JPH0326760A - Extrusion molded sheet - Google Patents

Abstract

PURPOSE:To obtain a sheet having excellent heat-resistance, mechanical properties, chemical resistance, etc., high smoothness and excellent elastic modulus, etc., and suitable for aerospace apparatuses, etc., by compounding a fibrous reinforcing material, etc., to polyphenylene sulfide and extrusion-molding the composition. CONSTITUTION:The objective sheet is produced by compounding 100 pts.wt. of a polyphenylene sulfide containing >=90mol% of the recurring unit of formula with (A) 2-50 pts.wt. (preferably 10-40 pts.wt.) of a fibrous reinforcing material (e.g. glass fiber) and (B) 5-50 pts.wt. (preferably 10-26 pts.wt.) of an inorganic compound having an average particle diameter of <=50mum and extrusion molding the obtained composition.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to extrusion molding of a polyphenylene sulfide resin composition having excellent heat resistance, mechanical properties, chemical resistance, hygroscopicity, dimensional stability, etc. The present invention relates to a sheet-like material useful in aerospace equipment, electrical and electronic equipment, automobiles, precision equipment, general equipment, etc.

(Prior technology) The field of application of engineering blastinok has been expanding rapidly in recent years, and its use in the automobile, electrical, and electronic fields in particular has increased significantly.As a result, the demands for plastics from users have also become more diverse. Functionality is becoming more sophisticated, and responding to this has become a technical challenge.However,
These diversified demands cannot be fully met with a single material or certain shape conditions, so it has recently become popular to meet these demands by adding composite fillers to thermoplastic resins. .

FRTP, which is a composite of polyphenylene sulfide (hereinafter referred to as PPS) and glass fiber, has been developed in response to such demands. A resin composite sole containing 30% by weight of such glass fibers has a bending strength of approximately 2550 kg.
/aj, flexural modulus approximately 150000kg/cd,
Heat distortion temperature (ASTM load 18.6 kg/d) approx. 250
°C,a Excellent flammability, UL standard 94 V-0,
It has a hygroscopicity of 0.02%, and is hardly attacked by organic solvents and is only attacked by oxidizing acids at high temperatures, and has extremely high resistance to hot water. However, although it has been used for injection molded products up until now, the mold for injection molding is complicated and expensive, and it is not economical to use thermoplastic resin composites made of PPS and glass fiber. Although attempts have been made to develop molded products, there have been no reported studies of attempts to improve this resin composition for use in extruded sheet-shaped products.

[Problem to be solved by the invention]

Based on the above situation, the purpose of the present invention is to maintain the excellent properties of a resin composite made of PPS and a fiber reinforced material such as glass fiber, and in addition, to improve the anisotropy in the MD/'I''D direction. The object of the present invention is to obtain a sheet molded product with less turbidity and excellent smoothness.

[Means and effects for solving the problem] As a result of the inventors' extensive research for this purpose, the general formula (+S-)
A thermoplastic resin composition comprising (A) 2 to 50 parts by weight of a fiber reinforcing material and (3) 5 to 50 parts by weight of an inorganic compound with an average particle size of 50 μ or less based on the parts by weight of ppstoo having a repeating unit of 90 mol % or more. The present invention was achieved by discovering that a sheet-like object made by extruding and shaping an object can be used as an object.

In other words, the excellent heat resistance, heat distortion temperature, flame retardance, and water absorption properties of PPS have been well known in the field of injection molded products, but as extruded sheet products, it has poor impact resistance and elasticity. Because the ratio is insufficient, ω) the fiber reinforcement of the precepts is 2~
It is necessary to add 50 parts by weight, and in order to deal with the anisotropy caused by adding the fiber reinforcement,
(2) It is necessary to add 5 to 50 parts by weight of an inorganic compound having an average particle size of 50 μm or less. Additionally, it has multiple functions such as a surface smoothing effect, a reinforcing effect, and a crystal nucleating agent.

In order to further improve the impact resistance, preferably (
It is preferable to add an ethylene/vinyl acetate/glycidyl methacrylate tripartite copolymer as a Q component. In addition, in order to further improve thermal stability, (
b) It is preferable to use tetrakis(methylene 3-(3.5-di-butyl-4-hydroxyphenyl)-brobiot)methane in combination.

Additionally, the sheet-like material of the present invention may further contain additives such as oxidation stabilizers, light stabilizers, lubricants, pigments, flame retardants, plasticizers, etc., if necessary. [Action] Component (A) is added to the PPS resin. The sheet-like material obtained by extruding and shaping the thermoplastic resin composition obtained by blending @ has a high elastic modulus, excellent impact resistance, and a smooth surface, and when it is crystallized by 10% or more, High elastic modulus,
Even during punching at room temperature, there was no cracking or delamination, and the heat resistance, impact resistance, and workability were significantly improved compared to conventionally used electrical insulation boards. The PPS resin used in the present invention has 90 mol% or more of repeating units of the general formula (→!tos - ), and 10 mol% or more of uncombined ( -i Q + ) as a copolymer component.
S-), sulfone bond (He→-SCh {one-S-), biphenyl bond (-8, where R represents an alkyl, nitro, phenyl, or alkoxy group), trifunctional phenyl sulfide bond properties, The copolymer content may be within a range that does not significantly affect the stretchability and coordination properties, but preferably the copolymer content is 5 mol % or less. Specific examples of the fibrous reinforcing material used as the (If) component of the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, and titanate fibers. Glass fiber is usually used. In addition, there are no particular restrictions on the diameter and length of the various fibers, but if the fiber length is too long, it will be difficult to mix and disperse uniformly with polyester and other compounding agents, and conversely, if the fiber length is too short, Since the effect as a reinforcing material becomes insufficient when O. A fiber with a fiber length of l = 10 m is used, and especially when the fibrous reinforcement is glass fiber, the fiber length is 0. 1~71Il
1 is preferable, more preferably 0. 3~4■ is desirable.

Further, the fibrous reinforcing material may be treated with various compounds as necessary in order to improve the interfacial adhesion with polyester and enhance the reinforcing effect. When using glass fibers as fibrous reinforcement, various surface treatment agents such as vinyltriethoxysilane, T-methacryloxypropylmethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane are used. ,
Silane-based treatment agents such as γ-glycidoxypropyltrimethoxysilane, T-aminopropyltriethoxysilane, T-chloropropylmethoxysilane, T-mercaptopyltrimethoxysilane, and chromium-based treatment agents such as methacrylate chromic chloride. The processed one is used. Next, the inorganic compound used as component (1) of the present invention is:
Depending on its particle size and shape, it can function as a smoothing agent for the sheet surface, a reinforcing material, an anisotropic relaxant for mechanical properties, and a crystal nucleating agent. To satisfy these functions, an inorganic compound with an average particle size of 50 μm or less is required. Specific examples of inorganic compounds with an average particle size of 50μ or less include mica, carbon black,
silica, calcium carbonate, silicic acid and silicates,
Zinc white, Yakuchi cytoclay, kaolin, basic magnesium carbonate, talc, quartz powder, wollastonite, dromaica powder, titanium oxide, barium acetate, calcium sulfate,
Examples include alumina, and the use of one or more of these inorganic compounds is particularly effective in the present invention.

Regarding the blending ratio of each precept in the resin composition of the present invention, (
If the amount of the fiber reinforcing material in the /l) component is less than 5 parts by weight, the effect as a reinforcing material will be insufficient, and if it exceeds 50 parts by weight, the smoothness of the sheet surface will deteriorate significantly. Therefore, the blending amount of the fiber reinforcement is 5 to 50 parts by weight, preferably 1
It is 0 to 40 parts by weight.

(B) Regarding the amount of inorganic compounds with an average particle size of 50μ or less in the precepts, the inorganic compounds with an average particle size of 50μ or less are PPS.
If it is less than 5 parts by weight based on the weight of IOO, its effect as a surface smoothing agent, an anisotropy relaxant for mechanical properties, and a reinforcing material will be insufficient, and conversely, if it is added in an amount exceeding 50 parts by weight, , the mechanical properties are significantly deteriorated. Therefore, the blending amount of component (1) is 5 to 50 parts by weight per 100 parts by weight of PPS.
Parts by weight, preferably 10 to 25 parts by weight. The sheet material of the present invention is produced using an extrusion sheet forming apparatus using a known T-die, but it is desirable to pre-dry the pellet made of the resin composition of the present invention at 150° C. for about 5 hours. The resin composite material extruded from the T-die is cooled on a casting roller and formed into a sheet. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 Melt viscosity at 300°C and shear rate of 100 sec-' is 2
,000 poise PPS ((-{:ris-) repeating unit is 100 mol%) 100 parts by weight, 20 parts by weight of glass fiber with a fiber length of 3M, and 20 parts by weight of mica with an average particle size of 40 μ or less A flat sheet was prepared by blending the mixture and melt-kneading it in a twin-screw extruder, which was then extruded and shaped into a sheet by an extrusion sheet-forming device using a T-die.
The sheet was press-molded for 20 minutes at a pressure of 30 kg/cj at C. The measurement results of the molded sheet are shown in Table 1.

Example 2 Melt viscosity at 300°C and shear rate of 100 sec is 2,
000-void PPS [(=(low-S-) repeating unit is 100 mol%) 100 parts by weight, 40 parts by weight of glass fiber with a fiber length of 3 strands, and 10 parts by weight of my strength with an average particle size of 40μ Pellets were prepared by blending them as follows and melt-kneading them in a twin-screw extruder. This was formed into a sheet using an extrusion sheet forming apparatus using a T-die to obtain a rigid sheet with a smooth surface and a thickness of 1 m. Table 1 shows the measurement results for the sheet.
Shown below.

Example 3 Melt viscosity at 300° C1 shear rate 100 sec-' is 2
To 100 parts by weight of PPS ((gold s-) repeating unit is 1OO mol%) of ,000 voids, 10 parts by weight of glass fiber with a fiber length of 3 m and 4 parts of mica with an average particle size of 40 μm were added.
A beleft was prepared by blending the ingredients so that the amount was 0 parts by weight and melt-kneading them using a twin-screw extruder. This was formed into a sheet using an extrusion sheet forming device using a T-die to obtain a rigid sheet with a thickness of 1a+s and a smooth surface. Table 1 shows the measurement results for the sheet.

Comparative Examples 1 to 4 Melt viscosity at 300°C and shear rate of 100 sec-' is 2
,000 poise pps ((→C←S-> repeating unit is 100 mol%)) 100 parts by weight of glass fiber with a fiber length of 3 min and mica with an average particle size of 40 μm were combined as shown in Table 1. A beleft was prepared by mixing and melt-kneading with a twin-screw extruder, and this was formed into a sheet using an extrusion sheet forming device using a T-die to obtain a sheet with a thickness of one circle. Table 1 shows the measurement results for the sheet.

〔Effect of the invention〕

Claims (1)

[Claims] For 100 parts by weight of polyphenylene sulfide having a repeating unit of the general formula (▲ mathematical formula, chemical formula, table, etc.) of 90 mol % or more, (A) 2 to 50 parts by weight of fiber reinforcement; (B) An extrusion-molded sheet product characterized by extrusion-molding a thermoplastic resin composition composited with 5 to 50 parts by weight of an inorganic compound having an average particle size of 50 μm or less.