WO2006025546A1

WO2006025546A1 - Thermoplastic resin composition

Info

Publication number: WO2006025546A1
Application number: PCT/JP2005/016163
Authority: WO
Inventors: Yoshiaki Taguchi; Toru Katsumata; Toshio Shiwaku
Original assignee: Polyplastics Co., Ltd.
Priority date: 2004-08-31
Filing date: 2005-08-29
Publication date: 2006-03-09
Also published as: JP2006070086A

Abstract

A thermoplastic resin composition which comprises 100 parts by weight of a polyethersulfone resin (A) and 5 to 80 parts by weight of a liquid crystalline polyesteramide resin (B) which comprises, as a component monomer, one or more of 4-aminophenol, 1,4-phenylene diamine, 4-aminobenzoic acid and the derivatives thereof and contains an amide component in a proportion of 15 to 35 mole % in the total bonds. The above thermoplastic resin composition exhibits high rigidity and high fluidity, is reduced in the exfoliation of the surface of a formed article and is excellent in appearance, and thus can be suitably used for parts of a mechanism for an automobile and for parts of a mechanism for electrical and electronic products.

Description

Technical Field Thermoplastic Resin Composition Technical Field

The present invention relates to a thermoplastic resin composition suitably used for injection-molded articles and the like, comprising a polyethersulfone resin, a liquid crystalline polyesteramide resin, and a force. More specifically, the present invention relates to a thermoplastic resin composition that significantly improves the fluidity of a polyethersulfone resin as a matrix and has high rigidity. Prior art

Liquid crystal resins have a good balance of excellent fluidity, mechanical strength, heat resistance, chemical resistance, and electrical properties and are therefore widely used as high-performance engineering plastics.

Along with the remarkable industrial development in recent years, the applications of such liquid crystal resins are also becoming increasingly sophisticated and specialized, and by utilizing the high fluidity of liquid crystal resins, they can be molded efficiently and economically by injection molding etc. Thus, it has been expected to obtain an injection molded product that retains its excellent physical properties. For example, automotive outer plate materials, electrical / electronic housings, etc. are also required to have high mechanical properties and high heat resistance in order to reduce the weight and thickness of molded products, and are large and have a high appearance. A resin material from which a molded body can be obtained is required. However, the appearance of molded products is not preferred for automotive outer plate materials and electrical / electronic housings, and from the viewpoint of cost, liquid crystal resins are difficult to use for large products. there were.

On the other hand, the conventional polyethersulfone resin has an excellent appearance, but it has been difficult to satisfy these requirements, particularly high mechanical properties and fluidity. Therefore, a resin composition of a polyethersulfone resin and a liquid crystal resin has been studied. For example, JP-A 1-2 5 2 6 5 7 attempts to improve mechanical properties by using a resin composition of a polyethersulfone resin and a liquid crystal resin. Further, JP_A 2 -140 0 2 6 7 studies the resin composition strength of a polyethersulfone resin, a liquid crystalline polyesteramide resin, and a reinforcing fiber. However, when used in automotive mechanical parts and electrical / electronic product mechanical parts, which have recently been required to have high required characteristics, it is difficult to say that these prior art techniques have solved this problem. Disclosure of the invention

The present invention solves the above-mentioned problems of the prior art, has high rigidity and high fluidity, and further has excellent appearance with little peeling of the surface of the molded body, mechanism for automobiles and mechanisms for electric and electronic products. It aims at providing the thermoplastic resin composition used suitably for components. As a result of diligent research to achieve the above object, the present inventors have formulated a specific polyethersulfone resin as a matrix by blending a specific liquid crystalline polyesteramide resin with the polyethersulfone resin as a matrix. The inventors have found that a thermoplastic resin composition having excellent fluidity and appearance can be obtained while significantly improving rigidity and maintaining heat resistance, and has completed the present invention.

That is, the present invention is based on 100 parts by weight of the polyethersulfone resin (A). As a constituent monomer, 4-aminophenol, 1,4_phenylenediamine, 4-aminobenzoic acid and one of these derivatives are used. Or a liquid crystalline polyester amide resin (B) containing at least 2 types and containing an amide component in a proportion of 15 to 35 mol% in the total bond It is a resin composition.

The thermoplastic resin composition comprising the polyethersulfone resin (A) of the present invention and the specific liquid crystalline polyesteramide resin (B) has high rigidity and high fluidity, and further the surface of the resulting molded article Is excellent in appearance without peeling. Excellent fluidity, heat distortion temperature Therefore, it is suitable for mechanical parts for automobiles and mechanical parts for electric / electronic products. Detailed Description of the Invention

Hereinafter, the resin composition constituting the present invention will be described in detail step by step. The polyethersulfone resin (A) used in the present invention has the following formula (I)

— P h _ S〇 ₂ — P h—〇一 (I)

(In the formula, Ph represents 1,4-phenylene)

And a copolymer containing such a unit, and is not particularly limited. Examples of commercially available polyethersulfone resins include Ultra Zone E manufactured by BASF and Sumikaxel P ES manufactured by Sumitomo Chemical Co., Ltd.

The liquid crystalline polyesteramide resin (B) used in the present invention refers to a melt-processable polyesteramide having a melting point in the range of 270 to 370 ° C. and capable of forming an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere. . When the liquid crystalline polyesteramide applicable to the present invention is examined between crossed polarizers, polarized light is usually transmitted even in the molten stationary state, and optically anisotropic.

The liquid crystalline polyester amide used in the present invention is not only sufficient to have the property of forming an optically anisotropic molten phase as described above, but must have a specific structural unit. is there. That is, examples of the monomer constituting the liquid crystalline polyesteramide resin (B) include aromatic hydroxycarboxylic acid, aromatic carboxylic acid, aromatic diol, etc. In addition to these monomers, 4-aminophenol, 1, It is necessary to include 4-phenylenediamine, 4-aminobenzoic acid and one or more of these derivatives, and that the amide component is contained in a proportion of 15 to 35 mol% in all bonds. . Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 6-hydroxy 2-naphthoic acid, and examples of aromatic carboxylic acids include terephthalic acid, isophthalic acid, and 4,4'-diphenyldicarboxylic acid. 2,6-Naphthalenedicarboxylic acid and the like, and aromatic diols include 2,6-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol and the like. In addition, derivatives of these compounds can also be mentioned as monomers.

Examples of the monomer for including the amide component in a proportion of 15 to 35 mol% include the aforementioned 4-aminophenol, 1,4-diphenylamine, 4-aminobenzoic acid, and derivatives thereof.

Specifically, the liquid crystalline polyesteramide resin (B) is preferably a wholly aromatic polyesteramide obtained by copolymerizing the monomers (i) to (iiii) below within the ranges described below.

(i) 6-hydroxy-2-naphthoic acid; 30-90 mol%

(Ii) 4-Aminophenol; 15-35 mol%

(i i i) terephthalic acid; 15-35 mol%

In the present invention, the blending ratio of the polyethersulfone resin (A) and the liquid crystalline polyesteramide resin (B) is 5 to 80% by weight of the liquid crystalline polyesteramide resin (B) with respect to 100 parts by weight of the polyethersulfone resin (A). Part. If the blending amount of the liquid crystalline polyester amide resin (B) is less than 5 parts by weight, the effect of improving the rigidity, which is the object of the present invention, is small. If the blending amount of the liquid crystalline polyester amide resin (B) is more than 00 parts by weight, The monotelsulfone resin (A) is not preferred because it is difficult to form a matrix. The amount of the liquid crystalline polyesteramide resin (B) is preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyethersulfone resin (A).

The resin composition of the present invention preferably contains a reinforcing fiber (C). Reinforcing fibers (C) include glass fibers, asbestos fibers, silica fibers, silica-lumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and wollastonite. Examples include silicate fibers, magnesium sulfate fibers, aluminum borate fibers, metal fibers such as stainless steel, aluminum, titanium, copper, and brass, and carbon fibers such as carbon fibers and carbon nanotubes. Typical reinforcing fibers are glass fiber and carbon fiber.

In addition, the resin composition of the present invention can be further supplementally supplemented with powdery and plate-like inorganic fillers other than the reinforcing fibers as long as the purpose of the present invention is not impaired.

As granular fillers, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium oxalate, aluminum oxalate, force orin, clay, diatomaceous earth, wollastonite Oxalates such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, Other examples include Ferri iron, silicon carbide, silicon nitride, boron nitride, and various metal powders.

Examples of the plate-like filler include My strength, glass flakes, talc, and various metal foils.

These inorganic fillers can be used alone or in combination of two or more. However, if a large amount of inorganic filler is included, the toughness is significantly reduced. It is preferable to make it into 5 to 40 weight% in a composition including this.

In using these fillers, a sizing agent or a surface treatment agent can be used if necessary.

Further, the thermoplastic resin composition of the present invention may be further supplemented with other thermoplastic resins other than those described above as long as the purpose of the present invention is not impaired.

Examples of the thermoplastic resin used in this case are: Polyolein such as polyethylene and polypropylene; Aromatic polyester composed of aromatic dicarboxylic acid and diol such as polyethylene terephthalate and polybutylene terephthalate; Polyacetate Tar (homo or copolymer), polystyrene, polyvinyl chloride, polycarbonate-soot, ABS, polyphenylene oxide, polyphenylene sulfide, fluorine resin and the like. These thermoplastic resins can be used as a mixture of two or more.

Production of the resin composition of the present invention includes a method in which each component such as a polyethersulfone resin, a liquid crystalline polyamide resin, and an inorganic filler used if necessary is melt-kneaded simultaneously using an extruder. In view of suppressing resin decomposition, the melting temperature during melt kneading is preferably 300 to 40 (T.

Further, kneading may be performed using a master batch obtained by melt-kneading any of them in advance. The resin composition obtained by melt-kneading with an extruder is preferably pressed into a pellet by a pelletizer and then obtained by injection molding. Example

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, the method of the physical-property measurement in an Example is as follows.

[Melting point]

With a differential scanning calorimeter (DSC 7 manufactured by PerkinElmer Co., Ltd.) Measured under temperature-decreasing conditions.

[Melt viscosity]

Measurement was performed with a Capillograph 1 B manufactured by Toyo Seiki using an orifice with an inner diameter of 1 mm and a length of 20 mm under the condition of a shear rate lOOOsec at a predetermined temperature.

[Flexural modulus]

125 thigh X 12.7mmX 0. 8 thigh injection-molded pieces were used, and flexural modulus was measured according to A S T M D 7 90.

Production Example 1 (Production of liquid crystalline polyesteramide <1>)

A polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen inlet, and vacuum outlet was charged with the following raw material monomers, catalyst, and acylating agent, and nitrogen substitution was started.

(A) 6-hydroxy-1-2-naphthoic acid 225. 90 g (60 mol%)

(B) Terephthalic acid 66. 48 g (20 mol%)

(0 4-acetoxyaminophenol 60. 48 g (20 mol%)

Potassium acetate 22.5mg

Acetic anhydride 166.67 g

After charging the raw materials, the temperature of the reaction system was raised to 140 and reacted at 140 ° C for 1 hour. Then, the temperature is further increased to 330 over 3.3 hours, and then reduced to lOTorr (that is, 1330 Pa) over 20 minutes to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. Polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from the reduced pressure state to the normal pressure state, and the polyester amide 1> was discharged from the lower part of the polymerization vessel.

Production Example 2 (Production of liquid crystalline polyesteramide <2>)

Polyesteramide <2> was obtained in the same manner as in Production Example 1 except that the following were used as raw material monomers, catalysts, and acylating agents, and the temperature was raised to 330 ° C over 3.5 hours. It was.

(A) 4-hydroxybenzoic acid 188.25 g (60 mol%)

(B) 6-Hydroxy-2-naphthoic acid 21.37 g (5 mol%)

(0 66.04 g (17.5 mol%) terephthalic acid)

(D) 4, 4'-biphenol 52.87 g (12.5 mol%)

(E) 4-acetoxyaminophenol 17.17 g (5 mol%)

Potassium acetate 50mg

Acetic anhydride 226.31 g

Production Example 3 (Production of liquid crystalline polyester 3)

Polyester <3> was obtained in the same manner as in Production Example 1, except that the following were used as the raw material monomer, catalyst, and acylating agent, and the temperature was raised to 330 ° C for 3.5 hours.

[0031]

(A) 4-hydroxybenzoic acid 226.4 g (73 mol%)

(B) 6-Hydroxy-2-naphthoic acid 114. lg (27 mol%)

Potassium acetate 22.5mg

Acetic anhydride 233.8 g

The obtained polyesteramide <1> to <2> and polyester <3> were observed in a 300 ° C molten state (<2> was 360 ° C molten state) with a polarizing microscope under crossed Nicols. It showed a clear optical anisotropy and was confirmed to be a thermopick liquid crystal resin. Table 1 shows the characteristics of each liquid crystal resin. table 1

Examples 1-2, comparative example :! ~ Four

As shown in Table 2, liquid crystalline polyesteramide <1> to 2>, liquid crystalline polyester <3>, polyethersulfone (BAS F E1010 (unreinforced? £ ≤), Mitsui Chemicals, Inc.) After dry blending SGN 202 OR (carbon fiber 20 wt% reinforced PES)) in the ratio shown in Table 2, use a twin-screw extruder (Ikegai Tekko Co., Ltd., PCM-30 type) and cylinder temperature It was melt-kneaded at 350 ° C and pelletized. From the pellets, the above test pieces were prepared and evaluated under the following conditions by an injection molding machine. The results are shown in Table 2.

(Injection molding conditions)

Molding machine: J SW J 75 S SII-A

Cylinder temperature; 350-350-340-330

Mold temperature: 150 ° C

Injection speed: 2mZmin

Holding pressure: 58.8MPa

Cycle: injection holding pressure 7 sec + cooling molding 20 sec

Screw rotation speed: lOOppm

Screw back pressure; 3.5 Pa Table 2

Comparative Example 1 Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 2 Non-reinforced PES (parts by weight) 100 100 100 100

Reinforced PES (parts by weight) 100 100 Polyesteramide <1> (parts by weight) 18 18 Polyesteramide <2> (parts by weight) 18

Polyester <3> (parts by weight) 18

Flexural modulus MPa 2700 4500 3500 3400 6300 8000 Melt viscosity ZPa's (380 ° C) 177 78 36 63 215 85

Claims

The scope of the claims

1. Polyethersulfone resin (A) With respect to 100 parts by weight, at least selected from 4-aminophenol, 1,4_phenylenediamine, 4-aminobenzoic acid and derivatives thereof as a constituent monomer Thermoplastic, characterized by containing 5 to 80 parts by weight of a liquid crystalline polyester amide resin (B) containing 1 type and containing an amide component in a proportion of 15 to 35 mol% in all bonds Resin composition.

2. The liquid crystalline polyesteramide resin (B) has a melting point in the range of 270 to 370 as measured by a scanning differential thermal analyzer (DSC) and exhibits optical anisotropy during softening flow. 1. The thermoplastic resin composition according to 1.

3. Liquid crystalline polyester amide resin (B) Power ^ Thermoplastic resin according to claim 1, which is a wholly aromatic polyester amide obtained by copolymerizing the following monomers (i) to (iii) within the following ranges: Composition.

(i) 6-hydroxy_2-naphthoic acid; 30-90 mol%

(i i) 4-Aminophenol; 15-35 mol%

(i i i) terephthalic acid; 15-35 mol%

4. The thermoplastic resin composition according to any one of claims 1 to 3, further comprising a reinforcing fiber (C).

5. The thermoplastic resin composition according to claim 4, wherein the reinforcing fiber (C) is glass fiber or carbon fiber.

6. An injection-molded article comprising the thermoplastic resin composition according to any one of claims 1 to 5.