JPH03126740A - Reinforced polypropylene resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition consisting of a polypropylene resin, polyamide resin which keeps a definite relationship with the polypropylene resin, modified polyolefin, inorganic filler and/or fibrous reinforcing material and especially having excellent form-rataining properties under high temperature atmosphere. CONSTITUTION:The objective composition obtained by blending 100 pts.wt. blend consisting of (A) 94-50wt.% propylene homopolymer and/or copolymer, preferably having 0.01-50g/10min melt flow, (B) 1-40wt.% modified polyolefin (e.g. ethylene/acrylic acid copolymer) having 0.01-100g/10min melt index and (C) polyamide resin, preferably having high terminal amino content with (D) 1-200 pts.wt. inorganic filler and/or fibrous reinforcing material and satisfying formula in a ratio of melt viscosity (etaPP) of the component A and melt viscosity (etaPA) of the component C.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a reinforced polypropylene resin composition, and more specifically, it has both the excellent properties of polypropylene resin and polyamide resin, and has excellent heat resistance, especially under high temperature atmosphere. This invention relates to a reinforced polypropylene resin composition that has excellent shape retention and heat-resistant rigidity and is suitable for various industrial parts such as automobile parts and OA equipment parts.

[Prior art and problems to be solved by the invention] In general, polypropylene resins are used in a wide range of fields because they are relatively inexpensive, have virtually no water absorption in practical use, and have good properties such as being soft. There is. However, it has a high degree of heat resistance, especially in high temperature atmospheres, e.g. 150-180'C
The shape retention (heat resistance rigidity) of polypropylene resin is generally insufficient in many cases because it is near the melting point of polypropylene resin. This has limited its application to fields that require heat resistance, specifically to automotive exterior parts that require baking at temperatures of about 150 to 170°C during the painting process.

Conventionally, in order to improve such properties, filling of various fillers, crosslinking of the resin portion, blending with other highly heat resistant resins, etc. have been carried out. However, the heat resistance of the resinous acid products obtained in this way is not improved to a satisfactory degree, or even if they are effective to some extent, other properties such as rigidity and moldability are significantly impaired, or There were problems such as a significant increase in price, and there were many cases where it could not be put to practical use. Temperature range near the crystal melting point of the polypropylene resin forming the matrix (160°C)
Even in the 1JIIli product filled with an inorganic filler, a significant decrease in rigidity was observed, and there was a limit to its use in fields where higher rigidity, especially heat resistance, was required.

Therefore, the present inventors conducted intensive research with the aim of improving the shape retention (heat-resistant rigidity) particularly in high-temperature atmospheres while maintaining the excellent properties of polypropylene resin and boriad resin. It has been found that the desired resin composition can be obtained by blending a polyamide resin and variable range polyolefin, which have a certain relationship with the polypropylene resin, as well as an inorganic filler and a fibrous reinforcing material, into the resin. The present invention is based on this knowledge.

[Means for solving the problem] That is, the present invention provides (A) polypropylene resin 94-5
0% by weight, (B) 1 to 40% by weight of modified polyolefin, and (C) 5 to 40% by weight of polyamide resin, (D) inorganic filler and/or fibrous reinforcing material 1 to 100 parts by weight. 200 parts by weight, and at a molding temperature and shear rate of 100 sec-'
) Polypropylene resin melt viscosity ηPP (pois
e) and (C) Melt viscosity ηrA (poi
se) is determined by the formula (I) η2. /η,>1... The present invention provides a reinforced polypropylene resin composition that satisfies (1).

In the present invention, (A) polypropylene resin (hereinafter (A)
) Ingredients. ), a propylene homopolymer and/or a propylene copolymer is used. Here, the propylene copolymer includes propylene-ethylene copolymer, propylene-butene-1 copolymer, etc.
These block copolymers and random copolymers are used.

In addition, for this polypropylene resin, a propylene homopolymer or a propylene copolymer may be used alone, or two or more types may be used in combination. At this time, the molecular weight of the propylene homopolymer and propylene copolymer is not particularly limited, but generally the melt flow rate (MFR
) is 0. OI ~50 g/10 min is preferably used.

Next, (B) modified polyolefin in the present invention (hereinafter ((
B) Mark as 1 minute. ) as carboxylic acid group (acetate group,
Acrylic acid group, methacrylic acid group.

fumaric acid group, itaconic acid group, etc.), carboxylic acid metal bases (sodium salt, calcium salt, magnesium salt, zinc salt, etc.), carboxylic acid ester group (methyl ester group,
It is a polyolefin having at least one functional group selected from ethyl ester group, propyl ester group, butyl ester group, vinyl ester group, etc.), acid anhydride group (maleic anhydride group, etc.), and epoxy group. Examples of the polyolefin include polyethylene, polypropylene, polybutene, ethylene/propylene copolymers, ethylene/butene copolymers, penta-functional ethylene/hexene copolymers, and copolymers containing a small amount of diene. can.

Specific examples of such modified polyolefins include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer 1 ethylene/methacrylic acid/zinc methacrylate copolymer, and ethylene/acrylic acid copolymer. Acid/sodium methacrylate copolymer, ethylene/
Isobutyl acrylate/meccrylic acid/zinc methacrylate copolymer, ethylene/methyl methacrylate/methacrylic acid/magnesium methacrylate copolymer, ethylene/
Ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, maleic anhydride Grafted polypropylene.

Maleic anhydride grafted ethylene/propylene copolymer, acrylic acid grafted ethylene/propylene copolymer,
Fumaric acid grafted ethylene/1-butene copolymer, ethylene/1-hexene-itacore M copolymer 11 Ethylene/propylene-endobicyclo[2,2,1,)-5-heptene-2,3 dihydric anhydride copolymer Polymer, ethylene/propylene-methacrylic acid grafted glycidyl copolymer maleic anhydride grafted ethylene/propylene/1.4-
These include hexadiene copolymers, fumaric acid-grafted ethylene/propylene/dicyclopentadiene copolymers, maleic acid-grafted ethylene/propylene/norbornadiene copolymers, and acrylic acid-grafted ethylene/vinyl acetate copolymers. Polyolefins may be used alone or in combination of two or more.

The above-mentioned modified polyolefin can be produced by known methods, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 4627527, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-436.
Publication No. 77, Special Publication No. 535716, Special Publication No. 53-
It can be produced according to the methods disclosed in Japanese Patent Publication No. 19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 569925, etc. Regarding ethylene ionomers, generally "Surlyn °", "Himilan", "゛'
Various grades commercially available under the trade name "Kobolene" can be used.Also, the degree of polymerization of the modified polyolefin used in the present invention is not particularly limited, but usually has a melt index of 0.01 to 100 g/10 min. You can arbitrarily select anything within the range.

Subsequently, (C) polyamide resin used in the present invention (hereinafter ((
C) Component. ), various materials can be used, specifically nylon 6, nylon 11. Polylactams such as nylon 12; nylon 66, nylon 6
10. Boria compounds obtained from dicarboxylic acids such as nylon 612 and nylon 46 and cyanogen; nylon 6/6
6. Nylon 6/I 2. Copolymer polyamides such as nylon 6/66/610; nylon 6/6T (T: terephthalic acid component), polyesters obtained from aromatic dicarboxylic acids such as isophthalic acid and metaxylene diamine or alicyclic cyanogens; Aromatic polyamides; mention may be made of polyesteramides, polyetheramides and polyesteretheramides.

As the polyamide resin of component (C), the various boria-based resins mentioned above may be used alone, or two or more types of polyamides may be used in combination.

Furthermore, the polyamide resin of the component (C) 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 polyamides described in (-) above. High acrylic acid-terminated polyesters are particularly preferred, although those with high acrylic acid terminals can be used. It is also possible to use a polyamide containing a large number of low molecular weight substances such as monomers and oligomers that remain or are produced during the polymerization of the polyamide.

Furthermore, in the present invention, (D) an inorganic filler and/or a fibrous reinforcing material (hereinafter referred to as (D) component) is used. That is, as component (D), one or both of an inorganic filler and a fibrous reinforcing material is used.

Here, as the inorganic filler, for example, iron oxide.

Alumina, magnesium oxide, calcium oxide.

Oxides such as zinc white, hydrated metal oxides such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate, calcium carbonate, magnesium carbonate Such as carbonate, talc, clay, hentonite, etc.
Silicates such as attapulgite etc., borates such as barium borate, zinc borate etc., phosphates such as aluminum phosphate, sodium tripolyphosphate etc., sulfates or sulfites such as gypsum etc. can be mentioned.

Examples of the fibrous reinforcing material include glass fiber potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wollastonite, carbon fiber aramid fiber, metal carbide fiber, and ultra-high elastic polyethylene fiber. . Other items include glass peas and glass balloons.

Spherical objects such as glass balloons, glass powder, glass flakes, mica, etc. can be used.

The type of these inorganic fillers or fibrous reinforcing phases can be selected as appropriate depending on the purpose. When using a mixture of various inorganic fillers and fibrous reinforcing materials, multiple inorganic fillers may be used. There are various cases in which a plurality of fibrous reinforcing materials are used.

In the composition of the present invention, various components as described above can be used as components (A) to (D), but among these,
Between component (A) and component (C), the melt viscosity of component (A) at molding temperature and shear rate of 100 sec-' is 77 + = r (poise), and the melt viscosity of component (C) is ηra (poise). It is necessary to select a combination of items whose ratio does not satisfy formula (1) % formula %. If the value of ηPP/ηPA is less than 1, the polygon resin will form a dispersed phase, making it impossible to impart the desired heat-resistant rigidity to the resulting resin composition, which is not preferable. The term "molding temperature" as used herein refers to the temperature at which various molded products are produced by molding the composition of the present invention, and is generally in the range of 180 to 350°C.

In the present invention, the blending ratio of the three components (A), (B), and (C) is 94 to 50% by weight of component (A), preferably 90 to 55% by weight of component (B), and 1 to 40% by weight of component (B). %, preferably 3 to 30% by weight, component (C) 5 to 40% by weight,
Preferably it is 10 to 40% by weight.

Here, if the blending ratio of component (A) is less than 50% by weight,
The resulting resin does not have the characteristics inherent to acidic polypropylene resins, and if it is blended in an amount exceeding 94% by weight, no improvement in heat resistance stiffness can be obtained, which is undesirable. In addition, if the blending ratio of component (B) is less than 1% by weight, (A)
It is insufficient to improve the compatibility between the component and component (C), and even if it is blended in an amount exceeding 40% by weight, the effect corresponding to the blending ratio is small, and rather the other two components of the resulting resin composition are This results in deterioration of various physical properties. Furthermore, if the blending ratio of component (C) is less than 5% by weight, the effect of improving heat resistance stiffness is insufficient, and if the blending ratio exceeds 40% by weight, (A)X
This is not preferable because the blending ratio of the polypropylene resin decreases and the original properties of the polypropylene resin are lost.

In addition, the blending ratio of component (D) added as a reinforcing material is the total of the three components (A), (B), and (C) mentioned above.
1 to 200 parts by weight, preferably 5 to 1 parts by weight
It is 80 parts by weight. Here, if component (D) is less than 1 part by weight, the desired heat resistance rigidity cannot be sufficiently improved, and even if it exceeds 200 parts by weight, the effect corresponding to the amount blended is small, and rather the resulting resin composition There is a risk that various physical properties of objects may be deteriorated.

The resin composition of the present invention has the above-mentioned four components (AL (B), (C), and (D) as main components, but if necessary, other additives may be added within a range that does not impede the properties of the above components. The additives that can be added here include: dye, pigment, nucleating agent, plasticizer, lubricant, mold release agent, coupling agent, blowing agent, heat resistant agent, weathering agent, flame retardant, antistatic agent. agent, sliding agent, etc.

The resin composition of the present invention is a resin composition formed by blending the above four components and additives added as necessary in predetermined amounts. There is no particular restriction on the order of blending, and each component may be blended sequentially or simultaneously. Further, components (B), (C) and ('D) may be blended with component (A) in powder or pellet form after the polymerization reaction is completed.

The resin composition of the present invention is prepared by mixing or kneading each component in the above-mentioned proportions, and a conventionally known melt-kneading method is preferred. Mixing is carried out using a Banbury i-kizer, a Henschel mixer, etc., and a single-screw or twin-screw extruder is generally used as the kneader. The temperature during melt-kneading may be appropriately selected depending on the components, blending amounts, etc., at a temperature at which the melting of each component progresses sufficiently and does not decompose. It is usually selected in the range of 180 to 350°C, preferably 200 to 300°C.

The obtained resin composition may be molded into any desired shape by extrusion molding, compression molding, injection molding, etc. to produce desired resin products such as pipes and tubes. Furthermore, it is possible to perform further processing such as polishing and painting.

〔Example〕

Next, the present invention will be explained in more detail based on Examples and Comparative Examples.

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

Test MBU' was prepared by molding the composition using a screw-in-line molding machine. The cylinder temperature at this time is (
C) The temperature was 280°C regardless of the type of polyamide resin.

Moreover, the mold temperature was 80°C.

Based on ASTM-D-648, bending stress 1B, 6k
The heat distortion temperature was measured at gf/c+Il.

5. Temperature set at 280° using a cavilograph made by Toyo Seiki.
The melt viscosity (ηPP) of the polypropylene resin and the melt viscosity (ηPA) of the polyamide resin at a C2 shear rate of 1005 ec-' were measured.

Examples 1 to 12 and Comparative Examples 1 to 4 Predetermined amounts of pellets of each of polypropylene resin, modified polyolefin, and polyamide resin shown in Table 1 were blended, and after dry mixing for 5 minutes with a Henschel mixer, The resulting mixture was melt-kneaded in a co-directional twin-screw extruder equipped with a hent (inner diameter 30 mm, L/D=17) to produce pellets.

In addition, the reinforcing material (D) component is used to suppress destruction.
I put it in from the extruder Hentro. Moreover, the heating temperature at the time of making this pellet was 280°C.

The obtained pellets were heated and dried under reduced pressure, and then made into test pieces using an injection molding machine, and the heat distortion temperature was measured. The results are shown in Table 1. In addition, this Table 1 shows 280°C3
The melt viscosity ratio (η2./ηPA) of the polypropylene resin and polyamide resin at a shear rate of 100 sec-' is also shown. In addition, the blending ratio of each component in Table 1 is (AL) (For components B) and (C), the breakdown of these three components is shown in weight percent, and for component (D), the above (A) and (B) as well as(
The ratio is shown in parts by weight based on the total of 100 parts by weight of component C).

(Left below) 18 *1: Propylene homopolymer, JIS K 675
Propylene homopolymer with MFR at 8 of 0.5 g/10 min *2: Propylene homopolymer, JIS K G75
Propylene homopolymer with MFR at El of 38/I 0 minutes *3: Brobylene block copolymer, JIS K
Propylene block copolymer with MFR of 0.8 g/10 min at 6758 *4: Propylene homopolymer, JIS K 675
Propylene homopolymer with MFR at B of 30 g/10 min *5: Brobylene block copolymer, JIS K
Propylene block copolymer with MFR of 30 g/I 0 min at 6758 *6: Graft modified polypropylene, MF of 230”C
Graft-modified polypropylene obtained by adding 0.35% by weight of maleic anhydride to tactical polypropylene having R of 1.0 g/10 minutes *7: Glycidyl methacrylate grafted ethylene-
Vinyl acetate copolymer was produced with reference to the method described in Japanese Patent Publication No. 5512449. That is, glycidyl meccrylate in which dicumyl peroxide had been dissolved in advance was mixed with ethylene-vinyl acetate copolymer pellets and allowed to penetrate at room temperature. Next, the glycidyl methacrylate-impregnated pellets were extruded at a tip temperature of 170°C using a co-directional twin-screw extruder with an inner diameter of 30 mm and a hent, to obtain graft-polymerized epoxy group-containing copolymer pellets (glycidyl methacrylate content: 2wt%).

*8: Nylon 66. Relative viscosity: 2.85.7 Mino terminal group degree: 5.2X10-5 equivalent/g*9: Nylon 66.
Relative viscosity 2.30. Amino end group concentration 5. lX10-
'Equivalent weight/g*10: Nylon 6. Relative viscosity 2.5' 2
, amino end group concentration 4.9X10-5 equivalent/g *11: Chop toss 1 with length 3+nm and diameter 10μm
-Rand fibers whose surface has been treated with a silane camping agent It is possible to manufacture various reinforced polypropylene resin compositions that have both the excellent properties of can be obtained.

Therefore, the reinforced polypropylene resin composition of the present invention is
It is suitable for applications that require heat-resistant rigidity, such as automobile parts (exterior 5 outer panels, etc.), electrical equipment mechanical parts, industrial parts, etc.

1

Claims (1)

[Claims] (1) (A) Polypropylene resin 94-50% by weight, (
1 to 100 parts by weight of a mixture consisting of B) 1 to 40% by weight of modified polyolefin and 5 to 40% by weight of (C) polyamide resin, 1 part by weight of (D) inorganic filler and/or fibrous reinforcing material.
~200 parts by weight, and the melt viscosity η_P_P (poise) of the polypropylene resin (A) and the melt viscosity η_P_A (poise) of the polyamide resin (C) at a molding temperature and a shear rate of 100 sec^-^1.
A reinforced polypropylene resin composition characterized in that the ratio e) satisfies the formula [I] η_P_P/η_P_A>1...[I].