JPH05311031A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic molding material which is excellent in mechanical strengths and moldability, is useful esp. as the material of an electrical part, and has such well-balanced properties that it is superior to a polyphenylene ether resin in solvent resistance and moldability and that it is superior to polypropylene in heat distortion resistance and bending modulus. CONSTITUTION:A thermoplastic resin compsn. is prepd. by compounding a modified propylene polymer with a polyphenylene ether resin. The modified propylene polymer is prepd. by mixing and kneading a propylene polymer melt with an arom. vinyl monomer or a mixture thereof with a polar vinyl monomer (esp. an epoxidized or carboxylated vinyl monomer) and thereby conducting the polymn. of the monomer or monomer mixture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin comprising a modified propylene polymer resin and a polyphenylene ether resin, which has excellent heat distortion resistance, impact resistance, rigidity and molding processability. It relates to a resin composition.

[0002]

2. Description of the Related Art Polyphenylene ether resins are excellent in electrical properties and mechanical properties, have a high heat distortion temperature and self-extinguishing properties, and are widely used in various mechanical parts materials as extremely useful engineering plastic resins. However, its drawbacks include remarkably inferior molding processability and poor solvent resistance. Due to such drawbacks, the application as an engineering resin is limited, and the excellent properties inherently possessed by polyphenylene ether resin cannot be utilized in many cases.

On the other hand, polypropylene is inferior to polyphenylene ether resin in heat distortion resistance and mechanical properties, but in terms of moldability and solvent resistance, not only polyphenylene ether resin but also polystyrene, polyvinyl chloride and the like. It is extremely superior to general-purpose resins and is widely used in various applications.

Since the polyphenylene ether resin and the polypropylene are in a relationship capable of compensating for each other's drawbacks, it is considered that the use thereof will be great if both of them can be alloyed. However, even if the polyphenylene ether resin and the polypropylene are simply blended by melt-kneading or the like, the compatibility between the two is poor, so that layer delamination occurs and the surface gloss and mechanical strength are poor and only practically usable ones can be obtained.

In order to improve the compatibility, Japanese Patent Publication No. 3-46495 and Japanese Patent Publication No. 56-22344 propose a technique of blending a polyolefin such as polypropylene graft-polymerized with a styrene monomer with a polyphenylene ether resin. Has been done.

However, it is difficult for the conventional composition to satisfy both the molding processability and the heat deformability and impact resistance, and it has not provided sufficient physical properties.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventional compositions and further improves the compatibility between the polyphenylene ether resin and polypropylene, and provides the polyphenylene ether resin with excellent heat distortion resistance and An object is to obtain a resin composition having both mechanical strength and properties such as solvent resistance and molding processability of polypropylene.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned drawbacks of the conventional method, the present inventors have found that in the presence of a propylene polymer in a molten state, an aromatic vinyl monomer and Alternatively, by adding a modified propylene-based polymer resin having a high graft ratio obtained by melt-kneading and polymerizing a polar functional group-containing vinyl monomer, it was found that the above objects can be achieved, and the present invention is completed. I arrived.

That is, the present invention is a modified propylene obtained by melt-kneading a propylene polymer in a molten state with an aromatic vinyl monomer or an aromatic vinyl monomer and a polar functional group-containing vinyl monomer. A thermoplastic resin composition comprising a polymer resin (A) and a polyphenylene ether resin (B). The present invention will be described in detail.

(Constitution) The propylene-based polymer of the present invention is
Propylene homopolymer and copolymers mainly composed of propylene and other olefins or ethylenic vinyl monomers (both of which are propylene 75% by weight or more and crystallinity is preferably 55 to 99%) Specifically, there are isotactic polypropylene, propylene-ethylene copolymer, propylene-butene copolymer and the like.
These propylene-based polymers can also be mixed and used. Further, other polymers can be used as long as the properties of the propylene polymer are not impaired.

As the aromatic vinyl monomer, for example, styrene, methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene,
Chlorostyrene, dichlorostyrene, bromostyrene and the like can be mentioned, and they can be used alone or in combination.

Furthermore, a polar functional group-containing vinyl monomer can be used in combination with the aromatic vinyl monomer. Examples of polar functional group-containing vinyl monomers include copolymerizable epoxy group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, carboxyl group-containing vinyl monomers, oxazoline group-containing vinyl monomers, and the like. Among these, epoxy group-containing vinyl monomers or carboxyl group-containing vinyl monomers are preferable.

Examples of the epoxy group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and methacryl glycidyl ether, which may be used alone or in combination. Glycidyl methacrylate is particularly preferable.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2
-Hydroxybutyl methacrylate and the like can be used alone or in combination.

The carboxyl group-containing vinyl monomer includes, for example, acrylic acid, methacrylic acid, maleic anhydride, maleic acid and the like and alkyl esters thereof, and these are used alone or in a mixture.

Examples of vinyl monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline and 2-isopropenyl-4-oxazoline.

The amount of the aromatic vinyl monomer added is 50% by weight or less of the propylene polymer, preferably 1 to 35% by weight, and most preferably 5 to 30% by weight. Fifty
If it exceeds 5% by weight, the performance of polypropylene is impaired, which is not preferable.

The addition amount of the polar functional group-containing vinyl monomer is 10% by weight or less, preferably 0.1 to 5% by weight based on the propylene polymer. If it exceeds 10% by weight, not only the product may have a low molecular weight, but also the composition may have adverse effects such as tackiness, hygroscopicity and mechanical properties. Further, the aromatic vinyl monomer is used for preventing lowering of the molecular weight of the modified propylene-based polymer and for improving the compatibility with the polyphenylene ether resin, at least the same amount or more of the addition amount of the polar functional group-containing vinyl monomer, preferably 1-5
It is preferable to add a double amount.

As a radical initiator, it is easily dissolved in an aromatic vinyl monomer due to the characteristics of the present invention, and in order to obtain a half-life of 1 minute because this reaction is carried out at a melt-kneading temperature of a propylene-based polymer. Decomposition temperature is preferably 130 to 260 ° C, and more preferably 170 to 250 ° C.
Is. Specific examples include t-butyl peroctate, bis (t-butyl peroxy) trimethylcyclohexane, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, dimethyl di (t-butyl peroxide). Oxy) hexane, dimethyldi (t-butylperoxy)
Hexin and the like can be mentioned. The amount of the organic peroxide used is
It is usually 0.1 to 10 with respect to 100 parts by weight of the vinyl monomer.
The amount is preferably 1 to 5 parts by weight, preferably 1 to 5 parts by weight.

As other additives, polypropylene is a radical-disintegrating polymer unlike polyethylene and the like, so that it is preferable to add a stabilizer. However, it is necessary to consider the kind and the addition amount so as not to hinder the graft polymerization of the aromatic vinyl monomer. For example, pentaerythrityl-
Tetrakis (di-t-butyl-hydroxyphenyl) propionate), ocdecyl (di-t-butyl-hydroxyphenyl) propionate, thiobis (methyl t)
-Butylphenol), trimethyl-tris (di-t-butylhydroxybenzyl) benzene and other hindered phenolic stabilizers, tetrakis (di-t-butylphenyl) biphenylene phosphite, tris (di-t-butylphenyl) phosphite And other phosphorus-based stabilizers, metal stearate such as zinc stearate and calcium stearate, and antacid adsorbents such as magnesium oxide and hydrotalcite. The amount of the stabilizer used is usually 0.01 to 1 part by weight, preferably 0.1 part by weight based on 100 parts by weight of the propylene polymer.
It is from 05 to 0.5 parts by weight.

The melt-kneading polymerization reaction between the propylene polymer and the aromatic vinyl monomer, or the vinyl monomer containing a polar functional group is carried out in a closed container such as a Banbury mixer or a continuous kneader such as an extruder. Can be done with. The extruder is
It is preferable when considering industrial production such as granulation. Further, the twin-screw extruder is easier to control the supply of reactants, kneading, polymerization time and the like.

As a manufacturing method, a propylene-based polymer in powder or pellet form is fed to an extruder and pressurized 1
The crystalline propylene-based polymer is melted by heating at 30 to 250 ° C., the aromatic vinyl monomer, or the polar functional group-containing vinyl monomer is melt-kneaded and polymerized, and then the strand discharged from the die is removed. Cool and pellet using a pelletizer.

The vinyl monomer may be mixed with the propylene-based polymer in advance and then fed to the extruder or may be fed to the propylene-based polymer in a molten state by using a liquid feeder. It is preferable to mix and impregnate the propylene-based polymer.

The radical initiator may be dissolved in the vinyl monomer in advance and then added, or may be added to the mixture of the propylene polymer and the vinyl monomer by using a liquid feeder. The stabilizer is preferably mixed in advance with the propylene polymer using a Henschel mixer or the like.

Since the propylene-based polymer is a radical-disintegrating polymer unlike the ethylene-based polymer, if the polymer is simply melt-heated, the molecular weight is apt to decrease due to the breaking of the main chain.
Therefore, a modified propylene-based polymer having a low molecular weight and inferior physical properties such as strength can be obtained even if a polar functional group-containing vinyl monomer melt-kneading reaction is performed in the presence of an organic peroxide. However, according to the melt-kneading reaction method of the present invention, an aromatic vinyl monomer, or a polar functional group-containing vinyl monomer is efficiently added to the propylene-based polymer by reacting in the presence of a stabilizer. Because of the graft reaction, a modified propylene-based polymer with no decrease in molecular weight can be obtained.

For that purpose, it is necessary to react under a polymerization condition in which the graft ratio of the modified propylene polymer is high, preferably more than 40%, and thereby the compatibility with the polyphenylene ether resin is improved. It can be a modified propylene-based polymer.

The polyphenylene ether resin in the present invention can be represented by the following general formula.

[0028]

[Chemical 1]

Here, the substituents R are each independently hydrogen, halogen, a hydrocarbon group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group. m is the degree of substitution and is an integer of maximum 4. n is the degree of polymerization and is usually at least 50.

The polyphenylene ether resin and the method for producing the same are not related to the present invention, and if necessary, various documents such as US Pat. Nos. 3,306,874 and 3,306,875 can be referred to. Examples of the polyphenylene ether resin suitable for use in the present invention are as follows.

Poly (2.6-dimethyl-phenylene) ether, poly (2-methyl-6-ethyl-1.4-phenylene) ether, poly (2.6-dipropyl-1.4)
-Phenylene) ether, poly (2-ethyl-6-propyl-1.4-phenylene) ether, poly (2.6-dilauryllou 1.4-phenylene) ether, poly (2
6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,3.6-trimethyl-1,4-phenylene) ether, poly (2,3,5,6-tetrapropyiene) Lou 1,4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether, poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-5-stearyloxy-1,4)
-Phenylene) ether, poly (2.6-dichloro 1)
・ 4-phenylene) ether, poly (2,3-dimethyl-5-chloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2.6-dibenzyl-1,4-phenylene) ether, poly (3) -Chloro-1.4-phenylene) ether, poly (3.5-dimethyl-1.4-phenylene) ether, poly (3-ethoxy-1.4-phenylene) ether, poly (2-chloro-1.4-phenylene) ether, poly (2.5-dibromune-1) -4-phenylene) ether.

These polyphenylene ether resins are generally marketed as a mixture with a styrenic polymer, and such a mixture can be the object of the present invention without departing from the object of the invention. Further, these polyphenylene ether resins may be a mixture with other resins such as polyamide resin and polysulfone resin.

The thermoplastic resin composition of the present invention contains the modified propylene polymer (A) in an amount of 5 to 95% by weight, preferably 20 to 85% by weight, and a polyphenylene ether resin (B).
It is 95 to 5% by weight, preferably 80 to 15% by weight.
When the content of the modified propylene-based polymer in the thermoplastic resin composition is less than 5% by weight, the effect of improving the solvent resistance and molding processability of the modified propylene-based polymer cannot be obtained. on the other hand,
If the polyphenylene ether resin content is less than 5% by weight, mechanical properties, heat distortion resistance, and
The effect of improving impact resistance cannot be obtained.

In addition to these essential components, additional components may be added to the thermoplastic resin composition of the present invention within a range that does not impair the effects of the invention. Unmodified polypropylene may be added as an additional component. In that case, the addition may be carried out after first mixing with the modified propylene-based polymer or when mixing with the polyphenylene ether resin, but the addition amount of the unmodified polypropylene is the modified propylene-based polymer 1
It should be 900 or less with respect to 00. Other additional components include, for example, other thermoplastic resins, rubbers, inorganic fillers, pigments, various stabilizers (antioxidants, light stabilizers, antistatic agents, antiblocking agents, lubricants) and the like.

The thermoplastic resin composition of the present invention is produced by dry blending these components with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, etc., and then mixing this mixture with a uniaxial or biaxial extruder or roll. It is melt-mixed with a kneading machine such as a Banbury mixer, pelletized or crushed, and then subjected to molding. For the molding, any method such as injection molding, hollow molding, extrusion molding and the like can be adopted.

By doing so, the thermoplastic resin composition of the present invention is a thermoplastic resin composition having excellent balance in solvent resistance, heat distortion resistance, rigidity, moisture resistance, paintability, surface property and the like. You can

[0037]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, all parts and% are based on weight unless otherwise specified.

The test methods for the physical properties of the thermoplastic resin composition and the target physical properties are as follows. Melt index (PP and modified PP): JIS K7
210 (2.16 Kg, 230 ° C) Formability: Melt Index (2.16 Kg, 27)
It was evaluated at 5 ° C. Target 1 to 10 Thermal deformability: Measurement JIS K7202 (HDT temperature load 4.6 Kg / cm) Target 130 ° C or higher Bending elastic modulus: Measurement JIS K7203 Target 1.8 * 1
0 ⁴ kg / cm ² or more Impact strength: Measurement ASTM D256 Target 6 or more Solvent resistance: Injection specimens (104 * 50 * 2 mm) were used to dip in toluene at 23 ° C for 4 hours, and then the presence or absence of craze was visually judged. did. No goal craze

(Example 1) <Production of modified polypropylene> A 30 mm twin-screw extruder manufactured by Brabender (Germany) was set to a barrel temperature of 200 ° C (however, a feeder section of 180 ° C) and a die temperature of 210 ° C. High Pole B200P (powdered polypropylene
Mitsui Petrochemical Co., Ltd.) 900 parts Irganox 1010
(Ciba-Gaiki Stabilizer) 0.5 part, phosphite 1
68 parts (stabilizer manufactured by Ciba-Gaiki) was mixed with 1 part of calcium stearate (stabilizer). Styrene 10
A mixture of 0 parts and 3 parts of Perhexin 25B (manufactured by NOF CORPORATION) was dry blended with the above powder polypropylene compound. The dry blend obtained is fed to an extruder 1
A graft reaction was performed by melt-kneading at 5 rpm, and 960 parts of product pellets were obtained through a pelletizer. Styrene content of the extruded product with a ratio of 700 cm ^-1 using infrared spectroscopy analysis of the product (attributable to styrene) and 1380 cm ^-1 (assigned to polypropylene) 9.5% from the calibration curve
Met. In order to determine the presence or absence of grafting of the styrene moiety in the extruded product, polypropylene is not dissolved but polystyrene is dissolved. Soxhlet extraction of the product is carried out under reflux using tetrahydrofuran, and the residual ratio of the styrene moiety in the product is determined. When the graft ratio was measured, it was 54%.

<Production of Thermoplastic Resin Composition> 400 parts of the modified propylene polymer obtained above and Iupiace AH
600 parts of 110 (polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Inc.) was blended, and this was mixed with a twin-screw extruder to produce 26 parts.
The mixture was kneaded at 5 ° C and pelletized. Using the IS50AM injection molding machine manufactured by Toshiba, test pieces were prepared from the obtained pellets at a resin temperature of 290 ° C., and various physical properties were evaluated. The results are shown in Table 2.

Example 2 In the production of the modified propylene polymer of Example 1, 20 parts of glycidyl methacrylate and 50 parts of styrene were used instead of 100 parts of styrene,
Along with that, a modified polypropylene was produced in the same manner as in Example 1 except that 930 parts of Hypol B200P (powdered polypropylene, manufactured by Mitsui Petrochemical Co., Ltd.) and 2.1 parts of Perhexin 25B (manufactured by NOF CORPORATION) were used. . The modified propylene polymer obtained had a styrene content of 4.9% and a graft ratio of 59%.

Modified propylene polymer 4 obtained above
00 parts and 600 parts of Iupiace AH110 (polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Inc.) were blended and kneaded at 265 ° C. using a twin-screw extruder to form pellets. Using the IS50AM injection molding machine manufactured by Toshiba, test pieces were prepared from the obtained pellets at a resin temperature of 290 ° C., and various physical properties were evaluated. The results are shown in Table 2.

Example 3 In the production of the thermoplastic resin composition of Example 2, 400 parts of the modified propylene polymer and Iupiace AH110 (polyphenylene ether resin)
(Manufactured by Mitsubishi Gas Chemical Co., Inc.) 600 parts of the modified propylene polymer and Iupiace AH110 4 instead of 600 parts
A thermoplastic resin composition was produced using 00 parts of Example 2
Various physical properties were evaluated in the same manner as. The results are shown in Table 2.

Example 4 In the production of the modified propylene-based polymer of Example 2, 30 parts of methacrylic acid and 50 parts of styrene were used in place of 20 parts of glycidyl methacrylate.
Part, and along with it, Hipol B200P (powdered polypropylene Mitsui Petrochemical Co., Ltd.) in 910 parts,
A modified polypropylene was produced in the same manner as in Example 1 except that 2.7 parts of Perhexin 25B (manufactured by NOF CORPORATION) was used. The obtained modified propylene-based polymer had a styrene content of 5.7% and a graft ratio of 49%.

300 parts of the above modified propylene polymer and 700 parts of Iupiace AH110 (polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Inc.) were blended and kneaded at 265 ° C. using a twin-screw extruder to form pellets. Using the IS50AM injection molding machine manufactured by Toshiba, test pieces were prepared from the obtained pellets at a resin temperature of 290 ° C., and various physical properties were evaluated. The results are shown in Table 2.

[0046]

[Table 1]

[0047]

[Table 2] (Comparative Example 1) Instead of using 400 parts of the modified propylene-based polymer in the production of the thermoplastic resin composition of Example 1, the same amount of Hypol J600 (manufactured by Mitsui Petrochemical Co., Ltd.) was used to prepare a thermoplastic resin composition. It was manufactured, and various physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 2) A separable flask having an internal volume of 5 l and equipped with a reflux apparatus was added with 2800 g of pure water and 35 g of calcium phosphate as a suspending agent to form an aqueous medium, and this was used as Hypol B200P (powdered polypropylene Mitsui Petrochemical Co., Ltd.). ) 900 parts were suspended by stirring. Separately, 3 g of perbutyl O (manufactured by NOF CORPORATION) as a polymerization initiator was dissolved in 100 g of styrene, and this was added to the above suspension system.
This aqueous suspension was heated to 80 ° C. under a nitrogen atmosphere and stirred for 7 hours to complete the polymerization. The product was washed with diluted hydrochloric acid and the like and then dried. The styrene-modified polypropylene had a styrene content of 9.4% and a graft ratio of 25%.

With respect to the modified propylene-based polymer obtained as described above, a test piece was prepared from a thermoplastic resin composition containing polypropylene and a polyphenylene ether resin in the same proportions as in Example 1, and the physical properties were evaluated. The results are shown in Table 4.

(Comparative Example 3) The same as Example 2 except that 50 parts of styrene was removed from the production of the modified propylene polymer of Example 2 and 0.6 parts of Perhexin 25B (manufactured by NOF Corporation) was added accordingly. Then, a modified polypropylene and a thermoplastic resin composition were produced and various physical properties were evaluated.
The results are shown in Table 4.

Comparative Example 4 Instead of using 400 parts of the modified propylene polymer in the production of the thermoplastic resin composition of Example 1, the same amount of Admer QF540 (commercially available carboxylic acid modified polypropylene manufactured by Mitsui Petrochemical Co., Ltd.) was used. Using it, a thermoplastic resin composition was produced, and various physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 4.

Reference Example 1 Instead of using the modified propylene-based polymer and the polyphenylene ether resin in the production of the thermoplastic resin composition of Example 1, Iupiace AH110 (polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Inc.) was used for the purpose of physical properties. A thermoplastic resin composition was produced by using it alone, and various physical properties were evaluated in the same manner as in Example 1.
The results are shown in Table 4.

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention is obtained by melt-kneading and polymerizing a propylene polymer in a molten state with an aromatic vinyl monomer or a polar functional group-containing vinyl monomer. By using the modified polypropylene, it has excellent mechanical properties and economical efficiency, and is particularly useful as a housing material for electric parts. It is possible to provide a thermoplastic molding material having a good balance of physical properties, such as being superior in solvent resistance and molding processability to polyphenylene ether resin, and superior to polypropylene in thermal deformability, impact resistance and rigidity.

Claims (4)

[Claims] 1. A modified propylene polymer obtained by melt-kneading a propylene polymer in a molten state with an aromatic vinyl monomer or an aromatic vinyl monomer and a vinyl monomer containing a polar functional group. A thermoplastic resin composition comprising a resin (A) and a polyphenylene ether resin (B). 2. A modified propylene polymer resin (A) containing 5 to 5 parts.
95 wt%, polyphenylene ether resin (B) 95
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is used in an amount of about 5% by weight. 3. The thermoplastic resin composition according to claim 1, wherein the polar functional group-containing vinyl monomer is an epoxy group-containing vinyl monomer or a carboxyl group-containing vinyl monomer. 4. A modified propylene polymer resin (A) is obtained by grafting an aromatic vinyl monomer or an aromatic vinyl monomer and a polar functional group-containing vinyl monomer onto a propylene polymer. The thermoplastic resin composition according to claim 1, which is a modified propylene-based polymer resin having a graft ratio of 40% by weight.