JPS59105042A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent mar resistance, comprising propylene homopolymer, a modified polyolefin and three specified kinds of inorg. fillers. CONSTITUTION:2-100pts.wt. wollastonite (A) having an aspect ratio of 2-30 and a particle size of 0.5-30mu, 1-50pts.wt. milled glass fiber (B) having an aspect ratio of 2-30 and a length of 30-300mu and 2-100pts.wt. mica (C) having an aspect ratio of 10-100 and a particle size of 1-100mu are bleaned with 100pts.wt. resin component consisting of 50-98wt% propylene homopolymer having an MFI of 1-100g/10min and 50-2wt% modified polyolefin [having an acid (anhydride) content of pref. 0.01-10wt%] obtd. by modifying a polyolefin with an unsaturated carboxylic acid (anhydride) in such a proportion that the combined quantity of components A, B and C is 5-250pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The object of the invention relates to leno-based polymer compositions. Further details include hepropylene homopolymer and zero-modified polyolefin.

0 wollastonite%0 milled glass fiber and D
The present invention relates to a propylene-based polymer composition comprising mica, and aims to provide a scratch-resistant and ready-to-wear composition.

■ Background of the Invention Olefin polymers have excellent mechanical properties, thermal properties (e.g. side heating properties), chemical properties (e.g. chemical resistance), electrical properties, etc., and are easy to process and are inexpensive heat sources. Since it is a plastic resin, it is widely produced industrially and used in many fields. Furthermore, various inorganic fillers are blended with olefin polymers, which are widely used in automobile parts, electrical equipment parts, and the like. However, molded products of olefin polymers or olefin polymers blended with inorganic fillers are not used in many fields because their surfaces are easily damaged. Furthermore, at present, the surface is painted for aesthetic reasons. In view of the above, there has been a demand for a composition containing an olefin polymer, resin, or filler that has excellent scratch resistance on the surface of a molded article.

However, polymers or compositions with excellent scratch resistance have not yet been developed. That is, ultra-high molecular weight ethylene polymers have excellent wear resistance, but do not have sufficient scratch resistance. In addition, a composition with good wear resistance has been proposed by blending a special filler with an olefin polymer75; however, the scratch resistance is not always satisfactory.

o]11 Structure of the Invention Based on the above, the present inventors have conducted various searches to obtain an olefin polymer or a composition thereof that has excellent scratch resistance. JISK-6758
[L'i'n75Ei, temperature is 230℃ and load is 2
．． A propylene homopolymer whose MFIj (hereinafter referred to as MFIj) is 1.0 to 1019710 minutes when measured at 16 Kg, 0 A modified polyolefin obtained by modifying a polyolefin with an unsaturated carboxylic acid and/or its anhydride. , Ω Y lastite has an aspect ratio (average diameter/average thickness) of 2 to 300 and a diameter of 0.5 to 30 microns, D has an aspect ratio of 2 to 30 and a length of 30
A composition consisting of milled glass fibers having a diameter of ~300 microns and mica having an average particle size of 1 to 100 microns and an aspect ratio of 10 to 100, the total amount of the propylene homopolymer and modified polyolefin. The proportion of propylene homopolymer in the mixture is 5.
The blending ratio of wollastonite is 2 to 100 parts by weight, and the blending ratio of milled glass fiber is 1 to 50 parts by weight, based on 100 parts by weight of the total amount of propylene homopolymer and modified polyolefin. Yes, and the blending ratio of mica is 2 to 100 parts by weight, but the total amount of propylene fluorescent polymer and modified polyolefin is 10 parts by weight.
The present invention has been achieved based on the discovery that a propylene-based polymer composition in which the total amount of wollastonite, milled glass fiber, and mica is 5 to 250 parts by weight based on 0 parts by weight is a composition with excellent scratch resistance. .

1. Effects of the Invention When the propylene polymer composition obtained by the present invention is molded, the following effects are exhibited.

(1) Since the surface of the molded product has excellent scratch resistance, it can be used without surface protection such as painting.

(2) Good weld strength and inconspicuous weld lines improve the appearance of the molded product surface.
It also has good impact resistance against drops.

(3) Not only does the surface have excellent smoothness, but the molded product does not warp or sink.

(4) It not only has high rigidity but also excellent heat resistance and creep resistance.

(5) There is extremely little wear on the screws, nozzles, etc. of the molding equipment.

Since the composition of the present invention exhibits the above-mentioned effects, it can be used in a wide variety of fields.

Typical examples of uses include parts for various automobiles (including motorcycles), household appliances, furniture, and miscellaneous goods for daily use.

M Detailed Description of the Invention Propylene Homopolymer The propylene homopolymer used in the present invention is prepared by supporting propylene alone on a transition metal compound (e.g., a titanium compound) or a carrier (e.g., a magnesium compound, a treated product thereof). Transition metal compounds and organometallic compounds (
For example, it can be obtained by polymerization in the presence of a catalyst system (so-called Ziegler catalyst) obtained from organic aluminum compounds. M of this propylene homopolymer
, FI is 1.0-10i/10min, 30-80g
/10 minutes is desirable, especially 5.0~60,! 9/
10 minutes is preferred. MFI is 1.0! If a propyleno homopolymer with less than J/10 minutes is used, the moldability of the resulting composition is poor. On the other hand, if a propylene homopolymer with a ratio exceeding 101'/10 minutes is used, moldability is good, but mechanical properties (particularly impact resistance) are deteriorated.

0 Modified polyolefin The modified polyolefin of the present invention 1) The polyolefin used to produce the olefin includes an ethylene homopolymer, a propylene homopolymer, a copolymer of ethylene and propylene, a copolymer of ethylene and/or propylene, and a copolymer of ethylene and/or propylene. Copolymer with other α-olefin having at most 12 carbon atoms (copolymerization ratio of α-olefin is at most 20M)
can be given. The molecular weight of these olefin polymers is generally from 20,000 to 1,000,000, preferably from 20,000 to 500,000, and particularly preferably from 50,000 to 300,000. Low-density and high-density ethylene homopolymers, propylene homopolymers, copolymers of ethylene and propylene, ethylene, propylene, and other α
- Copolymers with olefins are preferred.

These olefinic polymers can be obtained by using a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminium compound, or by supporting a chromium compound (for example, chromium oxide) on a carrier (for example, silica). They are obtained by homopolymerization or copolymerization of olefins using catalytic systems (so-called Phillips catalysts) or radical initiators (eg organic peroxides).

The modified polyolefin used in the present invention can be obtained by modifying the above polyolefin with an unsaturated carboxylic acid or a derivative thereof.

Representative examples of unsaturated carboxylic acids or their derivatives include:
monobasic carbonic acids having at most 10 carbon atoms and at least one double bond (*, e.g. acrylic acid, methacrylic acid) and at most 15 carbon atoms and having at least one double bond; Examples include dibasic carboxylic acids having a double bond (eg, maleic acid) and anhydrides of the dibasic carboxylic acids (eg, maleic anhydride, himic anhydride). Among these unsaturated carboxylic acids or derivatives thereof, maleic acid and maleic anhydride are especially preferred.

Modified polyolefins are generally obtained by treating polyolefins with unsaturation/L-bonic acids and/or derivatives thereof in the presence of organic peroxides.

In order to produce the modified polyolefin of the present invention, various known methods (eg, solution method, suspension method, melting method) can be employed.

Among the methods for producing Kowara, when polyolefin is modified with an unsaturated carboxylic acid and/or its derivative by a solution method, the polyolefin and the unsaturated carboxylic acid and/or its derivative are placed in a nonpolar organic solvent. A modified polyolefin can be obtained by further adding a radical initiator and heating at a high temperature. Examples of inorganic organic solvents used in this case include hexa/, hepta/, benzene, toluene, xyleph, chlorobenzene, and tetrachloroethane. 1, as a radical initiator, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexano, 2,5-dimethyl-
Organic peroxides such as 5,5-di(tertiary butylperoxy)hexino-3 and benzoyl peroxide may be mentioned. Furthermore, the processing temperature is the temperature at which the polyolefin used dissolves! ll1% generally 110~
The temperature is 160°C, particularly preferably 130 to 150°C.

When a polyolefin is modified with an unsaturated carboxylic acid or its derivative by the suspension method, the polyolefin and the unsaturated carboxylic acid and/or its derivative are added to a polar solvent (generally water), and then the above radical is added. It is obtained by adding an initiator and processing under high pressure at a temperature of 100° C. or higher.

When modifying polyolefin with an unsaturated carboxylic acid or its derivative by the melt method, a melt kneader used in the field of general synthetic resins (for example,
It can be obtained by melt-kneading polyolefin, an unsaturated carboxylic acid and/or a derivative thereof, and the radical generator described above using an extruder. The kneading temperature at this time varies depending on the type of polyolefin and radical generator used, but is in the temperature range from above the melting point of the polyolefin used to below 300°C. In the case of polyethylene, generally 12
0 to 270°C, and in the case of polypropylene, generally 160 to 270°C.

The total content of unsaturated carboxylic acids and derivatives thereof grafted into the modified polyolefin obtained as described above is 0.01 to 10% by weight, and 0.05 to 5% by weight.
．． A weight ratio of 0 is desirable, and a weight ratio of 01 to 50 is preferred. If the content of these grafted into the modified polyolefin is less than 0.01% by weight, almost no crosslinking reaction occurs.

Moreover, if the weight ratio exceeds 10, the moldability of the crosslinked product will be significantly impaired.

Ω Wollastonite Also, the wollastonite used in the present invention is a naturally occurring white needle-shaped mineral, and is calcium metasilicate, also called quartz gray, and has a structural formula of CaO-5in.
It is represented by 2. The average particle size is 0.5 to 30 microns, preferably 1 to 30 microns, and particularly 3 to 20 microns. When a composition is made using lastonite with an average diameter of less than 0.5 microns, the stiffness of the resulting composition is low (,
On the other hand, if a molded article is manufactured using a material having a diameter exceeding 30 microns, the appearance of the surface of the molded article will be unfavorable. Further, the average aspect ratio is 2 to 30, preferably 2 to 25, and preferably 3 to 20 by 9. If wollastonite with an aspect ratio of less than 2 is used, the stiffness of the composition will be reduced. On the other hand, if a molded product is manufactured using a material with a particle size exceeding 30, the appearance of the surface of the molded product will be poor, which is also not preferable in the case of a chair.

D. Milled Glass Fiber Furthermore, the milled glass fiber used in the present invention is obtained by crushing or grinding glass fiber. The average length is 30 to 300 microns, preferably 50 to 200 microns, particularly 50 to 150 microns. If the composition is made using milled glass fibers having an average length of less than 30 microns, the resulting composition will have low stiffness.

On the other hand, if a molded article is manufactured using a material with a diameter exceeding 300 microns, the appearance of the surface of the resulting molded article will be deteriorated, which is not desirable in either case. Further, the aspect ratio is 2 to 30, preferably 2 to 25, and preferably 3 to 20. If glass fiber is used in a mill with an aspect ratio of less than 2, the resulting composition will still have low stiffness. On the other hand, if molding is performed using a material with a molecular weight exceeding 30, the surface appearance of the resulting molded product will deteriorate, which is undesirable in either case.

D. Mica The mica used in the present invention is a naturally occurring platy mineral, and although its composition is complex, it is mainly composed of muscovite, phlogopite, and biotite. The average particle diameter is 1 to 100 microns, preferably 1 to 50 microns, and particularly preferably 2 to 50 microns.

If the composition is made using mica with a particle size less than 1 micron, the scratch resistance and stiffness of the assembly will be reduced. on the other hand,
If a molded product is manufactured using mica with a diameter exceeding 100 microns, the mica in the resulting molded product will quickly peel off.
Moreover, the weld line is noticeable, and in either case, it is not good. Furthermore, the aspect ratio is between 10 and 100, and 1
0 to 7o is preferable, and 9 to 20 to 7o is preferable.

If the composition is made using mica with an aspect ratio of less than 10, the scratch resistance and stiffness of the resulting composition will be reduced. On the other hand, if molding is performed using a material with a molecular weight exceeding 100, the mica in the resulting molded product will likely peel off.
In addition, weld lines are noticeable, which is not preferable in either case.

[F] Compositional ratio In producing the composition of the present invention, the compositional ratio of the propylene homopolymer in the total (total amount) of the propylene homopolymer and modified polyolefin is 50 to 980.
98 parts by weight 60-950-95 parts by weight, especially 70-9
30-93 parts by weight Al. If molding is performed using a diaphragm in which the proportion of prophylactic and German M combinations in the total amount of Kowara is less than 50% by weight, flow marks will be generated on the surface of the molded product and the appearance will deteriorate. At the same time, it is a problem in terms of cost. On the other hand, if the weight ratio exceeds 98, the rigidity and heat resistance of the composition will decrease, and the mica on the surface of the molded product will peel off, which is undesirable in either case. Furthermore, the content of the unsaturated carboxylic acid and its anhydride used in the production of the modified polyolefin in the total of the propylene homopolymer and the modified polyolefin is 0.01 to 201 to 201 as the total amount thereof.
20 parts by weight (preferably 0.1 to 5.0 parts by weight). If the content of unsaturated carvone and its anhydride in the total amount is less than 0.01% by weight, not only the rigidity and heat resistance of the resulting composition will decrease, but also the mica on the surface of the molded product will peel off. It is more likely to occur. On the other hand, if a composition exceeding 20% by weight is molded, flow marks are likely to occur on the surface of the molded product, which impairs its appearance.

Further, the blending ratio of wollastonite to 100 parts by weight of the total amount of propylene homopolymer and modified polyolefin is 2 to 100 parts by weight, preferably 2 to 70 parts by weight,
Particularly suitable is 5 to 70 parts by weight. Synthesis of propylene homopolymer and modified polyolefin il'ffl i 0
The blending ratio of wollastonite to 0 nfit part is 2
If the amount of the composition is less than 1 part by weight, the weld strength is poor, and even if the blending ratio of mica is reduced, the weld lines of the resulting molded product will be noticeable and the appearance will not be good. On the other hand, if a composition exceeding 100 parts by weight is molded, the resulting molded product will warp, which is undesirable in either case. Furthermore, the blending ratio of milled glass fiber to 100 parts by weight of the total amount of propylene homopolymer and modified polyolefin is 1 to 50 parts by weight, preferably 2 to 50 parts by weight, and particularly preferably 3 to 4 parts by weight. be. Probile/Total amount of homopolymer and modified poly No. 1 Nophin: 10
If a composition containing less than 1 part by weight of milled glass fiber is blended with respect to 0 parts by weight, the surface of the molded product will be easily damaged. On the other hand, if more than 50 parts by weight of the composition is used, not only will it cause problems in terms of cost, but also when manufacturing by kneading the composition and manufacturing molded products using the composition. This wears out the screws and cylinders of mixers and molding machines, which is undesirable in either case. In addition, the blending ratio of mica is 2 to 100 parts by weight, preferably 2 to 70 parts by weight, with respect to 100 parts by weight of the total amount of Proville/homopolymer and modified polyolefin.
Particularly suitable is 5 to 70 parts by weight. In a composition in which the blending ratio of mica is less than 2 parts by weight with respect to 100 parts by weight of the total amount of the homopolymer/modified polyolefin, the rigidity, heat resistance, and scratch resistance of the composition decrease. On the other hand, 5
If more than 0 parts by weight of the composition is molded, weld lines on the surface of the molded product will be noticeable and the weld strength will not only decrease, but also flow marks will occur on the surface of the molded product, resulting in poor appearance. Either case is unfavorable.Furthermore,
The total amount of wollastonite, milled glass fiber, and mica is 5 to 250 parts by weight, preferably 5 to 150 parts by weight, with respect to 100 parts by weight of the combined amount of polyolefin alone and modified polyolefin. 20~
150 parts by weight is preferred.

0 Production of composition, molding method, etc. To produce the composition of the present invention, the purpose is achieved by uniformly mixing the propylene homopolymer, modified polyolefin, wollastonite, milled glass fiber, and mica. I can do it. The mixing method is to mix propylene homopolymer and modified polyolefin in a bath molten state using mixers commonly used in the field of olefin polymers, such as extruders, mixing rolls, kneaders, roll mills, vanovary mixers, and continuous mixers. There is a method of kneading the processed material by using one type of stiff mixer in advance, and then mixing the resulting mixture using the same type of mixer or another type of mixer to make the processed material more uniform. can obtain a composition. In addition, before carrying out these mixing processes, the processed material is triblended in advance using a mixer such as a drum tumbler or a henoshell mixer, and the resulting mixture is further melt-kneaded to make the treated product more uniform. can get things. Furthermore, some of the mixed components (composition components) of Kowara are mixed by force and tightening to produce a so-called master patch, and the resulting masterbatch (mixture)
and the remaining mixed components (for example, by mixing part or all of the modified polyolefin, wollastonite, milled glass fin, and mica, and mixing the resulting mixture with the propylene homopolymer). or a method of mixing propyleno homopolymer with the remaining wollastonite, milled glass fiber and mica).

The propylene polymer composition obtained in this way may be used after being crushed, but depending on the purpose of use, oxygen, light (ultraviolet rays) and Heat stabilizer, flame retardant,
The above characteristics (effects) that the propylene polymer composition of the present invention has additives such as lubricants, processability improvers, fillers, colorants, antistatic agents, electrical property improvers, and adhesion improvers. It may be added as long as it does not cause any damage.

Furthermore, for the same reason as above, synthetic resins and/or
Alternatively, rubber may be blended, but the blending ratio of sora is at most 40 parts by weight per 100 parts by weight of the propylene homopolymer and modified polyolefin.

The thus obtained i+ propylene polymer composition or its blend (additive) can be processed by processing methods commonly used in the field of olefin polymers such as extrusion molding, blow molding, and injection molding. film form,
It is molded into sheet-like, container-like, and other shapes and is used in a wide variety of applications.

The kneading temperature at which the mixture is melt mixed and the molding temperature at which a molded article is manufactured by this processing method are both at or above the softening point of the propylene homopolymer and modified polyolefin, which are the mixed components. It is. However, if these are carried out at high temperatures,
Propylene homopolymers and modified mixtures undergo thermal degradation. For these reasons, these temperatures are usually 180~
The temperature is 250°C.

(2) Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, tart index C or less r M , 1. ) is JISK-67
According to 60, the temperature is 230℃ and the load is 2.16
Measured under K9 conditions. Further, yield strength and weld strength (using a dumbbell obtained by molding an ASTM No. 1 dumbbell so that a weld surface exists in the center) were measured according to ASTM D-638. Furthermore, the flexural modulus was measured according to ASTM D-790. Also.

Izod impact strength is AS'I"MD25
6 with a notch, and heat resistance was evaluated by measuring heat distortion temperature in accordance with ASTM D-648. Furthermore, the pencil hardness is according to JISK-5401, with the load being IK9 and the measurement mark being 100 in height.
A molded article was manufactured in which a flat part of a box-autumn article with a width of 200 mm, a height of 60 mm, and a wall thickness of 3 groups, and a hole of 50 mm x 30 mm were bored on both sides of a direct gate with a diameter of 5 mm. This molded product was evaluated by observing it with the naked eye. Furthermore, regarding warping, we evaluated the shape by forming a circle with a thickness of 2.3 mm and a diameter of 125 mm @ a center gate with a diameter of 1 mm, and measuring the maximum deformation part. Using an extruder (diameter 20 mm) with a dullage type screw, the wear of the dullage portion was evaluated after extrusion was carried out for 7 hours. Furthermore, the peeling of mica was evaluated by closely adhering cellophane tape to an injection molded test piece and rapidly peeling off the cellophane tape.

In the Examples and Comparative Examples, the propylene homopolymer, modified polyolefin/wollastonite, and milled glass f-bar mica manufactured by the following physical properties and manufacturing method were used.

[■ Propylene homopolymer]

As a propylene monopolymer, MF-'I Chikaradama 15g/
Propyleno homopolymer [hereinafter referred to as rPP (6)]
A propyl horn homopolymer [hereinafter referred to as rPP(B)1] with an MFI force of 30 g/l 0 minutes was used.

[0 modified polyolefin/] As the modified polyolefin, a propylene homopolymer with an MFI of 09 g/10 min (distillation degree 090 CNj/c
ttl) 100 parts by weight, 0.01 parts by weight of 2,5-dimethyl-2,5-di(butyl)-oxy)hexane (
(as an organic peroxide) and maleic anhydride in advance for 5 minutes using a shell mixer, and the resulting mixture was melt-kneaded using an extruder at a resin temperature of 230°C to form a modified polyolefin. / (hereinafter referred to as "modified PPJ") was produced and used. The content of maleic anhydride in the modified polyolefin was 0.075% by weight.

[Ω Wollastonite]

As wollastonite, the average particle size is 4 microns.
Wollastonite having an aspect ratio of 5 was used.

[0 Milled Glass Fiber] As the milled glass fiber, milled glass fiber (hereinafter referred to as rMGFJ) having an average particle diameter of 80 microns and an aspect ratio of 7.5 was used.

[■ Mica]

Furthermore, as mica, the average particle size is 7 microns,
Mica with an aspect ratio of 30 was used. .

Examples 1 to 5, Comparative Examples 1 to 9 PP Hachihetake PP ([31, Modified PP, Warastona, M, G, F, and mica are shown in Table 1 for famous confectionery in their respective blending amounts (all parts by weight) ) and triblended for 2 minutes each using a Henon El mixer to produce mixtures. Each of the resulting mixtures was mixed at a resin temperature of 230°C using a vented twin-screw extruder (diameter: 30 mm). Pellets were produced while kneading. Samples for measuring physical properties were produced using an injection molding machine (resin temperature: 230° C.) from each of the pellets, and each physical property was measured.

The results of Sonera are shown in Table 2.

From the results of the above Examples and Comparative Examples, it is clear that the molded product of the propylene polymer composition obtained by the present invention is 1ii
Not only does it have excellent scratch resistance, but the weld marks and flow marks on the first surface do not cause warping or deformation, and the lft molding stability is good, and it also has high heat resistance and rigidity. What is shown is clear. Therefore, the composition of the present invention can be applied to various automobile parts (not including motorcycle parts, for example, meter cases,
It can be used without painting on panel panel-related noise IS products), home appliance parts (e.g., housings for electric fans, speaker boxes, etc.), and daily miscellaneous goods (e.g., furniture, various cases, etc.). it is obvious.

Patent applicant: Showa Denko Co., Ltd. Agent: Patent attorney Sei Kikuchi

Claims (1)

[Claims] (2) Melt flow index is 1.0 to 100g
(1) A modified polyolefin obtained by modifying a polyolefin with an unsaturated carboxylic acid and/or its anhydride, (Ω) an aspect ratio of 2 to 30, and a diameter of 0.710 minutes.
wollastonite having an aspect ratio of 5 to 30 microns, milled glass fibers having an aspect ratio of 2 to 30 and a length of 30 to 300 microns, and υ having an average particle size of 1 to 100 microns and an aspect ratio of is a composition having a buoyancy force of 10 to 100, and the proportion of the propylene homopolymer in the total amount of the propylene homopolymer and modified polyolefin is 5.
The blending ratio of wollastonite is 2 to 100 parts by weight, and the blending ratio of milled glass fiber is 1 to 50 parts by weight, based on 100 parts by weight of the total amount of propylene homopolymer and modified polyolefin. Yes, and the blending ratio of mica is 2 to 100 parts by weight, but the total amount of propylene homopolymer and modified polyolefin is 10 parts by weight.
A propylene polymer composition in which the total amount of wollastonite, milled glass fiber, and mica is 5 to 250 parts by weight based on 0 parts by weight.