JPS581738A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To provide a glass-filled polyolefin compsn. having high tensile strength and flexural strength, and suitable as automobile parts, by blending a specified modified polypropylene and glass with a polyolefin. CONSTITUTION:100pts.wt. polypropylene, 0.05-20pts.wt. unsaturated carboxylic acid such as maleic anhydride or acrylic acid, 0.01-5pts.wt. org. peroxide such as benzoyl peroxide or lauroyl peroxide, and pref. further a rubbery material such as 1,2-polybutadiene are melt-kneaded together. The mixture is heat-treated to prepare a modified polypropylene. 0.5-40pts.wt. said polypropylene and 3- 40wt% (based on the total amount of compsn.) glass are blended with 100pts.wt. polyolefin such as polypropylene to obtain the desired glass-filled polyolefin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to glass-containing polyolefin compositions having high tensile (breaking) strength and sliver strength.

In recent years, demands for high rigidity and high tensile strength have been increasing in the application of polyolefins to automobile parts, electrical products, *materials, and various industrial products.

Therefore, glass, especially glass fines, is filled with polyolefin to achieve this purpose.

There are many things. However, in general, when polyolefin is simply filled with glass fibers, the flexural modulus increases, but the flexural strength and tensile (breaking) strength hardly increase.

Therefore, polyolefins modified with maleic acid, acrylic alcohol, coolsulfone alcohol, etc. are used in combination as modifiers to increase the tensile strength and bending strength. However, in order to increase the tensile strength and flexural strength of such modified polyolefins, not only is it necessary to add a large amount of the modified polyolefin, but also the flexural modulus tends to decrease as the amount of the modifier increases. That is, if an attempt is made to increase the tensile strength and flexural strength of a glass-containing polyolefin composition, the flexural modulus will conversely decrease.

As a result of intensive research to solve this drawback, the present inventors have developed a modified polypropylene composition obtained by melting and mixing a mixture of polypropylene, unsaturated carboxylic acids, and organic peroxides and then heat-treating the mixture. If used in combination with glass fiber as a modifier and used to fill polyolefin, high tensile strength and bending strength can be obtained with a small amount of modified filling, and surprisingly, when the amount of filling is increased, the bending modulus remains the same. They have discovered that, unlike modified materials, they actually increase, and have completed the present invention.

That is, according to the present invention, modified polypropylene (B) and glass (C) obtained by melting and mixing polyolefin (A), polypropylene, unsaturated carboxylic acids, and organic peroxide, and then heat-treating the mixture are blended. A polyolefin composition is provided.

The polyolefin (A) used in the present invention is a single heavy metal body of α-olefin such as ethylene, propylene, and zuthene (butylene).

Examples include copolymers of the α-olefin and other α-olefins, aromatic olefins, copolymerizable monomers such as dienes, and mixtures thereof. In particular, polyolefins containing polypropylene as a main component are preferably used. (
・Can be done.

As the polypropylene constituting the modified polypropylene (B), homopolypropylene which is a homopolymer of propylene, and copolymers such as random and block copolymers of ethylene, butylene, etc. and propylene are used.

Examples of unsaturated carboxylic acids include acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, itaconic acid, citrafuran, etc., and derivatives of unsaturated carboxylic acid such as silane anhydride, ester, amide, isodium, metal salts, etc., such as anhydrous maleic acid, anhydrous Citracon w, m water itacone, methyl acrylate.

Butyl methacrylate, methyl acrylate, ethyl methacrylate, methyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate.

Fumaric acid dimethyl ester, fumaric acid dimethyl ester, itafunic acid monomethyl ester, itamonosun diethyl ester, acryl 7mide, methacryl 7mide, maleic acid mono7mide, maleic acid doumareic acid N-monoethylamide, Maleic acid 11-N, N→diethyl 7Z-do, maleic acid-N-7-butylamide, maleic acid-N,N-dibutyl-7mide, fumaric acid monoamide, fumaric acid monoamide.

7malic acid-N-monoethyl 7mide, fumaric acid-N,N-
Diethyl 7mide, 7malic acid-N-motuptilamide, 7
Malic acid-N, N-dibutyl 7-mit, maleimide, N-butylmaleimide.

Examples include N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like. Among these, it is most preferable to use maleic anhydride.

In order to obtain modified polypropylene (B), unsaturated carboxylic acids are added to 100 parts by weight of polypropylene [generally 0 parts by weight].
．． It is necessary to add 0.05 to 20 parts by weight, preferably 0.1 to 5.0 parts by weight. The amount added is 0.05
If the amount is less than 20 parts by weight, the tensile strength and burr strength of the obtained polyolefin composition of the present invention will not be sufficient, and if it exceeds 20 parts by weight, the bow 1 tensile strength and burr strength will be saturated. On the contrary, the self-elastic modulus decreases.

Combined with the actual cost, this becomes a disadvantage.

Furthermore, in order to obtain the modified polypropylene composition (B),
Organic peroxides are used to promote the grafting reaction between polypropylene and unsaturated carboxylic acids. Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, 7zobisimpcinidolyl,
dicumylno(-oxide, α, α1-bis(t-butylperoxydiisobutyl)benzene 2,5-dimethyl-2,5-di(1-butylperoxy)hexane, 2
, 5-dimethyl-2,5-di(t-butyl/<-oxy)hexyne-3, dinot-t-butyl/<-oxide.

Examples include cumene hydroperoxide and t-butyl hydroperoxide. The amount of organic peroxide added is 0.01 to 5.0 parts by weight, preferably 0.02 to 30 parts by weight, per 100 parts by weight of polypyrene. If the amount added is less than 0.01 parts by weight, the grafting reaction amount of the unsaturated carboxylic acid or its derivative will not be sufficient, and if it exceeds 5.0 parts by weight, the MFI of the resulting polyolefin composition will be too large, making it difficult to mold. The disadvantage is that it becomes difficult.

In order to improve the tensile (breaking) strength and bending strength of the glass-containing polyolefin composition obtained in the present invention, 1. When obtaining the above-mentioned modified polypropylene (B),
It is preferable to further blend a rubbery substance. That is, such modified polypropylene (B) is polypropylene 100
parts by weight, 1 to 400 parts by weight of rubbery substance, 0.05 to 100 parts by weight of unsaturated carboxylic acids, and 0.0 parts by weight of organic peroxide.
01 to 10.0 parts by weight are melt-kneaded and then heat-treated. The rubber-like substance may be a solid rubber substance or a liquid rubber substance without any limitation in percentage, such as a low-density poly-11 ethylene:ethylene-p-pyrene random copolymer, ethylene-butene-1 random copolymer.

Ethylene-α- such as ethylene-propylene polymer
Olefin random copolymer; others 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene,
Polychloroprene, styrene-tadiene copolymer, acryonitrile-tadiene copolymer, etc. are used.

As mentioned above, the amount of the rubbery substance added is 1 to 400 parts by weight, preferably 1 to 100 parts by weight of polypropylene.
0 to 300 parts by weight is required, and if it exceeds 400 parts by weight, the tensile strength and bending strength of the polyolefin composition tend to decrease.

The production of modified polypropylene (B) involves polypropylene,
Unsaturated carboxylic acids and organic peroxyoxides, if required, add rubber-like substances and mix thoroughly in tumbler 1/shell mixer, etc., above the melting point of the wrinkled polyppyrene, generally above the melting point ~ The grafting reaction is carried out by melting and kneading at a temperature of 280'C or less. The method of melting and kneading is 1lI
Although tKFIk is not determined, it can be carried out using, for example, a screw extruder, a Banbury mixer, a mixing roll, or the like.

The temperature and time of melt cross-talk vary depending on the degree of decomposition of the organic peroxide used, but are generally 160 to 280°C and 0.5°C.
for 3 to 30 minutes, preferably at 170 to 250°C for 1 to 10 minutes.
minutes is appropriate. Note that the melt-kneading may be performed in an inert gas stream. Further, when melting is carried out using a screw extruder, unreacted upper material may be removed by venting.

However, the glass-containing polyolefin composition obtained by blending the modified polypropylene obtained by melt-kneading as described above is difficult to obtain. The l (breaking) strength and peeling strength are still insufficient.

However, in the present invention, a glass-containing polyolefin composition with improved tensile (breaking) strength and bending strength k is obtained by using modified polypropylene (B) obtained by further heating II & developing the above-mentioned melt-kneaded modified propylene. It is possible. The reason for this is not clear, but it is achieved by removing unreacted particles of unsaturated carboxylic acids from the modified polypropylene under sufficient pressure, particularly by heat treatment. That is, unreacted monomers of unsaturated carboxylic acids inevitably remain in the modified polypropylene obtained by melt-kneading, and therefore, these unreacted monomers cause tension (breakage) in the glass-containing polyolefin composition.
It is also presumed that this hinders the improvement of bending strength.

Heating of modified polypropylene is generally carried out at a temperature of 0°C or higher, preferably 100°C or higher and lower than the melting point, and the heat treatment can be carried out to reduce the amount of unreacted unsaturated carboxylic acids/acids to 0.1 mol% or less. preferable.

The modified polypropylene of the present invention is unmodified polypropylene,
For example, it has good compatibility with homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene bootsk copolymer, etc., so these materials can be mixed with appropriate fines for purposes such as cost reduction and rigidity. It can also be used as In addition, the modified polyp-pyrene composition (B) contains heat-resistant stabilizers, weather-resistant stabilizers, lubricants, anti-static agents, nucleating agents, fillers, S materials, dyes, flame retardants, slip It may also contain agents.

In the present invention, the amount of modified polypropylene (B) added is:
Generally 0.0% per 100 parts by weight of polyolefin (A).
It is 5 to 40 parts by weight, preferably 1.0 to 30 parts by weight. The amount of modified polypropylene/composition (B) added is 0.
If it is less than 5 parts by weight, the tensile strength and flexural strength of the final polyolefin composition will not be sufficiently increased, and conversely, if it exceeds 40 parts by weight, the tensile strength and flexural strength of the polyolefin composition will not increase sufficiently. Not only is there no increase, but the heat distortion temperature and heat deterioration resistance deteriorate, which is not preferable.

The glass used in the present invention has a particle size of 0.1
Commonly used materials are preferably used, such as powder or granular materials with a thickness of ~100μ, preferably 0.1-50μ, foil-like materials with a thickness of 0.1-20μ, and fibrous glass with a thickness of 1-50μ. can. Examples of fibrous glass include so-called glass p-ping, which is made by binding long fibers with a sizing agent, 11 Bingtsuros, which is made using glass roving for the warp and weft, and strands cut into appropriate lengths, such as P-ping. There are chopped strand mats made by randomly dispersing the rovings and bonding them with a binder, and chopped strands made by cutting glass roving into lengths of 0.5 to 10 mm, but chopped strands are particularly preferred. . In addition, chopped strands are made by bundling single fibers with various sizing agents to create a 0.
A rod-shaped product of 5 to 3 cm and a product treated with a 7-minosilane or acrylic acid-based camping agent are preferably used for 41 because they can be easily manufactured using an extruder.

The content of the glass is 3 to 40% by weight, preferably 5 to 35% by weight of the entire composition.

If the glass content is less than 3% by weight, the resulting polyolefin composition will have insufficient tensile strength and bending strength, while if it exceeds 40% by weight, the kneading process in an extruder will result in a solid phase, which is not desirable. do not have.

The method of obtaining the lyolefin composition of the present invention is not particularly limited, and the blending components consisting of polyolefin (A), modified polypropylene (B), and glass (C) are mixed in a predetermined amount to form a predetermined amount. The mixing order is not specified and each component may be mixed at the same time, or several components may be mixed in advance and the rest may be mixed later.Also, the mixing method is not specified. The process is generally carried out using a tumbler-equipped printer, a Henschel mixer, a ribbon mixer, etc.K used for the glass mat cloth-like material is a mixture of polyolefin (4) and modified polypropylene (B) in advance. A glass mat-like material may be impregnated with the molten material.

In the present invention, the polyolefin composition basically consists of the polyolefin (A), modified polypropylene (B), and glass (C), but in addition to these components, it also contains an antioxidant, an ultraviolet absorber, a lubricant, and a charging agent. inhibitor, nucleating agent,
pigment.

Enkal, Ri/L Ri, barium sulfate, mica, asbestos, silica, magnesium hydroxide, basic magnesium carbonate, aluminum hydroxide.

Various inorganic substances such as rock wool fiber, kaolin, and silicate may be added.

In order to explain the present invention more specifically, reference example 1#! Although the present invention will be described with reference to Examples and Comparative Examples, the present invention is not limited to these Examples.

Reference Ml Polypropylene (manufactured by Tokuyama 1 company; RB 410゜MI
o, 6 random copolymer with an ethylene content of 20% by weight) to 100 parts by weight of maleic anhydride II 2 weight 1
11t, 0.2 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,6-dit
0.1 part by weight of -butyl-4-methylphenol and 0.1 part by weight of calcium stearate were mixed in a Henschel mixer for 5 minutes, and then melted and mixed in a 40cm extruder (resin temperature 250''C) to pelletize.

In the following modified examples and comparative examples, the polypropylene composition obtained above is referred to as polypropylene composition (I).

Reference Example 2 The polypropyref composition-(I) obtained in Reference Example 1 was heat-treated at 145° C. for 4 hours using a hot air constant temperature dryer.

In the following examples and comparative examples, the polypropylene composition obtained above is referred to as polypropylene composition (1).

Reference example 3 Polypropylene (manufactured by Tokuyama 1 company; RB 110゜MI
o, 6 homopolymer), 5 parts by weight of anhydrous maleic a, 2 parts by weight of benzoyl peroxide, 0.
1 part by weight, 0.2
Parts by weight and 0.1 parts by weight of stearinized calcium were mixed for 5 minutes in a Henschel mixer, and then melted and mixed (resin temperature 220° C.) using an extruder with a niegu, and pelletized.

In the following examples and comparative examples, the polypropylene composition obtained above is referred to as polypropylene composition (1).

Reference Example 4 The polypropylene composition (1) obtained in Reference Example 3 was heat-treated at 150''C for 2 hours in a hot air constant temperature dryer.

In the following examples and comparative examples, the polypropylene composition obtained above is referred to as polypropylene composition (ff).

Reference example 5 Polypropylene (manufactured by Myama Kyodatsusha: M E 630゜M
I2.5 block polymer with ethylene) 100 parts by weight, maleic anhydride 525 parts by weight.

1 part by weight of dicumyl peroxide, 2,6-Z-t-7
'Tyl-4-methylphenol 01 parts by weight, heat stabilizer I
RG 凰NC) did.

In the following examples and comparative examples, the volip p obtained above
Pyrene mtt, coating is polypropylene composition (%').

Reference Example 6 Polypropylene composition obtained in Reference Example 5 CV) t130°C
The mixture was heat-treated for 10 hours.

In the following examples and comparative examples, the polypropylene composition obtained above is referred to as polypropylene composition (11).

Reference example 7 Polypropylene (manufactured by Tokuyama 1 company; M E, 140+
MI9 homopolymer) 100 parts by weight, ethylene-propylene random 1 combination (MI5.3 engineered tyrene content 70% by weight) 30 parts by weight, maleic anhydride 30 parts by weight, organic persulfide Kayahexa AD-50C (trade name) 5 Weight part, B
0.1 part by weight of -220 (product name: 7 Deforce Argus, phosphorus antioxidant) and 0.1 part by weight of calcium stearate.
1 part by weight was mixed for 5 minutes using a Henschel mixer, melt mixed using an extruder with a kneader (resin temperature: 250°C), and pelletized.

In the following examples and comparative examples, the polypropylene composition obtained above is referred to as polypropylene composition 1).

Reference Example 8 The polypropylene composition ('W) obtained in Reference Example 7 was
Heat treatment was performed at 0°C for 20 hours.

In the following Examples and Comparative Examples, the polypropylene composition obtained above is referred to as polypropylene composition (w).

Example 1 and Comparative Example 1 Polypropylene (manufactured by li1 Yamasoda Co., Ltd., M 8684)
100 parts by weight of various modified polypropylene compositions (B) in the proportions shown in Table 1 and 30% by weight in the total composition.
Glass fiber (made by Nippon Glass Textile Co., Ltd., product number RES-03-TP 37) w/77
Mixed in a 5-e blender.

Next, using a 4o pent extruder (using a full-flight screw), the mixture was melt mixed and pelletized. 13. , molded using an injection molding machine, ASTM
A tensile test piece and a bending test piece were obtained according to D638°DF91C. Using this test piece, a tensile test (AsTM, D6
38), Illage EM (ASTM, D-790) was performed to measure the tensile strength and bending strength. This value is also listed in Table 1.

Table 1 The square mark indicates a comparative example.

Example 2 and Comparative Example 2 Various modified polypropylene compositions (B) in the proportions shown in Table 2 based on 100 weight 11K of polypropylene (manufactured by Tokuyama 1 Hansha Co., Ltd., ME140) and 20% by weight in the total composition. Glass fibers (manufactured by Nippon Glass Fiber Co., Ltd., product number RES-06-TP 37) were mixed in a tumbler set.

Thereafter, tensile strength and ridge strength were measured in the same manner as in Example 1. This value is also listed in Table 92.

The mark indicates a comparative example.

Example 3 and Comparative Example 3 Various modified polypropylene compositions (B) in the proportions shown in Section B@, based on 100 parts by weight of polypropylene (manufactured by Tokuyama 1 Hansha, ME440), and 5% by weight in the total composition Glass fiber blended as follows (manufactured by Asahi Fiberglass Co., Ltd., 03-M
A-411) was mixed in a pre-tumbler set.

Hereinafter, tensile strength and bending strength were measured in the same manner as in Example 1. This value is also listed in Table 3.

Part 3 Shishi The bottle mark indicates a comparative example.

Example 4 and Comparative Example 4 Polypropylene (manufactured by Tokuyama Ichidasha, M E 240) 1
00 parts by weight of various modified polypropylene compositions
Glass beads (manufactured by Tokyo Shibaura Electric Co., Ltd., product number GB73) to make 7 parts by weight and 20% by weight of the total coin composition
1).

Glass powder (manufactured by Unitika NM Glass Co., Ltd., product number GP-1) and glass flakes (manufactured by Nippon Glass Fiber Co., Ltd., product number GF-48) were blended,
Mixed in a tumbler set.

Hereinafter, tensile strength and bending strength were measured in the same manner as in Example 1. This value is also listed in Table 4.

Table 4 * indicates a comparative example.

Example 5 and Comparative Example 5 Polyethylene (manufactured by Mikata Petrochemical Co., Ltd.) Izetskus 210
Glass fiber (tRE8-0 manufactured by Nippon Glass Fiber Co., Ltd.
3-TP37) was blended and mixed in a tumbler set.

Hereinafter, tensile strength and breakage strength were measured in the same manner as in Example 1. This value is also listed in Table 5.

No. 511! The square mark indicates a comparative example.

Claims (9)

[Claims] (1) Polyolefin (A) is polybupylene. After melting and kneading the unsaturated carboxyl group and organic peroxide,
A polyolefin composition comprising modified polypropylene (B) obtained by heat treatment and glass <C>. (2) The polyolefin composition according to claim 1, wherein a rubber-like substance is added when obtaining the modified polypropylene (B). (3) Modified polypropylene (B) is present in a proportion of 5 to 40 parts by weight based on 100 parts by weight of polyolefin (A), and glass (C) is present in a proportion of 3 to 40% by weight based on the total composition. The polyolefin composition according to Item 1 or 2 of Category 121. (4) Modified polypropylene (B) is obtained by blending 100 parts by weight of polypropylene, 0.05 to 2 parts by weight of unsaturated carboxylic acids, and 0.01 to 5 parts by weight of organic peroxide. The polyolefin composition described in . (5) When obtaining modified polypropylene (B), 100 parts by weight of polypropylene, 1 to 400 parts by weight of a rubbery substance, 100 parts by weight of unsaturated carboxylic acid @O,OS, and 10 parts by weight of organic peroxide 0.01 to 1O The polyolefin composition according to claim 2, which contains the following. (6) The polyolefin composition according to claim 1, wherein the polyolefin (A) is polypropylene. (7) The polyolefin composition according to claim 1, wherein the unsaturated carboxylic anhydride is maleic anhydride. (8) =/ The polyolefin composition according to claim 2, wherein the mucilage substance is a calcium ethylene-α-olefin random copolymer. (9) The polyolefin composition according to claim 1, wherein the glass is a glass fibrous material. (Ill) The polyolefin composition according to claim 11j11, wherein the temperature of the heat treatment is 60"C or higher. A polyolefin composition according to claim 1, which is melt-kneaded in a screw extruder. It will be less than mol%5
The polyolefin composition according to claim 1, which is subjected to a heat treatment.