JPH0625480A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. excellent in flowability in molding and also in heat resistance, mechanical strengths, and chemical resistance. CONSTITUTION:This compsn. comprises 10-90 pts.wt. polyarylate and 90-10 pts.wt. modified polyolefin consisting mainly of polypropylene. The modified polyolefin has at least one structural unit having both at least one amide group and at least one glycidyloxy or glycidyl group based on 4-5,000 carbon atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent heat resistance, mechanical strength, chemical resistance and fluidity during molding.

[0002]

Polyarylate is an engineering plastic obtained by polycondensation of aromatic dicarboxylic acid or its derivative with bisphenol or its derivative, and has high heat distortion temperature and thermal decomposition temperature, and further, tensile strength, It is known to have excellent mechanical strength such as bending strength. However, polyarylate has the drawbacks of poor fluidity during molding and poor chemical resistance due to the aforementioned thermal properties and high melt viscosity.

In order to improve the fluidity of polyarylate during molding, for example, Japanese Patent Application Laid-Open No. 48-51946 discloses a method of adding polypropylene to the above polyarylate. However, in the above method, the mechanical strength such as tensile strength and elongation at break of the obtained polyarylate is remarkably reduced. Therefore, it is difficult to use such a polyarylate as a molding material.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks, and its object is to provide excellent fluidity during molding, and excellent heat resistance, mechanical strength and chemical resistance. It is to provide a resin composition.

[0005]

The thermoplastic resin composition of the present invention comprises 10 to 90 parts by weight of polyarylate (A) and 90 to 90 parts of modified polyolefin (B) containing polypropylene as a main component.
A thermoplastic resin composition containing 10 parts by weight, wherein the modified polyolefin (B) comprises at least one amide group and at least one group selected from the group consisting of glycidyloxy groups and glycidyl groups. The above-mentioned object is achieved by having one structural unit having 4 to 5000 carbon atoms.

Next, the present invention will be described in detail.

The thermoplastic resin composition of the present invention contains a polyarylate (A) and a modified polyolefin (B).

As the polyarylate (A) contained in the resin composition of the present invention, bisphenol and / or its derivative as a diol component and aromatic dicarboxylic acid and / or its derivative as an acid component are constituent components. Are preferred aromatic polyesters.

The bisphenol is preferably a compound represented by the following general formula [I].

[0010]

[Chemical 4]

(In the formula, X represents O, S, SO ₂ , CO, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 2 to 20 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom,
Represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms).

Examples of the hydrocarbon group in the above general formula [I] include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a cyclohexyl group and an octyl group; a propenyl group and a butenyl group. Alkenyl groups such as groups; benzyl groups, phenyl groups, aryl groups such as naphthyl groups, and the like.

Specific examples of the compound represented by the following general formula [I] include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and bis (4-hydroxyphenyl).
Methane, bis (4-hydroxy-3,5-dimethylphenyl)
Methane, bis (4-hydroxy-3,5-dichlorophenyl)
Methane, 1,1-bis (4-hydroxyphenyl) cyclohexylmethane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, 1,
1-bis (4-hydroxyphenyl) -1-phenylethane,
4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5
-Dimethylphenyl) sulfone, 4,4'-dihydroxybenzophenone, 2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane and the like. The bisphenol derivative is, for example, the above-mentioned alkali metal salt of bisphenol or diacetate.

The above bisphenol and its derivatives are
Each may be contained alone, or two or more kinds may be contained. Further, if necessary, other diol components such as 4,4′-bisphenol, hydroquinone, resorcinol, and 2,6-dihydroxynaphthalene are contained in the diol component of the polyarylate (A) in an amount of 20% by weight or less. Can be done.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyl ether-4,
4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid and the like can be mentioned. Of these compounds, isophthalic acid and terephthalic acid are particularly preferable. Examples of the aromatic dicarboxylic acid derivative include dihalides such as dichloride and diesters such as dialkyl esters and diaryl esters. The aromatic dicarboxylic acid and its derivative may be contained alone or in combination of two or more.

As a measure of the molecular weight of the polyarylate (A), the intrinsic viscosity (chloroform solution, 30 ° C.) is 0.2.
The range is preferably from to 1.5, more preferably from 0.4 to 0.8. When the intrinsic viscosity of the polyarylate (A) is outside the above range, the mechanical strength of the resulting thermoplastic resin,
The heat resistance and the fluidity during molding may decrease, which is not preferable.

Further, the above polyarylate (A) is prepared by using various polymerization methods such as an interfacial polycondensation method, a solution polycondensation method, a melt polycondensation method and the like, and the bisphenol and the aromatic dicarboxylic acid are mixed at a ratio of 1: 1. It can be produced by mixing in a molar ratio.

The modified polyolefin (B) contained in the resin composition of the present invention contains polypropylene as a main component.

The modified polyolefin is preferably
The constituents contained as repeating units are 100 to 80% by weight of propylene monomer, and ethylene, 1-butene, 1-
Pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 5-norbonanodiene, 1,3-cyclohexadiene, 1,
4-cyclohexadiene, 1,5-cyclohexadiene, 1,3-
It is 0 to 20% by weight of at least one monomer selected from cyclooctadiene, α, ω-non-conjugated dienes and the like.

Further, the modified polyolefin (B) is
One or more kinds of other unsaturated compounds, for example, vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylonitrile, styrene and the like may be contained in a small amount.

The modified polyolefin (B) has a structural unit having at least one amide group and at least one group selected from the group consisting of a glycidyloxy group and a glycidyl group and having 4 to 5000 carbon atoms. Have one per. When the number of carbon atoms is less than 4, a reaction occurs between the modified polyolefins, a reaction with the polyarylate (A) does not occur, and mechanical strength decreases. On the other hand, when the number of carbon atoms exceeds 5,000, the modification ratio in the modified polyolefin is small, so that the reaction with the polyarylate (A) is insufficient and the mechanical strength is lowered. Here, the glycidyloxy group is introduced into the polyolefin so that the modified polyolefin (B) can react with the carboxyl group, the hydroxyl group and the ester group in the polyarylate (A), and the amide group. The purpose of introducing is to impart hydrolysis resistance to the modified polyolefin (B) and prevent decomposition of the modified olefin (B) in the resin composition.

The above structural unit is preferably a structural unit represented by the following general formula [II].

[0023]

[Chemical 5]

(In the formula, Ar represents an aryl group having at least one glycidyloxy group and having 6 to 23 carbon atoms, and R ⁹ represents a hydrogen atom or a methyl group).

The structural unit is particularly preferably a structural unit represented by the following formula [III].

[0026]

[Chemical 6]

The structural unit having a glycidyloxy group represented by the general formula [II] is represented by the following general formula [IV]

[0028]

[Chemical 7]

(In the formula, Ar represents an aryl group having at least one glycidyloxy group and having 6 to 23 carbon atoms, and R ⁹ represents a hydrogen atom or a methyl group).

The modifier having a glycidyloxy group represented by is introduced by radical addition or copolymerization with the above polyolefin. Such a modifier can be produced according to the method described in Japanese Patent Publication No. 2-051550. The structural unit represented by the above formula [III] is introduced by the modifier represented by the following formula [V].

[0031]

[Chemical 8]

Further, the structural unit may be grafted to the polyolefin, or may be randomly copolymerized or block copolymerized in the polyolefin.

The amount of the modified polyolefin (B) grafted is preferably in the range of 0.1 to 50%, particularly preferably 0.5.
It is in the range of ~ 20%. If the graft amount is less than 0.1%, the mechanical strength of the resulting resin composition may be reduced, which is not preferable, and if the graft amount is more than 50%, the fluidity at the time of molding is lowered. It is not preferable because it may occur. Here, the graft amount means the weight ratio of the modifier contained in the modified polyolefin.

The method for producing the modified polyolefin (B) is not particularly limited, but the polyolefin and the modifying agent are melt-kneaded by using various blenders such as an extruder, a heat roll, a Brabender, and a Banbury mixer. Or a method of copolymerizing the above-mentioned polyolefin-constituting monomer and the above-mentioned modifier by a general polymerization method such as radical polymerization, cationic polymerization, anionic polymerization or coordination polymerization.

The thermoplastic resin composition of the present invention contains 10 to 90 parts by weight of polyarylate (A) and 90 to 10 parts by weight of modified polyolefin (B). When the content of the polyarylate (A) is less than 10 parts by weight, heat resistance is deteriorated, which is not preferable, and when the content of the polyarylate (A) exceeds 90 parts by weight, it is not preferable during molding. Is unfavorable because the fluidity and chemical resistance of the product deteriorate.

The method for producing the resin composition of the present invention is not particularly limited, but the melt mixing method is most preferable,
For example, melt mixing is performed by using various blenders such as an extruder, a hot roll, a Brabender, and a Banbury mixer. Further, at the time of mixing, the reaction between the polyarylate (A) having a carboxyl group, a hydroxyl group and an ester bond and the modified polyolefin (B) having a glycidyloxy group can be promoted by adding an appropriate catalyst. The catalyst is not particularly limited, but preferably includes amine compounds such as tertiary amines and quaternary ammonium salts; phosphorus compounds such as phosphonium salts and phosphines; imidazole compounds and the like, which may be used alone or Two or more kinds can be mixed and used.

If necessary, the resin composition of the present invention contains a lubricant such as wax, a phosphorus-based or phenol-based stabilizer, an ultraviolet absorber, a pigment, a flame retardant, a plasticizer, an inorganic filler, and a reinforcing agent. New functionality may be imparted by containing fibers and the like.

[0038]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto.

[Production of Polyarylate (A-1)] 52 parts by weight of bisphenol A and 47 parts by weight of a mixture of isophthalic acid dichloride and terephthalic acid dichloride (8: 2 molar ratio) were mixed, and the mixture was mixed with an interfacial weight. Polycondensation was carried out by law. The intrinsic viscosity of the obtained polyarylate was 0.57.

[Production of Modified Polypropylene (B-1)] Polypropylene having a melt flow rate (measured by JIS K6758) of 0.4 g / 10 minutes (Sumitomo Chemical Co., Ltd., Sumitomo Noblen D501, hereinafter D501) 100 parts by weight, the following formula [V]

[0041]

[Chemical 9]

3 parts by weight of a modifier having a glycidyloxy group represented by: and α, α'-bis (t-butylperoxy-m-isopropyl) benzene (manufactured by NOF Corporation)
Perbutyl P) 0.02 parts by weight, each of which is added at room temperature and mixed, and this mixture is a twin-screw extruder (TEX44 manufactured by Japan Steel Works).
Was extruded at 180 ° C. and pelletized. After the obtained pellets were dissolved in xylene heated to 130 ° C, this xylene solution was added dropwise to acetone to reprecipitate only the modified polypropylene, and the unreacted modifier and its undissolved modifier dissolved in the solution. The homopolymer was removed.

The amount of grafts obtained from the elemental analysis value of nitrogen in the obtained modified polypropylene was 1.2%, and this modified polypropylene was 1 per 511 propylene units.
It was found to have a number of structural units (the following formula [III]).

[0044]

[Chemical 10]

[Production of Modified Polypropylene (B-2)] In the production of the above modified polypropylene (B-1), α, α′-bis (t-butylperoxy-m-isopropyl) benzene is mixed with 0.0
Modified polypropylene (B-2) was prepared in the same manner as in the production of modified polypropylene (B-1) except that 1 part by weight was used.

The amount of graft of the modified polypropylene obtained was 1.3%, and it was found that this modified polypropylene had one structural unit (the above formula [III]) per 471 propylene units.

[Production of Modified Polypropylene (B-3)] In the production of the modified polypropylene (B-1), except that the extrusion temperature by the twin-screw extruder is 190 ° C. Modified polypropylene (B-
3) was created.

The amount of grafted modified polypropylene obtained was 1.6%, and it was found that the modified polypropylene had one structural unit (the above formula [III]) per 382 propylene units.

[Production of Modified Polypropylene (B-4)] In the production of the modified polypropylene (B-1), except that the modifier is 5 parts by weight and the extrusion temperature by the twin-screw extruder is 200 ° C., A modified polypropylene (B-4) was prepared in the same manner as the modified polypropylene (B-1).

The amount of grafted modified polypropylene obtained was 1.9%, and it was found that this modified polypropylene had one structural unit (the above formula [III]) per 321 propylene units.

[Production of Modified Polypropylene (B-5)] In the production of the modified polypropylene (B-1), except that the modifier is 7 parts by weight and the extrusion temperature by the twin-screw extruder is 200 ° C., A modified polypropylene (B-5) was prepared in the same manner as the modified polypropylene (B-1).

The graft amount of the modified polypropylene obtained was 3.0%, and it was found that this modified polypropylene had one structural unit (the above formula [III]) per 201 propylene units.

[Production of Modified Polypropylene (B-6)] In the production of the above modified polypropylene (B-1), a modifier is used in an amount of 10
Modified polypropylene (B-6) was prepared in the same manner as in the production of modified polypropylene (B-1) except that the weight part was used and the extrusion temperature by the twin-screw extruder was 200 ° C.

The amount of grafted modified polypropylene obtained was 4.1%, and it was found that the modified polypropylene had one structural unit (the above formula [III]) per 145 propylene units.

[Production of Modified Polypropylene (B-7)] Polypropylene having a melt flow rate (measured by JIS K6758) of 3.5 g / 10 minutes (Sumitomo Chemical Co., Ltd., Sumitomo Noblen H501, hereinafter referred to as H501) 100 parts by weight, 3 parts by weight of the modifier used in the production of the modified polypropylene (B-1),
0.07 parts by weight of α, α'-bis (t-butylperoxy-m-isopropyl) benzene was added and mixed at room temperature, and the mixture was mixed with a twin-screw extruder (TEX44 manufactured by Japan Steel Works)
Extruded at ° C and pelletized. The pellets obtained were freeze-pulverized, and then the unreacted modifier and its homopolymer were washed away with acetone.

The amount of grafted modified polypropylene after washing was 2.1%, and it was found that this modified polypropylene had one structural unit (the above formula [III]) per 290 propylene units.

Examples 1 to 10 Predetermined amounts of the above polyarylate (A-1) and modified polypropylene (B-1) to (B
-7) and were mixed, and the mixture was extruded at a temperature of 240 ° C. using a twin-screw extruder (TEX44 or LABOTEX manufactured by Japan Steel Works) to obtain a pellet-shaped resin composition.

Comparative Example 1 The above polyarylate (A-1) 100
Parts by weight were extruded at a temperature of 320 ° C. using a twin-screw extruder (LABOTEX manufactured by Japan Steel Works) to obtain a pellet-shaped resin composition.

(Comparative Example 2) The above polyarylate (A-1) 50
By weight, 50 parts by weight of polypropylene (D501) are mixed, and this mixture is twin-screw extruder (TEX44 manufactured by Japan Steel Works).
Was extruded at a temperature of 240 ° C. to obtain a pellet-shaped resin composition.

Comparative Examples 3 to 6 A predetermined amount of the above polyarylate (A-1) shown in Table 1 and polypropylene (H501) were mixed, and this mixture was mixed into a twin-screw extruder (made by Japan Steel Works, TEX4).
Using 4), it was extruded at a temperature of 240 ° C. to obtain a pellet-shaped resin composition.

Comparative Example 7 Polypropylene (H501) 100
After drying part by weight, it was molded as it was.

The physical properties of the resin compositions obtained in the above Examples and Comparative Examples were evaluated by the following methods.

1. Melt Viscosity The samples obtained in the above Examples and Comparative Examples were treated at 120 ° C.
After drying under reduced pressure for 15 hours at room temperature, melt viscosity measuring instrument (Toyo Seiki Co., Capirograph PD-C, die size: 1mmφ × 10m
m), melting time 5 minutes, measurement temperature 280 ° C, shear rate 121
The melt viscosity was measured under the measurement conditions of 6 s ^-1 . However, in Comparative Example 1, the measurement temperature was 300 to 320 ° C., and the melt viscosity at 280 ° C. was estimated.

2. Tensile Elongation at Break and Maximum Tensile Strength The samples obtained in the above Examples and Comparative Examples were treated at 120 ° C.
After drying under reduced pressure for 15 hours, injection molding was performed to obtain JIS No. 1 type dumbbell test pieces. ASTM-D63 for each test piece
Tensile breaking elongation and maximum tensile strength were measured according to 8.

3. Heat distortion temperature The samples obtained in the above Examples and Comparative Examples were treated at 120 ° C.
After drying under reduced pressure for 15 hours, injection molding was performed to prepare a test piece. For each test piece, a 1/4 inch bar was loaded and the heat distortion temperature was measured according to ASTM-D648.

4. Gasoline resistance The samples obtained in the above Examples and Comparative Examples were treated at 120 ° C.
After vacuum drying for 15 hours, injection molding was performed to obtain JIS No. 1 type dumbbells. A strain of 1% was applied to this test piece, and the state after standing in gasoline at 23 ° C. for 48 hours was evaluated according to the following criteria.

◯: Almost no change in appearance and cracks was observed Δ: Change in appearance or cracks were observed ×: Significant change in appearance or breakage.

The results of the above evaluation methods are shown in Table 1.

[0069]

[Table 1]

From Table 1, it can be seen that the resin composition of this example is excellent in moldability, mechanical strength, heat resistance and chemical resistance. First, as compared with the polyarylate-only resin compositions of Comparative Examples 1, 3 to 5 and 7, the resin composition of this example has an appropriate melt viscosity at 280 ° C., so injection molding at this resin temperature was performed. Is possible. Further, the resin composition of Comparative Example 1 breaks in the gasoline resistance test, but the resin composition of this example does not change its shape at all, and the chemical resistance is remarkably improved. Furthermore, the resin composition of this example has a higher tensile breaking elongation and a higher maximum tensile strength, and a higher heat distortion temperature than the resin compositions of Comparative Examples 2 to 7. From this, it is understood that the mechanical strength and heat resistance can be improved by incorporating the modified polypropylene having a glycidyloxy group.

[0071]

As is clear from the above description, the thermoplastic resin composition of the present invention has excellent fluidity during molding,
It also has excellent mechanical strength, heat resistance and chemical resistance. The molded product obtained from this composition can provide a suitable molding material for, for example, automobile parts, machine parts, electric / electronic device parts and the like.

Claims (10)

[Claims] 1. A polyolefin (A) of 10 to 90 parts by weight and a modified polyolefin (B) containing polypropylene as a main component.
A thermoplastic resin composition containing 90 to 10 parts by weight, wherein the modified polyolefin (B) comprises at least one amide group and at least one selected from the group consisting of glycidyloxy groups and glycidyl groups. A thermoplastic resin composition having one structural unit having a group per 4 to 5000 carbon atoms. 2. The polyarylate (A) comprises at least one diol component selected from the group consisting of a bisphenol represented by the following general formula [I] and a derivative of the bisphenol, an aromatic dicarboxylic acid and the The thermoplastic resin composition according to claim 1, which is an aromatic polyester having at least one dicarboxylic acid component selected from the group consisting of aromatic dicarboxylic acid derivatives as a constituent component. [Chemical 1] (In the formula, X is O, S, SO ₂ , CO, or 1 to 20 carbon atoms.
Represents an alkylene group or an alkylidene group having 2 to 20 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms or atoms). 3. The heat according to claim 1, wherein the polyarylate (A) is an aromatic polyester containing bisphenol A and a dicarboxylic acid selected from the group consisting of terephthalic acid and isophthalic acid as constituent components. Plastic resin composition. 4. The thermoplastic resin composition according to claim 1, wherein the intrinsic viscosity of the polyarylate (A) measured in chloroform at 30 ° C. is 0.2 to 1.5. 5. The structural unit of the modified polyolefin (B) is represented by the following general formula [II].
The thermoplastic resin composition according to. [Chemical 2] (In the formula, Ar represents an aryl group having at least one glycidyloxy group and having 6 to 23 carbon atoms, and R ⁹ represents a hydrogen atom or a methyl group). 6. A constituent component contained as a repeating unit other than the structural unit of the modified polyolefin (B),
100-80% by weight of propylene monomer, ethylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 5-norbonanodiene, 1,3-cyclohexadiene, 1,4-cyclo The resin composition according to claim 1, wherein the content of at least one monomer selected from the group consisting of hexadiene, 1,5-cyclohexadiene and 1,3-cyclooctadiene is 0 to 20% by weight. 7. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin (B) has a melt flow rate of 0.01 to 100 g / 10 minutes at 230 ° C. measured according to JIS K6758. 8. The thermoplastic resin composition according to claim 5, wherein the modified polyolefin (B) is grafted with the structural unit. 9. The thermoplastic resin composition according to claim 5, wherein the structural unit is randomly copolymerized or block copolymerized in the modified polyolefin (B). 10. The resin composition according to claim 1, wherein the structural unit contained in the modified polyolefin (B) is represented by the following formula [III]. [Chemical 3]