomethyl maleate 1 dimethyl maleate, and dalicidyl maleate.

Among these, anhydrides are preferred, especially maleic anhydride-anhydride? is suitable.

The grafting ratio of the graft monomer in the modified ethylene-α-olefin copolymer CD) used in the present invention is in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the ethylene-α-olefin copolymer. The content is preferably in the range of 0.1 to 4 parts by weight. If the grafting ratio of the grafting monomer is less than 0.01 part by weight, the grafting monomer loses its compatibility with polyamide, delamination occurs, and the effect of improving impact resistance becomes small. Furthermore, if the grafting ratio exceeds 5 parts by weight, the degree of crosslinking of the graft modified product increases, and the effect of improving the impact resistance of the propylene copolymer composition decreases.

Furthermore, modified ethylene-α-olefin copolymer CD)
melt flow rate) (MFR, ASTM D 1
23B, L) is usually in the range of 0.01 to 20 g/IQ min, preferably 0.05 to 10 g/10 min.

A graft monomer selected from unsaturated carboxylic acids or derivatives thereof is added to an ethylene-α-olefin copolymer (a).
Various conventionally known methods can be used for graft copolymerization. For example, ethylene-α-olefin copolymer (0) is melted or dissolved in a solvent,
There is a method of graft polymerization by adding a graft monomer. During graft polymerization, other vinyl monomers such as styrene may also be present. In particular, the modified ethylene-〇-olefin polymer (D) obtained by efficiently performing graft polymerization using a radical generator,
The raw material ethylene-α-olefin copolymer (C) is less likely to be decomposed by oxidation, making it suitable for this purpose. Examples of radical generators include organic peroxides, organic bersesters, such as benzoyl peroxide, di'chloropenzyl peroxide, dicumyl peroxide, di-t
ert-butyl peroxide, 2,5-dimethyl-2,
5-di(peroxidebenzoate)hexyne-6,1
, 4-ibis('ter-butylperoxyisopropyl)benzene, latate, 2,5-dimethyl-2,5°-b.

Uroylperoxide, tert-buteracetylperoxy)hexyne-3,2,15-dimethyl-2,
5-di(tert-butylperoxy)hexane, t
er t-butyl perbenzoate, tert-butyl perphenylacetate), tert-butyl perisobutyrate, tert-butylperu SθC-oc)
), tert-'f-thyl perbivalate, cumyl perbivalate and t6rt-butyl perdiethyl acetate, as well as other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide),
Dialkyl peroxides such as -butylperoxy)hexane-3,2,5-dimethyl-2,5-di(t'ert-butylperoxy)hexane and 1,4-bis(ter't-butylperoxyisopropyl)benzene are preferable.

The propylene polymer composition of the present invention contains 40 to 98 parts by weight of the propylene polymer (A), preferably 50 to 90 parts by weight, 50 to 2 parts by weight, preferably 45 to 10 parts by weight of polyamide CB), and The modified ethylene/α-olefin copolymer (rr) is (A) ten (B) =
It is composed of 1 to 50 parts by weight, preferably 10 to 40 parts by weight per 100 parts by weight.

If the propylene polymer (A) is less than 40 parts by weight, the propylene polymer phase may form a matrix and the physical properties will change significantly due to humidity, while if it exceeds 98 parts by weight, the polyamide (B) will improve heat resistance, rigidity, and paintability. , oil resistance etc. are not improved. Furthermore, if the modified ethylene/α-olefin copolymer (D) is less than 1 part by weight, the compatibility between the propylene polymer (A) and the polyamide (B) cannot be improved, resulting in extremely low impact resistance, surface gloss, etc. On the other hand, if it exceeds 50 parts by weight, the rigidity, heat resistance, oil resistance, surface hardness, etc. of the composition will decrease.

In order to obtain the propylene polymer composition of the present invention, the propylene polymer (A), polyamide (B) and modified ethylene/α-olefin copolymer CD) are mixed in the above range using various known methods such as a Henschel mixer, (2) After mixing with a blender, ribbon blender, tumbler blender, etc., melt-kneading with a screw extruder, twin screw extruder, Niegoo-Banbury mixer, etc., followed by granulation or pulverization may be adopted.

The propylene polymer composition of the present invention includes heat stabilizers, weather stabilizers, antistatic additives, lubricants, slip agents, nucleating agents, flame retardants, oil agents, pigments or dyes, glass fibers, carbon fibers, and potassium titanate. Inorganic or Organic reinforcing materials and fillers may be blended within the range that does not impair the purpose of the present invention.

In addition, the propylene polymer composition of the present invention may contain a small amount of 1%, for example, up to 50 parts by weight, within a range that does not impair the object of the present invention.
Polyethylene, ethylene/propylene copolymer 1-ethylene/1-butene copolymer, ethylene/4-methyl-1-
Pentene copolymer, ethylene/1-octene copolymer,
Polyolefins such as poly-1-butene and poly-4-methyl-1-pentene, ethylene/vinyl acetate copolymers, ethylene/vinyl alcohol copolymers, polyvinyl acetate, vinyl compound polymers such as polyvinyl chloride, polyethylene terephthalate, Polar 4fU'a such as (r)e thermoplastic polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyacetal, etc. may be blended.

The propylene polymer composition of the present invention is characterized by the use of the above-mentioned specific modified ethylene/α-olefin copolymer as a dispersant for polyamide in the hepropylene polymer, which allows good dispersion of polyamide in the composition. The present invention is characterized in that the effect of modifying the propylene polymer by the polyamide can be sufficiently exhibited, and the impact resistance of the composition can be significantly improved.

The propylene polymer composition of the present invention has extremely superior specific impact resistance and good appearance compared to conventionally known polypropylene/polyamide compositions, so it can be used for rigidity and heat resistance in automobile parts, electrical appliances, mechanical parts, industrial parts, etc. It is also suitable for applications requiring impact resistance.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples unless they go beyond the gist of the invention.

The measurement method used in the examples of the present invention is as follows.

Tensile strength ASTM D6 filter 8 Tensile strength after immersion in water ASTM D6 after immersion in water for 24 hours
'58 Bending modulus ASTM D790 Surface hardness ASTM D785 R scale Izot impact strength ASTM D256 Notched heat distortion temperature ASTM D6;8 Load 4.6 to 9/cr1
2 Surface gloss Visually determined in 3 stages <Production example of modified ethylene/α-olefin copolymer> Ethylene content 80 mol%, crystallinity 2%, 'MFR1,
100 parts by weight of the ethylene/propylene random copolymer of No. 2, 1.0 parts by weight of acetone, 0.02 parts by weight of α,α'-bis-t-butylperoxy-diisopropylbenzene, and 1.0 parts by weight of maleic anhydride. After dropwise mixing the mixed liquid with a Henschel mixer,
By granulating at 40°C, -1 crystallinity 2%,
MF'R0.8, maleic anhydride graft amount skin 80
A maleic anhydride-grafted ethylene/propylene random copolymer (modified EPo-1) of % by weight was obtained.

Example 1 Propylene homopolymer (MFR:ASTMD 1238
．． 260°C18, hereinafter referred to as PP-1) 90 parts by weight,
10 parts by weight of nylon 6 (ηr: 2.25) and modified x
1,20 parts by weight of pa-1 in a tumbler-type blender.
After mixing for 0 minutes, the mixture was granulated using a 40 mmφ extruder with L/D=28 at a resin temperature of 240°C.

This pellet was injection molded using a 5-50 injection molding machine manufactured by Toshiba Machine Co., Ltd. at a resin temperature of 250°C to prepare a test piece. The measurement results of physical properties are shown in Table 1.

Examples 2 to 3, Comparative Example 1 The same procedure as in Example 1 was carried out except that the blending ratio of p P -,1 and nylon 6 was changed. Results Example 4 The blending ratio of the composition was PP-175 parts by weight and nylon 625.
The same procedure as in Example 1 was carried out except that the parts by weight and the parts by weight of modified EPO-11o were changed. The results are shown in Table 1.

Example 5 The same procedure as in Example 1 was carried out except that a propylene/ethylene block copolymer (x7IFp, 6.0% ethylene content 18% by weight, hereinafter referred to as PP-2) was used instead of pp-i. Ta. The results are shown in Table 1.

Example 6 110 parts by weight of the composition of Example 4 was added with an ethylene/propylene random copolymer (MFR 1,5,190°C, crystallinity 10%, ethylene content 83 mol%, hereinafter E'PC-A).
A composition to which 10 parts by weight (10 parts by weight) was further added was evaluated. The results are shown in Table 1.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the blending ratio of the composition in Example 1 was changed to 75 parts by weight, 625 parts by weight of nylon, and 160 parts by weight of modified EPO-'.

The results are shown in Table 1.

Comparative Example 3 Example 2 except that vpc'Qh used in Example 6 was used instead of modified ICPC-1 in the composition of Example 2.
I did the same thing. The results are shown in Table 2.

Comparative Example 4 In the composition of Example B, maleic anhydride daraftpropylene homopolymer (MFll) was used instead of modified EPC-1.
B, 230°C, maleic anhydride draft ratio 1.5% by weight
・The same procedure as in Example 2 was performed except for using M A HP P). The results are shown in Table 2.

Comparison to Comparative Example 5 In the composition of Example 4, ethylene/ethyl acrylate copolymer (manufactured by Nippon Yukocar,
The same procedure as in Example 4 was carried out except that EF:A DPDJ6169 (trade name) was used. The results are shown in Table 2.

Comparative Example 6 In the composition of Example 4, ethylene-meccrylic acid copolymer (MFR 12, 190°
The same procedure as in Example 4 was carried out except that C-ethylene content (88% by weight) was used. The results are shown in Table 2.

Example 7 PP-175 parts by weight, nylon 625 parts by weight, modified EP
After mixing 110 parts by weight of C-10 and 30 parts by weight of talc (average particle size 3μ) in a Henschel mixer for 3 minutes, the diameter was 3Qmmφ.
The mixture was granulated using a twin-screw extruder at a resin temperature of 240°C.

This pellet was molded into a test piece in the same manner as in Example 1,
evaluated. The results are shown in Table 2.

Example 8 Example 7 was carried out in the same manner as Example 6 except that the amount of modified EP δ-1 in the composition was increased to 20 parts by weight. The results are shown in Table 2.

Comparative Example 7 Modified EPC in Example 7! -1 instead of RPC-A
The same procedure as in Example 7 was carried out except that . The results are shown in Table 2.

Comparative Example 8 Modified EP (MAHPP instead of 3-1) in Example 7
The same procedure as in Example 7 was carried out except that .

Claims (1)

[Claims] (1) Propylene polymer (A) 40 to 98 parts by weight, polyamide (B) 60 to 2 parts by weight, and (A)
+ (B) = 100 parts by weight, an ethylene/α-olefin copolymer ((1
1 to 50 parts by weight of a modified ethylene/α-olefin copolymer (D) obtained by graft-modifying 0.01 to 5 parts by weight of a graft monomer selected from unsaturated carboxylic acids or derivatives thereof to 100 parts by weight. A propylene amount coalescing composition characterized by: