JPH02305850A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To form a thermoplastic resin composition excellent in the balance among properties such as chemical resistance, impact resistance, heat distortion resistance and processability by mixing a resin composition comprising an aromatic polyester, a polyamide and an impact resistance modifier with a specified lubricant. CONSTITUTION:This thermoplastic resin composition comprises 100 pts.wt. resin composition (A) comprising 20-80wt.% aromatic polyester, 20-80wt.% polyamide and at most 40wt.% impact resistance improver; and 0.01-5 pts.wt. at least one lubricant (B) selected from among a carboxylic acid, a metal carboxylate, an amide compound and an ester compound. As the aromatic polyester in component A, for example, one obtained by reacting terephthalic acid with a bisphenol can be used, or one having a weight-average MW (in terms of polystyrene) of 10000-100000 and an acid value of 20-150mu equivalents/g is desirable. Examples of the above impact resistance improver include a modified polyolefin polymer and a graft copolymer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a resin composition having a specific composition consisting of an aromatic polyester, a polyamide, and an impact modifier.
Regarding the thermoplastic resin composition formed by blending the agent, for example, it is suitable for use as a molding material, has heat deformation resistance, chemical resistance,
The present invention relates to a thermoplastic resin composition with an excellent balance of physical properties such as impact resistance and processability.

[Prior Art and Problems to be Solved by the Invention] Conventionally, thermoplastic resin compositions comprising aromatic polyesters, polyamides, and impact modifiers have been widely known as plastic molding materials.

Although the conventional thermoplastic resin compositions described above are excellent in heat deformation resistance, chemical resistance, and impact resistance, their processability is not fully satisfactory.゛When trying to obtain a product with particularly excellent heat deformation resistance, the melt viscosity during processing is high (
It is known that the flowability as indicated by the spiral flow value (flow length) is poor (because of this, the processability tends to be poor).

Various proposals have been made to overcome these drawbacks; for example, thermoplastic resin compositions made of aromatic polyester, polyamide, and linear hydrocarbons having a weight average molecular weight of 300 to 10,000 are known ( JP-A-57-1
(See Publication No. 90042).

However, since the aromatic polyesters and polyamides and the hydrocarbons have greatly different polarities, the thermoplastic resin compositions have a problem in that peeling occurs on the surface of the resulting molded product.

As a result of extensive research, the present inventors solved the above problem by blending aromatic polyester, polyamide, and impact modifier in a predetermined ratio with a predetermined amount of a specific lubricant. We have obtained knowledge that it can be solved.

The present invention has been made based on this knowledge, and aims to provide excellent chemical resistance, impact resistance, heat deformation resistance, and workability, as well as to prevent discoloration, discoloration, silver, and silage due to processing. There are few surface defects such as (
The object of the present invention is to provide a thermoplastic resin composition that does not easily peel off and has an excellent balance of physical properties.

[Means to solve espionage J]

The thermoplastic resin composition according to the present invention to achieve the above object (hereinafter referred to as "the composition of the present invention") is an aromatic polyester (hereinafter referred to as "boaryarylate") 20 to 8
Resin composition (A) consisting of 0% by weight, 20 to 80% by weight of polyamide, and 40% by weight or less of impact modifier (A) 10
0 parts by weight, and 0.01 to 5 parts by weight of at least one type of lubricant (B) selected from the group consisting of carboxylic acids, carboxylic acid metal salts, amide compounds, and ester compounds.

The polyarylate, which is a component of the resin composition (A), is represented by the following general formula (1) and at least one dibasic acid selected from the group consisting of, for example, isophthalic acid, terephthalic acid, and derivatives thereof. It is synthesized by reacting a small amount of bisphenols or their derivatives.

(However, in the above formula, -X- is -0-1-S-1SO2-
1-CO-, alkylene group or alkylidene group; R1
, R2, R3, R4, R5, R1, R? and R1 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group. ] As the bisphenols represented by the above formula (1), 4.4°-dihydroxydiphenyl ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone, Bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethyl)methane, 1.1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)-diphenylmethane, 2.2-bis(4-hydroxy-3,5-
dichlorophenyl)propane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4
-hydroxynaphthyl)propane, 2,2-bis(4-
hydroxyphenyl) propane (also known as "bisphenol AJ"), bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, Examples include 4.4'-dihydroxybenzophenone.

Derivatives of the above bisphenols include their alkali metal salts, diacetates, and the like.

Note that, if necessary, a small amount of a divalent compound such as 4,4°-biphenol, hydroquinone, resorcinol, or 2,6-hydroxynaphthalene may be added to the bisphenols or derivatives thereof.

Examples of the derivatives of isophthalic acid or terephthalic acid include dichloride of isophthalic acid or terephthalic acid; or diesters of alkyl, aryl, etc., in which the hydrogen atom in the phenylene group is substituted with a halogen atom or an alkyl group, etc. It's okay.

The bisphenols represented by the above formula (1) may be used alone or in combination of two or more.

The above polyarylate is composed of isophthalic acid or a derivative thereof, terephthalic acid or a derivative thereof, and the above formula (1
) and a bisphenol represented by () or a derivative thereof using a conventionally known polymerization method such as an interfacial polymerization method, a solution polymerization method, or a melt polymerization method.

The weight average molecular weight of the above polyarylate is based on polystyrene standards! If the weight average molecular weight is outside this range, the balance of physical properties such as heat deformation resistance, impact resistance, chemical resistance and processability will deteriorate.

In addition, the above polyarylate has an acid value (unit: 2μ equivalent/gram (μ; 10”)), which is the value obtained by titrating a solution dissolved in tetrachloroethane with a benzyl alcohol solution of sodium hydroxide using phenol red as an indicator. ) is preferably within the range of 20 to 150; if the acid value is outside this range, impact resistance or thermal stability may decrease.

More preferably, the acid value is within the range of 30 to 110.

Examples of the polyamide that is another component of the composition of the present invention include those represented by the following general formula (2) or (3).

[However, in the above formulas (2) and (3), R1, R111 and R1+ are each independently a phenylene group or an alkylene group. ] The polyamide blended in the present invention includes those produced by polycondensation reaction of diamine and dibasic acid, self-condensation reaction of amino acid, and ring-opening polymerization reaction of lactam.

Specific examples include polytetramethylene adipamide, polyhexamethylene adipamide, poly(ε-caprolactam), and polyhexamethylene sebacamide.

Moreover, the above-mentioned polyamide may be a copolymer of two or more types, or a mixture of two or more types.

Furthermore, the above polyamide has a melt viscosity of 2 in terms of relative viscosity.
．． 0-5.0 (i11 degrees 1% concentrated sulfuric acid solution, 25'
Those within the range of C) are preferred; outside this range,
This is undesirable because impact resistance, chemical resistance, or processability decreases.

Furthermore, the above polyamide has an amine value (unit: μ
Equivalent/g, a solution dissolved in m-cresol at a temperature of 80° C. in a nitrogen stream was prepared using thymol blue as an indicator. It is preferable that the value (as determined by titration with IN hydrochloric acid) is within the range of 20 to 80. Outside this range, the thermal stability or impact resistance will deteriorate, which is not preferable.

Examples of the impact modifier include modified polyolefin polymers and graft copolymers.

The modified polyolefin polymer has 2 to 2 carbon atoms.
30 α-olefins, or 1-butene, 4-methyl-1-pentene, isobutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, butadiene, isoprene, etc. The main component is a diene compound, and at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, an acid anhydride group, an epoxy group, an acid amide group, and an imide group. Examples include those modified by introducing a monomer having the following.

Examples of monomers having one type of functional group include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Itaconic acid, methyl hydrogen maleate, methyl acrylate, ethyl acrylate, acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, aminoethyl methacrylate, dimethyl maleate, sodium acrylate, methacrylate sodium acid, potassium acrylate, potassium methacrylate, magnesium acrylate, magnesium methacrylate, zinc methacrylate, maleic anhydride, itaconic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylamide, methacrylamide , maleimide, and phenylmaleimide.

Even if not mentioned above, a monomer having one kind of functional group can be introduced by copolymerizing with an α-olefin or the like or a polyolefin polymer. The monomer having this functional group is preferably used in an amount of 0.1 to 30% by weight based on 100% of the total amount of the impact modifier.

Outside this range, impact resistance and workability may deteriorate, which is not preferable.

The above modified polyolefin polymer as an impact modifier has a melt index of 0.05 to 50 grams71
Those having a polymerization degree within the range of 0 minutes, preferably 0.1 to 30 grams/10 minutes may be appropriately selected and used.

Examples of the above-mentioned graft copolymers include those obtained by graft-polymerizing a specific component onto a rubber-like elastic body.

The rubber-like elastic body preferably has a glass transition temperature of 0°C or lower, more preferably -40°C or lower.

Examples of the rubber-like elastic body include diene rubbers such as polybutadiene, butadiene-styrene copolymer, and butadiene-butyl acrylate copolymer; acrylic rubbers such as butyl polyacrylate and 2-ethylhexyl polyacrylate;
Examples include olefin rubbers such as ethylene-propylene copolymer and ethylene-propylene-diene copolymer.

The gel content of the rubber-like elastic body is not particularly limited, but
The content is preferably 10% by weight or more.

The rubber-like elastic body can be in various shapes such as powder, pellet, latex, etc.
When using a latex-like material, the average particle diameter is 0.
It is preferable to use a material with a diameter of 05 to 2 μm. 'Specific components to be graft-polymerized to the rubber-like elastic body include a vinyl monomer, a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, an acid Examples include monomers containing at least seven types of functional groups selected from the group consisting of anhydride groups, epoxy groups, acid amide groups, and imide groups.

Examples of the vinyl monomers include aromatic vinyl monomers such as styrene, methylstyrene, chlorostyrene, and α-methylstyrene, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Ru.

Monomers having the above functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and methacrylic acid. 2-ethylhexyl, maleic anhydride, itaconic anhydride, glycidyl acrylate, acrylamide,
Examples include methacrylamide, maleimide and phenylmaleimide.

The composition weight ratio of the rubber-like elastic body and the specific monomer is preferably 30 to 95% by weight of the rubber-like elastic body and the balance of the specific monomer.Out of this range, impact resistance, rigidity, etc. This is not preferable because it may cause a decrease in the temperature or cause molding defects.

The composition of the above-mentioned specific component is not particularly limited, but it is preferably a monomer containing 50 to 99.9% by weight of vinyl monomer and the remainder having functional groups.If it is outside the above range, impact resistance will decrease. This is undesirable because it may cause the process to deteriorate or the processability to deteriorate.

In addition, the composition of the vinyl monomer is not particularly limited, but
It is preferable that the aromatic vinyl monomer is 40 to 90% by weight and the balance is vinyl cyanide monomer. Outside the above range, it is not preferable because the impact resistance and thermal stability will decrease. .

The above-mentioned graft copolymer can be produced using various conventionally known polymerization methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization.

The lubricant (B) used in the present invention is a carboxylic acid, a carboxylic acid metal salt, an amide compound, or an ester compound.

Examples of the above carboxylic acids include lauric acid, palmylatic acid, stearic acid, oleic acid, montanic acid, etc. having a carbon number of 1.
Examples include 2 to 50 fatty acids.

Examples of the carboxylic acid metal salts include lauric acid, balmitic acid, stearic acid, montanic acid, etc. having 12 to 5 carbon atoms.
Examples include calcium salts, barium salts, aluminum salts, magnesium salts of fatty acids, and partially saponified calcium salts of montanic acid esters.

Examples of the above-mentioned amide compound include palmylatinamide, stearamide, oleic acidamide, methylenebisstearylamide, and ethylenebisstearylamide.

The above ester compounds include octyl stearate,
Examples include stearyl stearate, hardened mustard oil, alcohol esters of fatty acids such as ethylene glycol monostearate, polyhydric alcohol esters, glycol esters, and polyhydric glycol esters.

The composition ratio of the resin composition (A) is polyarylate 20-8
0% by weight, 20-80% by weight of polyamide and 40% by weight of impact modifier. A suitable blending ratio of the impact modifier is 0.01 to 40% by weight.

If the composition ratio of the above three components is out of this range, the balance of physical properties such as heat deformation resistance, impact resistance, rigidity, workability, etc. will deteriorate. The preferred composition ratio of the resin composition (A) is 25 to 70% by weight of polyarylate, 25 to 75% by weight of polyamide, and 5 to 20% by weight of impact modifier (the total amount of the three components is 100%).
).

The lubricant (B) is blended in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition (A). 0.0
If the amount is less than 1 part by weight, the effect of addition will not be fully expressed, and if it exceeds 5 parts by weight, the effect of addition corresponding to the increase in amount will not be obtained and it will be uneconomical.
, heat deformation resistance, etc. may actually deteriorate.

The method for producing the composition of the present invention is not particularly limited, and for example, a resin composition (A) consisting of a polyarylate, a polyamide, and an impact modifier and a lubricant (B) are simultaneously premixed.
The resin composition may be fed into a single-screw or twin-screw extruder and melt-kneaded to form pellets, or after a part of the resin composition is melt-kneaded, the remaining part may be added thereto and melt-kneaded to form pellets. (A) may be pelletized by various methods, and the lubricant (B) may be added thereto.

In addition, if necessary, stabilizers such as phosphorus-based and phenol-based stabilizers; pigments; waxes, metal soaps, ultraviolet absorbers; flame retardants; plasticizers; fillers such as glass fiber and talc may be added as appropriate. It may be added to impart new functionality to the composition of the present invention.

〔Example〕

Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to the following Examples, and can be implemented with appropriate changes within the scope of the gist.

A. Preparation of each component ■ By polyarylate interfacial polymerization method, polyarylate 1 and polyarylate 2 having the following composition, weight average molecular weight, and acid value were obtained.
was manufactured.

(Bolyarylate 1) Obtained by reacting binary phthalic acid with a molar ratio of terephthalic acid and isophthalic acid of 7/3 and 2,2bis(4゛-hydroxyphenyl)propane in an equimolar ratio. , a polyarylate having a weight average molecular weight (M w ) of 60,000 and an acid value of 35.

(Bolyarylate 2) A polyarylate having a weight average molecule i1 (M w ) of 70,000 and an acid value of 80, obtained by reacting isophthalic acid and 2.2bis(4°-hydroxyphenyl)propane in an equimolar ratio.

(2) Polyamide Poly(ε-caprolactam) (manufactured by Ube Industries, Ltd., trade name: rLO22B) having a solution viscosity of 3.1 in relative viscosity and an amine value of 35 was used as the polyamide.

■Impact resistance modifier As an impact resistance modifier, the following impact resistance modifier-1 is used.
~Impact resistance modifier-4 was used.

(Impact resistance modifier 1) Ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name "Bondfirth" EJ).

(Impact resistance modifier 2) Ethylene-ethyl acrylate-maleic anhydride copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: “Bondine AX-8390J”)
).

(Impact resistance modifier 3) Ethylene-propylene copolymer grafting (maleic anhydride copolymer) (manufactured by Japan Synthetic Rubber Co., Ltd., trade name rT-771
13PJ).

(Impact resistance modifier 4) A product obtained by graft copolymerizing 70% by weight of polybutadiene with an average particle diameter of 0.25 μm and a gel content of 83%, 7% by weight of acrylonitrile, 20% by weight of styrene, and 3% by weight of glycidyl methacrylate. .

■Lubricant (B) The following B-1 to B-5 were used as lubricants.

(Lubricant B-1) Stearic acid (Lubricant B-2) Calcium stearate (Lubricant B-3) Ethylene bisstearylamide (Lubricant B-4) Stearyl stearate (Lubricant B-5) Paraffin wax (weight average molecular weight) B, Preparation of thermoplastic resin composition The above polyarylates 1 to 9, polyamide, impact modifiers 1 to 4, and lubricants B-1 to B-5 were premixed in the proportions shown in the table, and the mixture was mixed at a temperature of 80''C for 10 minutes. After vacuum drying for an hour,
The mixture was melt-kneaded using a twin-screw extruder to obtain a pellet-shaped thermoplastic resin composition. In addition, in Example 9, lubricant (
B) was added to the pellet-shaped resin composition (A) consisting of polyarylate, polyamide, and impact modifier and blended by melt-kneading.

C0 various evaluation tests Each resin composition obtained was injection molded to prepare a test piece,
For each test piece, Izot impact strength, heat distortion temperature, tensile strength, spiral flow length, and moldability were measured using the following measuring methods.

<Izotsu impact strength (kg-cm/cm)>AST
Measured according to MD-256 (punch diameter 1/8 inch, ambient temperature 23°C).

<Heat distortion temperature ('C)> Load 4.6 kg/c according to ASTM D-648
4 (measured for case D).

Tensile strength (kg/C11) > Measured in accordance with ASTM D-638 (environmental temperature 2
3°C).

<Spiral flow value (■)> Using a 5-ounce injection molding machine, the cylinder temperature was 280°
Under the conditions of C1 injection pressure 120 kg/d (gauge pressure) and mold temperature 80°C, the gate cross section is 3III11×31!
A spiral mold with a width of 1I11 and a thickness of 3III11 was installed to measure the flow length.

<Moldability l> Using a 35-ounce injection molding machine, the cylinder temperature was 280°C.
'C1 injection pressure 110 kg/cm (gauge pressure),
A box-shaped molded product weighing approximately 500 grams was molded at a mold temperature of 80°C, and the molded product was colored, flow marks, silver,
The uniformity of the surface was visually observed, and the moldability was evaluated based on the following criteria.

O: There are almost no defects.

Δ: Some defects are present.

×: There are significant defects.

Molding processability ■〉 Using the same molded product as that manufactured in the molding processability test above, cut the area near the gate with a knife, observe the presence or absence of peeling on the surface, and evaluate the moldability according to the following criteria. was evaluated.

O: No peeling was observed.

×: Peeling is observed.

The table shows the results of each measurement.

(Hereinafter, blank space) As is clear from the table, the composition of the present invention has a large spiral flow value (and has excellent processability, such as a uniform surface of the resulting molded product and is less likely to peel off), as well as heat resistance. It can be seen that it is a plastic molding material with an excellent balance of physical properties since it is excellent in all points of deformability, impact resistance, and tensile strength (Examples 1 to 9).

On the other hand, all of Comparative Examples 1 to 4 were inferior in either surface uniformity or peeling resistance, and except for Comparative Example 4, all had small spiral flow values and poor workability. In addition to being inferior, the physical properties of heat deformation resistance, impact resistance, and tensile strength are unbalanced, and there are practical problems as a molding material.

(Effects of the Invention)' As explained in detail above, when the composition of the present invention is used as a molding material and molded by various molding methods such as injection molding, extrusion molding, blow molding, and compression molding, various automobile parts and mechanical parts , heat deformation resistance suitable for use as electrical/electronic parts, etc.
The present invention has excellent effects, such as making it possible to obtain a plastic molded product with an excellent balance of physical properties such as impact resistance and processability.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a resin composition (A) comprising 20 to 80% by weight of aromatic polyester, 20 to 80% by weight of polyamide, and 40% by weight or less of an impact modifier; and a carboxylic acid, carboxylic acid. A thermoplastic resin composition comprising 0.01 to 5 parts by weight of at least one lubricant (B) selected from the group consisting of acid metal salts, amide compounds, and ester compounds. 2. Aromatic polyester 20-80% by weight, polyamide 20-80% by weight and impact modifier 0.01-40%
100 parts by weight of a resin composition (A) consisting of % by weight, and 0.01 to 5 parts by weight of at least one lubricant (B) selected from the group consisting of carboxylic acids, carboxylic acid metal salts, amide compounds, and ester compounds. The thermoplastic resin composition according to claim 1, comprising: 3. Aromatic polyester 25-70% by weight, polyamide 25-70% by weight and impact modifier 5-20% by weight
100 parts by weight of a resin composition (A) consisting of 0.01 to 5 parts by weight of at least one lubricant (B) selected from the group consisting of carboxylic acids, carboxylic acid metal salts, amide compounds, and ester compounds. The thermoplastic resin composition according to claim 1. 4. The thermoplastic resin composition according to claim 1, wherein the aromatic polyester has a weight average molecular weight (polystyrene equivalent) of 10,000 to 100,000 and an acid value of 20 to 150 μeq/g. 5. The thermoplastic according to claim 1, wherein the aromatic polyester has a relative viscosity of 2.0 to 5.0 (1% concentrated sulfuric acid solution, 25°C) and an amine value of 20 to 80 μeq/g. Resin composition. 6. The impact modifier has at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, an acid anhydride group, an epoxy group, an acid amide group, and an imide group. Claims 1 to 3 are modified polyolefin polymers containing as a main component an α-olefin having 2 to 30 carbon atoms, into which at least one monomer having the following is introduced:
5. The thermoplastic resin composition according to any one of 5. 7. The impact resistance modifier includes a rubber-like elastic body containing a vinyl monomer, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an epoxy group, an acid amide group, and an imide group. The thermoplastic resin composition according to any one of claims 1 to 5, which is a graft copolymer obtained by graft copolymerizing with at least one selected monomer having at least one selected functional group.