JP3326893B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION This invention is a hydrogenated diene-based copolymer having a specific structure to polypropylene, et styrene -α- olefin - (non-conjugated diene) random copolymer, an inorganic filler further optionally By adding, it has high flexibility and high strength, and relates to a thermoplastic resin composition excellent in non-orientation, by processing into sheets, films, tubes or injection molded products, automotive interior and exterior materials, OA equipment related parts, AV / home appliances related parts, stationery products, office equipment parts, civil engineering building materials, electric wire coating materials,
It can be used for semiconductor-related parts, medical materials and the like.

[0002]

2. Description of the Related Art Polypropylene is used in various fields because of its excellent balance of physical properties and the lightest weight among general-purpose thermoplastic resins. Although flexible PVC is a material excellent in cost performance, its use is beginning to be restricted from the viewpoint of protection of the global environment, and olefin-based materials such as polypropylene are being replaced in some fields. However, in order to give polypropylene the same flexibility as soft PVC, it is common to add a large amount of various existing elastomers, or to add an oil or a plasticizer. However, when a polypropylene composition containing a large amount of an existing elastomer is molded by a molding method such as extrusion molding or injection molding, which tends to cause molecular orientation, a difference in performance such as strength occurs in the longitudinal direction and the transverse direction, which results in quality variation. Cause and problem. In addition, the polypropylene composition containing an oil or a plasticizer sticks to the surface of a molded article due to bleeding of the composition, which is also a problem.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is directed to a hydrogenated diene-based copolymer specially designed as a modifier for polypropylene and an ethylene-α-polymer. Olefin- (non-conjugated diene)
By adding a random copolymer and, if necessary, an inorganic filler, it has high flexibility and high strength, and does not leave orientation in a molded product after extrusion molding or injection molding (that is, non-orientation). It is intended to obtain an (excellent) thermoplastic resin composition.

[0004]

According to the present invention, there are provided (a) 5 to 90% by weight of polypropylene, (b) a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a vinyl aromatic compound and a conjugated diene. (A)-(B) or (A)-comprising a random copolymer block (B) of
(B)-(A) a block copolymer or (A)-(B)-comprising a taper block (C) comprising a vinyl aromatic compound and a conjugated diene and gradually increasing the vinyl aromatic compound.
(C) a block copolymer, wherein the ratio of vinyl aromatic compound / conjugated diene is 5/95 to 60/4 by weight.
0, the amount of the vinyl aromatic compound in the components (A) and (C) is 3 to 50% by weight of the total monomers, and the amount of the vinyl aromatic compound in the component (A) is 3% by weight or more of the total monomers. Hydrogenation of a block copolymer having a vinyl bond content of the conjugated diene portion in the component (B) of more than 60%,
5 to 90% by weight of a hydrogenated diene copolymer in which the double bond of the conjugated diene portion is saturated by 80% or more, (c) ethylene-α
-Olefin- (non-conjugated diene) random copolymer 5
90 wt%, and (d) inorganic filler over (a) +
0 to 500 based on 100 parts by weight of the total amount of (b) + (c)
An object of the present invention is to provide a thermoplastic resin composition composed of parts by weight and having excellent non-orientation .

Hereinafter, the present invention will be described in detail. In the present invention, the polypropylene constituting the component (a) is isotactic polypropylene or syndiotactic polypropylene, and may be a homo-type, a block type containing a comonomer, or a random type. The polypropylene is a gas phase polymerization method, a bulk polymerization method,
The polymer is polymerized by a solvent polymerization method or the like, and the number average molecular weight is not particularly limited, but is preferably 10,000 to 1,000,000.
It is adjusted to. (A) in the thermoplastic resin composition of the present invention
The amount of the component is 5 to 90% by weight, preferably 10 to 90% by weight.
To 80% by weight, more preferably 20 to 80% by weight. If it is less than 5% by weight, the strength is poor, and if it exceeds 90% by weight, flexibility, non-orientation and low-temperature impact resistance are poor.

Next, the hydrogenated diene copolymer as the component (b) will be described. The component (A) is a polymer block mainly composed of a vinyl aromatic compound, and may be a copolymer of a copolymerizable vinyl compound at 10% by weight or less, preferably 5% by weight or less. Examples of the vinyl aromatic compound constituting the hydrogenated diene copolymer include styrene, α-methylstyrene, p-methylstyrene, and the like. These may be used alone or as a mixture, and the conjugated diene may be butadiene. And isoprene, butadiene is particularly preferred. The weight ratio of vinyl aromatic compound / conjugated diene is 5 / 95-60 / 40, preferably 7 / 93-50.
/ 50, more preferably 8/92 to 40/60. If the vinyl aromatic compound is less than 5% by weight (the conjugated diene exceeds 95% by weight), the strength is poor, and the vinyl aromatic compound exceeds 60% by weight. (The conjugated diene is less than 40% by weight), the flexibility is poor.

The amount of the vinyl aromatic compound in the component (A) or (C) is 3 to 50% by weight of the total monomers,
Preferably 5 to 40% by weight, more preferably 5 to 25%
% By weight. If it is less than 3% by weight, the strength is poor, and if it exceeds 50% by weight, the flexibility and the low-temperature impact resistance are poor. Also,
The amount of the vinyl aromatic compound bound in the component (A) is at least 3% by weight, preferably 5 to 40% by weight of the total monomers.
If it is less than 3% by weight, the strength is poor. The vinyl bond amount of the conjugated diene part in the component (B) exceeds 60%, preferably 7%.
0% or more, more preferably 75% or more. 60%
Below, flexibility and non-orientation are inferior. The hydrogenation rate of the double bond in the conjugated diene portion is 80% or more, preferably 90% or more, and more preferably 95% or more. 8
If it is less than 0%, the strength is poor. The number average molecular weight of the hydrogenated diene copolymer is not particularly limited, but is usually 100,000 or more, preferably 200,000 to 600,000, and more preferably 20 to 600,000.
400,000.

[0008] The hydrogenated diene copolymer of the present invention is produced by living anionic polymerization and further hydrogenation as disclosed in JP-A-3-72512. The hydrogenated diene copolymer used in the present invention may be a block copolymer having a polymer molecular chain extended or branched as represented by the following general formula by adding a coupling agent. . [(A)-(B)] nX, [(A)-(B)-
(C)] nX or [(A)-(B)-(A)]
nx [wherein (A), (B) and (C) are the same as above. n is 2
X represents an integer of 4 to 4 and represents a coupling agent residue. Examples of the coupling agent at this time include diethyl adipate, divinylbenzene, methyldichlorosilane, and silicon tetrachloride. The hydrogenated diene copolymer used in the present invention may be modified with a functional group, and may be at least one functional group selected from an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group and an epoxy group. It can be modified with an extruder or the like using an unsaturated compound having a group. The compounding amount of the component (b) in the thermoplastic resin composition of the present invention is 5 to 90% by weight, preferably 5 to 80% by weight, and more preferably 10 to 80% by weight.
% By weight. If it is less than 5% by weight, the non- orientation is poor and 90%
If the content exceeds% by weight, the strength is poor.

Next, the ethylene-α-olefin- (non-conjugated diene) random copolymer as the component (c) will be described. In the ethylene-α-olefin- (non-conjugated diene) random copolymer used in the present invention, the α-olefin has 3 to 12 carbon atoms, Mooney viscosity ML _{1 + 4} , 1
00 ° C is 3 to 120, Mw / Mn is 1.3 to 10 (where Mw indicates a weight average molecular weight), ethylene / α-
The olefin / non-conjugated diene ratio is 30 to 95 by weight.
/ 5 to 70/0 to 8 The ethylene-α-olefin- (non-conjugated diene) random copolymer used in the present invention is prepared by, for example, using ethylene and α using a Ziegler-based catalyst.
-Obtained by copolymerizing an olefin or a non-conjugated diene with it.

[0010] The α-olefin has 3 to 1 carbon atoms.
Α-olefin of No. 2 and specific examples thereof include propylene, butene-1, pentene-1, 4-methylpentene-
1, hexene-1, heptene-1, octene-1 and the like. Preferred are propylene and butene-1.
These α-olefins can be used alone or in combination of two or more. Specific examples of the non-conjugated diene include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbonadiene, and 5-cyclopentadiene.
Methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,
5-isopropylidene-2-norbornene, 5- (1-
Butenyl) -2-norbornene, cyclooctadiene,
Vinylcyclohexene, 1,5,9-cyclododecatriene, 1,4-hexadiene, 1,6-octadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-
Decadiene, 3,6-dimethyl-1,7-octadiene and the like. Preferred are 5-ethylidene-2-norbornene and dicyclopentadiene.

The ethylene-α-olefin- (non-conjugated diene) random copolymer used in the present invention may be modified with a functional group, and may be an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group. It can be modified with an extruder or the like using an unsaturated compound having at least one functional group selected from epoxy groups and epoxy groups. The amount of the component (c) in the thermoplastic resin composition of the present invention is 5 to 90% by weight, preferably 5 to 80% by weight, and more preferably 10 to 80% by weight. If it is less than 5% by weight, the low-temperature impact resistance is poor.

Next, the inorganic filler as the component (d) will be described. The inorganic filler used in the present invention includes glass flake, kaolin, clay, silica, carbon black, glass balloon, glass beads, mica, talc, calcium carbonate, potassium titanate whisker, barium sulfate, shirasu balloon, Aerogel, and the like. Particularly, calcium carbonate and talc are preferred. The amount of component (d) is from 0 to 500 parts by weight, preferably from 0 to 300 parts by weight, more preferably from 0 to 300 parts by weight, per 100 parts by weight of the total of components (a), (b) and (c). ~ 200
Parts by weight. The thermoplastic resin composition of the present invention contains the above components (a), (b), (c) and, if necessary, component (d) as main components, and includes an antioxidant, an antistatic agent, a weathering agent,
UV absorbers, lubricants, fungicides, antibacterial agents, foaming agents or titanium oxide, coloring agents such as carbon black, or other rubbery polymers, thermoplastic resins, etc. to the extent that the effects of the present invention are not impaired. They can be appropriately blended.

The composition of the present invention can be obtained by melt-kneading with an extruder, roll, kneader, Banbury mixer, or the like, or by dry-blending with an injection molding machine. In order to produce the composition of the present invention, each component may be mixed at once, or any components may be preliminarily mixed and then the remaining components may be added and mixed. The most preferred mixing device is a single-screw or twin-screw extruder, which can continuously and efficiently knead and pelletize. Using the obtained pellet,
Extrusion molding, inflation molding, calender molding, compression molding, injection molding or hollow molding can be performed, and in some cases, added value such as foaming can be added and processed into a molded product. Examples of the extruded product obtained by using the composition of the present invention include a sheet, a film, a tube, and a foamed sheet, and can be used for various applications.

[0014]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, parts and% are
Unless otherwise specified, it is based on weight. Various measurements in the examples and comparative examples were based on the following methods. Each component used in Comparative Examples and Examples will be described below.

(1) Polypropylene A commercially available polypropylene was used. P-1: Random PP [EX-6, Mitsubishi Yuka Corporation] P-2: Homo PP [J5010B, Tosoh Corporation] P-3: Block PP [BJ500, Tonen Chemical Corporation] (2) Table 1 shows the structure of the hydrogenated diene copolymer. (3) ethylene-α-olefin- (non-conjugated diene)
Random copolymer The following commercially available product was used. E-1: ethylene-propylene copolymer [EP07P,
Japan Synthetic Rubber Co., Ltd.] E-2: Ethylene-propylene-ENB copolymer [EP
57P, Nippon Synthetic Rubber Co., Ltd.

(4) Inorganic filler Calcium carbonate was used. Hereinafter, the analysis method and the evaluation method will be described. The content was measured by infrared spectroscopy based on the absorption of a phenyl group at a bound vinyl aromatic compound content of 679 cm ^-1 . Vinyl bond content of conjugated diene Calculated by the Hampton method using infrared analysis. Hydrogenation rate 100 MHz, ¹ H-N using ethylene tetrachloride as solvent
It was calculated from the MR spectrum. Number average molecular weight of hydrogenated diene copolymer Trichlorobenzene was used as a solvent, and was determined in terms of polystyrene using gel permeation chromatography (GPC) at 135 ° C. Flexibility (Hardness) Using a sheet molded with a 50 mmφ single screw extruder (220 ° C.), the hardness was evaluated by the hardness measured according to JIS K6301. The lower the hardness, the more flexible, and if the hardness exceeds 100, the flexibility is poor. Strength (tensile breaking strength) JIS K630 using a dumbbell cut out of a sheet formed by a 50 mmφ single screw extruder (220 ° C) in the longitudinal direction.
Evaluation was made based on the tensile strength at break measured according to 1. Strength 1
If it is less than 00 kgf / cm ^2, it is not preferable because it has no meaning as a structure.

Non-Orientation (Transverse / Vertical Ratio of Tensile Rupture Strength) Using a dumbbell, a sheet formed by a 50 mmφ single-screw extruder (220 ° C.) was cut out in a machine direction and a machine direction, using JI.
Evaluation was made based on the transverse / aspect ratio of the tensile strength at break measured according to SK6301. The following criteria were provided to clarify the determination. Determine the constant evaluation intensity of the horizontal / vertical ratio ◎ orientation without any very good 0.9 or more ○ orientation less satisfactory than 0.7 × less than There 0.7 orientation increases problems than 0.9 low-temperature impact resistance ( Drop weight impact energy) A sheet formed by a 50 mmφ single screw extruder (220 ° C.) is cut out and subjected to a drop weight impact test under an environment of −30 ° C. at a hole diameter of 30 mmφ, a weight diameter of 25.4 mmφ, and a speed of 5 mm / sec. And the energy required for destruction. If the energy value is 200 kgf / cm or less, the probability of causing brittle fracture is high, which is not preferable.

Examples 1 to 8, Comparative Examples 1 to 8 The performances of the resin compositions having the compositions shown in Table 1 were evaluated, and the results are shown in Tables 2 and 3. From the results of Examples 1 to 8 shown in Table 2, the resin composition of the present invention is superior in flexibility, strength, non-orientation and low-temperature impact properties as compared with Comparative Examples 1 to 8 shown in Table 3. I understand. In Comparative Examples 1 to 4, since the hydrogenated diene copolymer is out of the range of the present invention, the balance of flexibility, strength, non-orientation and low-temperature impact properties is inferior. Comparative Examples 5 to 8 are inferior in the balance of flexibility, strength, non-orientation, and low-temperature impact because the mixing ratio is out of the range of the present invention.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

According to the present invention, if a conventional rubbery polymer is blended with polypropylene to give the same flexibility as soft vinyl chloride, there is a problem that a significant decrease in strength and a variation in quality due to orientation appear. The present invention relates to a hydrogenated diene copolymer having a specific structure in polypropylene, and ethylene-
α-olefin- (non-conjugated diene) random copolymer, by adding an inorganic filler if necessary,
A thermoplastic resin composition having excellent flexibility, strength, non- orientation, and low-temperature impact resistance is obtained, and it is used for AV interior and exterior materials such as instrument panel skin materials and bumper materials, OA equipment-related parts, and vacuum cleaner bumper materials. Home appliance related parts, stationery products such as cutting mats, office equipment parts, civil engineering construction materials such as decorative films and civil engineering waterproofing sheets, electric wire coating materials, semiconductor related parts such as dicing films, medical materials, cap liners and water purifier tubes, etc. It can be used for food-related materials and has a great industrial value.

Continuation of front page (72) Inventor Yoshihisa Fujinaga 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-3-72512 (JP, A) JP-A-4-57848 (JP, A) JP-A-3-172339 (JP, A) JP-A-61-34048 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23 / 36 C08L 53/00-53/02

Claims (1)

(57) [Claims] (A) 5 to 90% by weight of polypropylene; (b) a random copolymer block of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a vinyl aromatic compound and a conjugated diene (B) (A)
-(B) or (A)-(B)-(A) block copolymer, or taper block (C) comprising a vinyl aromatic compound and a conjugated diene and gradually increasing the vinyl aromatic compound
(A)-(B)-(C) block copolymer comprising a vinyl aromatic compound / conjugated diene in a weight ratio of 5
/ 95-60 / 40, the binding amount of the vinyl aromatic compound in the components (A) and (C) is 3-50% by weight of all monomers, and the binding amount of the vinyl aromatic compound in the component (A) is all monomers (B) the conjugated diene moiety in component (B) has a vinyl bond content of 60% or more.
%, More than 5% by weight of a hydrogenated diene-based copolymer in which the double bond of the conjugated diene portion is saturated by 80% or more by hydrogenating the block copolymer. (C) ethylene-α-olefin- ( Non-conjugated diene)
The total amount of the random copolymer from 5 to 90 wt%, and (d) inorganic filler over (a) + (b) + (c) 1
Non-oriented consisting of 0 to 500 parts by weight with respect to 00 parts by weight
Excellent thermoplastic resin composition.