JPH0649340A - Thermoplastic bisphenol resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic bisphenol resin composition improved in lightweightness and injection moldability while retaining the strength and suitable for molded industrial parts and to provide a method for producing it. CONSTITUTION:The composition consists of 70-90 pts.wt. thermoplastic bisphenol resin (A) containing a bisphenol compound as the constituent monomer, 30-10 pts.wt. crystalline polypropylene (B) (the total of component A and component B being 100 pts.wt.), 20-200 pts.wt. (based on 100 pts.wt. component B) crystalline polyamide (C), and 20-100 pts.wt. (based on 100 pts.wt. component B) composition (D) consisting of 30-70 pts.wt. hydrogenated styrene/butadiene copolymer (D1) and 70-30 pts.wt. hydrogenated styrene/butadiene copolymer (D2) containing an acid radical (the total of component D1 and component D2 being 100 pts.wt.) and in which the peaks observed by the DSC with lowering temperature and assignable to component B and component C are combined into a single peak.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bisphenol-based thermoplastic resin suitable for an industrial part molded product which is lightweight and improved in injection moldability while maintaining strength, and a method for producing the same.

[0002]

2. Description of the Related Art Bisphenol-based thermoplastic resins such as polycarbonate and polyarylate are excellent in the balance of heat resistance, dimensional stability, mechanical strength and electrical characteristics.
It is used for components and housings in the fields of electronics and automobiles. That is, it is amorphous due to the conformation of bisphenol, and due to this, it has excellent dimensional stability, high rigidity, and excellent heat resistance. However, since the melt viscosity is high and the injection moldability is inferior to that of the crystalline thermoplastic resin, various improvements have been made.

However, in recent years, (1) weight reduction of specific gravity of about 1.20 to 1.25, (2) improvement of fluidity during injection molding and condition range during injection molding (in particular, injection pressure and There is an increasing demand for improving the susceptibility to burrs and shorts with respect to speed).

In order to meet these requirements, it has been proposed to blend a lightweight resin or a resin having good injection moldability with the above. Typical examples thereof are crystalline polypropylene and polyamide.

Regarding the blend of the bisphenol thermoplastic resin and the crystalline polypropylene, crystalline polypropylene modified with α, β-unsaturated acid or glycidyl ester of α, β-unsaturated acid is used as a compatibilizer. Many methods have been proposed. For example, JP-A-64
Japanese Patent Publication No. 75547 discloses a composition comprising an aromatic polycarbonate, a polyolefin, a modified polyolefin and polybutylene terephthalate.

The above modified polypropylene is used as a compatibilizing agent when the modified polypropylene reduces the interfacial tension between the continuous phase and the dispersed phase, reduces the particle size of the dispersed phase, and when these are coordinated to the metastasis. Is thought to have functioned as an adhesive phase. Although this technique is effective in reducing the weight and improving the injection moldability, the elongation and the toughness are largely reduced, and the field of use as a molding material is limited.
This is because polypropylene is a crystalline resin and therefore undergoes a large volume shrinkage, and the modified polypropylene, which is essentially poor in toughness, functions as a buffer phase against the behavior of interfacial peeling caused by this during the cooling and solidification process of the blend composition. It seems that it is not possible (the same problem occurs when the composition is subjected to impact when used as a molded article), and that it does not have an adhesive ability to compensate for these. .

Also proposed is a method of adding a copolymer having a reactive functional group to various bisphenol-based thermoplastic resin end groups and forming a compatibilizing agent by reacting the end group with the reactive functional group. Has been done. However, in this method, it is generally difficult to control the reaction because the content of the reactive functional group is large, and the viscosity of the composition may be further increased and the fluidity may be impaired if the addition amount is such that the effect becomes remarkable. Many. Further, if the molecular weight of the product of the reaction is excessively large, it acts as a gel or a foreign substance in the composition, so that the elongation is impaired.

[0008]

A method for obtaining a composition comprising a bisphenol-based thermoplastic resin and crystalline polypropylene using a hydrogenated styrene-butadiene block copolymer as a compatibilizer, or α, such as maleic anhydride, A method of using a hydrogenated styrene-butadiene block copolymer modified with β-unsaturated acid as a compatibilizing agent to obtain a composition consisting of a bisphenol-based thermoplastic resin and a polyamide is also considered. Problems related to insufficient toughness and deterioration of fluidity of the agent are solved to some extent.

However, when these blends are individually examined, the former is effective in improving the fluidity and the condition range at the time of injection molding and reducing the weight, but the strength is insufficient.
The latter is excellent in strength, but the fluidity and the condition range at the time of injection molding are improved, but the effect is not as great as the former and the effect of weight reduction is insufficient.

Therefore, a composition having both advantages is desired.

[0011]

In view of the above demands, the present inventor has selected a bisphenol-based thermoplastic resin suitable for an industrial part molded product, which has various characteristics while being lightweight and improved in injection moldability. The present invention has been achieved as a result of extensive studies to obtain the above.

That is, the first aspect of the present invention is: (A) 70 to 90 parts by weight of a bisphenol thermoplastic resin containing a bisphenol compound as a constituent monomer, (B) 30 to 10 parts by weight of a crystalline polypropylene (component A and The total amount of component B is 100 parts by weight.), (C) 20 to 200 parts by weight of crystalline polyamide (component B)
(Based on 100 parts by weight of crystalline polypropylene) and (D) a composition comprising the following component D1 and component D2 2
0 to 100 parts by weight (Component B crystalline polypropylene 1
(Per 00 parts by weight) (D1) Hydrogenated styrene-butadiene copolymer 30
To 70 parts by weight, (D2) acid group-containing hydrogenated styrene-butadiene copolymer 70 to 30 parts by weight (the total of the component D1 and the component D2 is 100 parts by weight), and the temperature-decreasing DSC. The present invention relates to a bisphenol-based thermoplastic resin composition, wherein the peaks attributed to the crystalline polypropylene (B) and the crystalline polyamide (C) observed above are combined into a single peak.

The second aspect of the present invention is the step (I): 70 to 90 parts by weight of a bisphenol thermoplastic resin containing a bisphenol compound as a constituent monomer of the component (A), and a crystalline polypropylene 30 to 10 of the component (B). Parts by weight (total of components A and B is 100 parts by weight), and component (D1) hydrogenated styrene-butadiene copolymer 30 to 70 parts by weight and component (D2) acid group-containing hydrogenated styrene-butadiene. The composition (component D) consisting of 70 to 30 parts by weight of the copolymer (the total of the components D1 and D2 is 100 parts by weight) is used as the component (B) 2 per 100 parts by weight of crystalline polypropylene.
A step of melt kneading 0 to 100 parts by weight to obtain a composition, and

Step (II): Component (C) crystalline polyamide is added to the composition obtained in the above step (I) as component (B).
20 to 200 per 100 parts by weight of crystalline polypropylene
A single peak in which the peaks attributed to the component (B) crystalline polypropylene and the component (C) crystalline polyamide observed on the temperature-lowering DSC are combined. Which is a bisphenol-based thermoplastic resin composition.

The present invention will be described in detail below.

The bisphenol-based thermoplastic resin containing a bisphenol-based compound as a constituent monomer used as the component (A) is a bisphenol A-based compound such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane). It refers to a thermoplastic resin that is contained as a main constituent monomer. Among these, in addition to the aromatic polycarbonate containing bisphenol A,
A wholly aromatic polyester (polyarylate) composed of a bisphenol A compound as a diol component such as bisphenol A and a phthalic acid compound as a dicarboxylic acid component such as terephthalic acid has preferable properties.

The crystalline polypropylene used as the component (B) means polypropylene and propylene-
A crystalline polymer containing propylene as a main monomer, such as an ethylene block copolymer, a propylene-ethylene random copolymer, and a propylene-α-olefin copolymer, which is clarified between 150 to 170 ° C. at a temperature rising DSC. Has an endothermic peak and a flexural modulus of 7,000 kgf
/ Cm ² or more. These may be used alone or in combination of two or more.

In the present invention, the bisphenol thermoplastic resin containing a bisphenol compound as a constituent monomer of the component A is 70 to 90 parts by weight, and the crystalline polypropylene as the component C is 30 to 10 parts by weight. Parts (however, the total of the components A and B is 100 parts by weight). Anything outside this range is difficult to achieve the effects of the present invention.

The "crystalline polyamide" used as the component (C) means an acid amide bond (-CONH-) in the molecule.
And specifically, ε-caprolactam,
Polymers or copolymers obtained from 6-aminocaproic acid, ω-enanthlactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone; hexamethylenediamine, nona Examples are polymers or copolymers obtained by polycondensation of diamines such as methylenediamine, undecamethylenediamine, dodecamethylenediamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid or mixtures thereof. To be done.

The crystalline polyamide as the component C is 20 per 100 parts by weight of the crystalline polypropylene as the component B.
-200 parts by weight are compounded. Anything outside this range is difficult to achieve the effects of the present invention.

Component (D) is hydrogenated styrene-
Butadiene copolymer (D1) 30 to 70 parts by weight and acid group-containing hydrogenated styrene-butadiene copolymer (D
2) A composition comprising 70 to 30 parts by weight. However,
The total of the components D1 and D2 is 100 parts by weight. Then, as the component D, 20 to 100 parts by weight is blended per 100 parts by weight of the crystalline polypropylene as the component B. Anything outside this range is difficult to achieve the effects of the present invention.

The "hydrogenated styrene-butadiene copolymer" used as the component (D1) is a carbon-carbon di-carbon which is present in the butadiene component of the styrene-butadiene block copolymer or the styrene-butadiene random copolymer. It is a polymer obtained by selectively hydrogenating only heavy bonds. The weight ratio of styrene / butadiene in the styrene-butadiene block copolymer or styrene-butadiene random copolymer before hydrogenation is 10/90 to
70/30. If it is less than 10/90, the strength is insufficient, and if it exceeds 70/30, it becomes brittle, which is not preferable. The preferred styrene / butadiene weight ratio is 20 /
80 to 50/50. The weight average molecular weight is 1 to 1.
If it is less than 10,000, the mechanical strength will be lowered, and if it exceeds 1 million, the dispersion in the composition will be deteriorated. The styrene portion may be composed of only styrene, or may be one obtained by polymerizing or copolymerizing substituted styrene such as methylstyrene. For example, Clayton G1652 (trade name, styrene / rubber weight ratio = 29/71) manufactured by Shell Chemical Co., Ltd., H1041, H1051 manufactured by Asahi Kasei Corporation, and Dynaron 1320P, 1910P manufactured by Nippon Synthetic Rubber Co., Ltd. can be exemplified. .

The acid group-containing hydrogenated styrene-butadiene copolymer used as the component (D2) means hydrogenated styrene-containing acid group such as carboxyl group.
It means a butadiene copolymer. Here, the definition of the styrene-butadiene copolymer is the same as that of the component D1.

In order to contain an acid group, an α, β-unsaturated carboxylic acid is copolymerized with styrene and butadiene, or the styrene-butadiene copolymer is modified by the copolymerization in the styrene-butadiene copolymer. An acid group is introduced into. The content of the acid group is preferably in the range of 0.05 to 5% by weight. If it is less than 0.05% by weight, the toughness may not be improved, and if it exceeds 5% by weight, the fluidity may deteriorate. None of them are preferable because they exist.

Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid.
Examples include β-unsaturated mono- or dicarboxylic acids and their anhydrides. Among these, acrylic acid and maleic anhydride are preferable. The content of these components is preferably in the range of 0.05 to 5% by weight. If the content is less than 0.05% by weight, the toughness may not be improved, and if it exceeds 5% by weight, the fluidity may deteriorate. .

To modify the styrene-butadiene copolymer, the styrene-butadiene copolymer and α, β-unsaturated carboxylic acid are heated and melted in the presence of a peroxide or heated in a suitable solvent. This is achieved by chemically bonding the two by dissolving them.

The styrene-butadiene copolymer in the component D2 is hydrogenated. The hydrogenation is usually carried out after copolymerization or modification of α, β-unsaturated carboxylic acid. If it is possible to introduce an acid group, it may be modified after hydrogenation. Here, the hydrogenation is to selectively hydrogenate only the carbon-carbon double bonds present in the butadiene constituent portion as in the case of the component D1.
These are, for example, Kraton FG1901X manufactured by Shell Chemical Co., Ltd. and Tuftec M manufactured by Asahi Kasei Corporation.
1943, M1911, M1913, Z513, Z51
4 etc. are illustrated

The components D1 and D2 can be blended separately, but it is usually appropriate to blend them as a composition in which they are premixed as the component D.

The composition of the present invention comprises the component (B) crystalline polypropylene and the component (C) observed on the temperature-decreasing DSC.
It is characterized by showing a single peak in which the peaks attributed to the crystalline polyamide are combined. That is, the blending amount of each component is adjusted so that a single peak appears.

Regarding the peaks of crystalline polypropylene and crystalline polyamide, the crystalline polyamide alone usually shows higher peaks. However, in the composition of the present invention, the component (B) crystalline polypropylene and the component (C) are used.
As for the peaks attributed to the crystalline polyamide, the peaks independently attributed are not detected, and instead, the respective peaks independently attributed are combined into a single peak. In the composition of the present invention, the peak attributed to the bisphenol-based thermoplastic resin containing the bisphenol-based compound as the component (A) constituent monomer is such that, as in the case of polycarbonate, the peak does not appear by itself. Naturally, it does not exist, and if it exists, it exists separately.

This indicates that the component (B) and the component (C) have a strong interaction in the composition of the present invention, and the composition which does not have this phenomenon is added. A composition in which each of crystalline polypropylene and crystalline polyamide exhibits a peak separately is not preferable because the effect of the present invention cannot be sufficiently exhibited. The peak position of the new single peak is usually located alone between the peaks assigned to crystalline polypropylene and crystalline polyamide, respectively.

Here, the temperature drop DSC is measured by lowering the temperature from the molten state of the resin at a rate of 20 ° C./min.

In the composition of the present invention, the crystalline polypropylene (component (B)) and the crystalline polyamide (component (C)) are not independently present in the bisphenol thermoplastic resin (component (A)), It is considered that the existence of the phase structure state having strong interaction gives the excellent properties.

Although the present composition has sufficient toughness, it is effective to further enhance the effect of the present invention by making the toughness inherent to the component (A) insufficient with a proper modifier. . That is, such a modifier can be appropriately added to the composition of the present invention.

Preferred modifiers satisfying these conditions are ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-
Ethylene / polar monomer copolymers such as ethyl acrylate-glycidyl methacrylate copolymer and ethylene-vinyl acetate-glycidyl methacrylate copolymer; graft copolymerization of polystyrene, polymethacrylate, polyacrylonitrile-styrene copolymer with these polar monomers Polymer; ethylene-propylene copolymer mainly composed of ethylene; hydrogenated styrene-butadiene-styrene block copolymer glycidyl methacrylate modified product; hydrogenated styrene-butadiene-styrene block copolymer, crosslinked acrylic rubber or Examples thereof include a rubber having a core-shell structure in which a butadiene-based rubber is used as a core and a copolymer containing a glycidyl ester of an α, β-unsaturated acid is used as a shell. These may be appropriately mixed and blended.

In order to obtain the composition of the present invention, the components A, B, C and D may be appropriately blended. However, in order to maximize the effects of the present invention, first, in step (I), a bisphenol-based thermoplastic resin containing a bisphenol-based compound as a component (A) constituent monomer, (B) crystalline polypropylene and (D) component. A method of obtaining a composition by melt-kneading a composition comprising D1 and component D2, and then adding a crystalline polyamide component (C) to the composition obtained in step (I) in step (II) It is preferable to adopt.

Although step (I) and step (II) can be carried out separately, step (I) and step (II) are preferably carried out continuously. That is, for example, component (A), component (B) and component (D) are melt-kneaded using a continuous kneading extruder, while a predetermined amount of component (C) is added to the kneading part of the kneader from the side feeder. And further melt-kneading.

The reason why the above method is preferred is not clear, but after the dispersed phase consisting of the component (B) and the component (D) is formed in the component (A), the component (C) becomes the “component (B)”. React with the component (D2) in the dispersed phase consisting of the component (D),
It seems that having strong interactions gives favorable results. Further, it is considered that this action also increases the viscosity of the dispersed phase and stabilizes the phase structure, which also gives favorable results.

As a device for melt kneading, conventionally known devices such as an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader and a twin screw extruder can be appropriately used.

Inorganic fillers and organic fillers can be added to the composition, if necessary. Further, a nucleating agent, a release agent, an antioxidant, a weather resistance agent, a lubricant, a heat stabilizer,
A colorant, an inorganic flame retardant, an organic flame retardant, a flame retardant aid, a foaming agent and the like may be added, within a range that does not impair the effects of the present invention.
Other thermoplastic resins may be added.

Since the composition of the present invention has excellent moldability, mechanical properties, chemical properties, electrical properties, heat resistance, weather resistance, paintability, etc., it is injection molded, blow molded, extrusion molded, press molded. Various useful molded products can be obtained by the thermoplastic resin molding technology currently used. A preferable method for molding a molded product is injection molding. Further, as an example of a product used as a molded product, it is suitable for a field where high performance is conventionally required as an engineering plastic, for example, a field of electrical / electronic parts such as a connector, a coil bobbin, a coupler, a housing, a keyboard, etc. Examples include the field of office equipment, the field of automobiles such as door handles, instrument panels, bumpers, and outer panels, and various other industrial containers, food containers, and the like.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples.

The contents of each component used in Examples and Comparative Examples are as follows. Component (A) (A1) Bisphenol A polycarbonate; trade name "UPILON S-2000" (manufactured by Mitsubishi Gas Chemical Co., Inc.) (A2) Porelate; trade name "U polymer U-10"
0 "(manufactured by Unitika Ltd.) (wholly aromatic polyester obtained by polycondensing bisphenol A and a mixed acid of terephthalic acid and isophthalic acid)

Component (B) (B1) polypropylene (homopolymer); MFR = 1.
5 (230 ° C / 2.16 kg load) (B2) polypropylene (ethylene-propylene block copolymer); MFR = 1.5 (B3) polypropylene (ethylene-propylene block copolymer); MFR = 1.5

Component (C) (C1) Polyamide-6; Medium viscosity product Trade name "MC-1"
20 "(made by Kanebo Co., Ltd.)

Component (D1) (D1-1) Hydrogenated styrene-butadiene-styrene block copolymer; styrene: butadiene ratio = 40: 60; MFR = 1.0 (230 ° C./2.16 kg load) (D1- 2) Hydrogenated styrene-butadiene-styrene block copolymer; styrene: butadiene ratio = 30: 70; MFR = 5.0 (230 ° C./2.16 kg load)

Component (D2) (D2-1) Hydrogenated styrene-butadiene-styrene block copolymer Maleic anhydride modified product; Styrene: butadiene ratio = 30: 60; MFR = 5.0 (230 ° C./2.16 kg) Load); Maleic anhydride addition amount = 0.3% by weight (D2-2) Hydrogenated styrene-butadiene-styrene block copolymer maleic anhydride modified product; Styrene: Butadiene ratio = 30: 60; MFR = 5.0 (230 ° C / 2.16kg load); Addition amount of maleic anhydride = 2.0% by weight

Other added components (E1) Hydrogenated styrene-butadiene-styrene block copolymer glycidyl methacrylate modified product; styrene: butadiene ratio = 30: 60; MFR = 5.0 (230 ° C./2.16 kg load); Amount of glycidyl methacrylate added = 0.4% by weight (E2) Core-shell type rubber; Core (acrylic rubber)
/ Shell (methyl methacrylate / methacrylic acid glycidyl ester copolymer); Methacrylic acid glycidyl ester content = 2% by weight Product name “Paraloid KCA-304” Kureha Chemical Industry Co., Ltd.

Production Method of Composition (1) Components (A), (B), (D1) and (D2) are blended in the predetermined amounts shown in the table, and further Irganox 1010 and Irgafos 168 (Japan) are added as antioxidants. 0.2 parts by weight of each was added and mixed with a Henschel mixer.

(2) Using the mixture obtained above,
Melt-kneading is carried out using a twin-screw continuous kneading extruder, and in the course of this melt-kneading, a predetermined amount of component (C) shown in the table is added from the side feeder to the kneading section of the kneader and further melt-kneaded. The strand was cut to obtain pellets of the composition.

(3) The above pellets were injection molded under the following conditions to obtain test pieces. Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 800-1,000 kg / cm ² Molding temperature 230-300 ° C Mold temperature 40-110 ° C

(4) The characteristics were evaluated by the following measuring methods. ● Mechanical Properties Tensile Yield Strength; ASTM D630 Tensile Fracture Elongation; ASTM D630 Flexural Modulus; ASTM D790 Izod Impact Value; ASTM D256

Injection molding condition range The obtained composition was subjected to a good injection molding condition, and the injection speed of injection molding was increased or decreased. The superiority or inferiority was evaluated as follows. It can be said that it is excellent as it is possible to set a wide range of conditions. ◎ = Extremely good ○ = Good Good △ = Narrow

● DSC Temperature Drop Characteristics A thin piece was cut out from each composition pellet, and the DSC characteristic curve was measured by lowering the temperature from the molten state of the resin at 20 ° C./min. The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

[0055]

EFFECT OF THE INVENTION The thermoplastic resin composition according to the present invention exhibits an extremely excellent balance of mechanical strength, elongation, impact resistance, light weight and moldability. Therefore, it can be widely used in various fields such as electric / electronic parts, office equipment, automobile parts, and containers, which require high performance.

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Claims (2)

[Claims] 1. A bisphenol-based thermoplastic resin containing a bisphenol-based compound as a constituent monomer (A).
70 to 90 parts by weight, (B) crystalline polypropylene 30 to 10 parts by weight (total of component A and component B is 100 parts by weight), (C) crystalline polyamide 20 to 200 parts by weight (component B)
(Based on 100 parts by weight of crystalline polypropylene) and (D) a composition comprising the following component D1 and component D2 2
0 to 100 parts by weight (Component B crystalline polypropylene 1
(Per 00 parts by weight) (D1) Hydrogenated styrene-butadiene copolymer 30
To 70 parts by weight, (D2) acid group-containing hydrogenated styrene-butadiene copolymer 70 to 30 parts by weight (the total of the component D1 and the component D2 is 100 parts by weight), and the temperature-decreasing DSC. A bisphenol-based thermoplastic resin composition, wherein the peaks attributed to the component (B) crystalline polypropylene and the component (C) crystalline polyamide observed by the above are combined into a single peak. 2. Step (I): 70 to 90 parts by weight of a bisphenol-based thermoplastic resin containing a bisphenol-based compound as a constituent monomer of component (A), 30 to 10 parts by weight of crystalline polypropylene of component (B) (with component A) The total amount of component B is 100 parts by weight), and component (D1).
Hydrogenated styrene-butadiene copolymer 30 to 70 parts by weight and component (D2) acid group-containing hydrogenated styrene-
Butadiene copolymer 70 to 30 parts by weight (the total of component D1 and component D2 is 100 parts by weight) A composition (component D) is a component (B) crystalline polypropylene 100.
A step of melt-kneading 20 to 100 parts by weight per part by weight to obtain a composition, and step (II): Component (C) crystalline polyamide is added to the composition obtained in step (I) above as component (B) crystal Of 20 to 200 parts by weight per 100 parts by weight of the crystalline polypropylene, and melt-kneading, characterized in that the component (B) crystalline polypropylene and the component (C) crystalline polyamide observed by temperature-falling DSC belong to the crystalline polyamide. A method for producing a bisphenol-based thermoplastic resin composition having a single peak in which the peaks are combined.