KR100673777B1 - Polyphenylene sulfide thermoplastic resin composition and molded article thereof - Google Patents

Abstract

The present invention is prepared by adding an organosilane compatibilizer and a fluorinated polyolefin resin to a resin composition composed of a polyphenylene sulfide resin and a polyether sulfone resin which is incompatible with the polyphenylene sulfide resin, and a polyphenylene sulfide thermoplastic resin composition Since the molded article is provided, it has excellent compatibility, rigidity, appearance, impact strength, and flame retardancy, and thus may be usefully used in electrical and electronic device parts, automotive parts, or chemical device parts requiring such properties.

Description

Polyphenylene sulfide thermoplastic resin composition and molded article thereof {POLYPHENYLENE SULFIDE THERMOPLASTIC RESIN COMPOSITION AND MOLDING PRODUCT THEREOF}

The present invention relates to a polyphenylene sulfide thermoplastic resin composition and its molded article having improved compatibility and flame retardancy, and more particularly, to a polyphenylene sulfide resin having excellent mechanical strength, flame retardancy, and chemical resistance, and excellent heat resistance and high rigidity characteristics. The present invention relates to a polyphenylene sulfide thermoplastic resin composition and a molded article of which an organic silane compound and a fluorinated polyolefin resin are added to a blend of a polyether sulfone having a maximal compatibility and greatly improved flame retardancy. .

Generally, polyphenylene sulfide resin is a high melting point heat resistant resin having excellent mechanical strength, chemical resistance, flame retardancy, and fluidity. However, like general crystalline resins, polyphenylene sulfide resins are disadvantageous in terms of impact resistance and brittleness. In recent years, polyphenylene sulfide resins are blended together with polyether sulfone resins having excellent heat resistance, rigidity and toughness, and thus have excellent impact strength, heat resistance and flame resistance. There has been a continuing search for greatly improved polyphenylene sulfide resin compositions.

Recently, functional resins having excellent properties such as mechanical strength, heat resistance, flame resistance, and chemical resistance have been demanded as materials for electric and electronic device parts, automotive device parts, and chemical device parts. One of the thermoplastic resins that satisfies these requirements is polyphenylene sulfide resin, but polyphenylene sulfide resin has a large drop in rigidity at high temperature, and its heat resistance is not good as the glass transition temperature is about 90 ° C. Reported.

In order to solve the above problem, a method of increasing mechanical strength and heat resistance using an inorganic filler such as glass fiber having a high content has been proposed.

Therefore, in order to improve the physical properties of polyphenylene sulfide resin, a method of blending with various thermoplastic resins has been attempted. Among them, polyether sulfone resin has excellent heat resistance, high temperature rigidity, toughness, and dimensional stability, and thus polyphenylene sulfide It has been widely used as a resin suitable for blending with resins.

However, in a simple blend system, the compatibility between the two resins is insufficient, poor extrudability, the phase separation occurs, and the appearance of the molded product is also poor, in particular, there is a problem that the dropping of the resin during combustion in the non-reinforced resin products.

In order to solve this problem, studies have been conducted to improve compatibility between two resins. For example, Japanese Patent Laid-Open No. 59-164360 discloses a resin composition in which novolak-type epoxy resins are added to improve compatibility and impact resistance, and Japanese Laid-Open Patent Publication No. 9-3325 commercializes alkali metal salts. A resin composition used zero has been disclosed.

 However, in recent years, the demand for polyphenylene sulfide resin materials has been materialized, and as a result of demanding improvement of various physical properties such as tensile elongation characteristics along with better mechanical properties, heat resistance and flame retardancy, the prior art can secure desired levels of physical properties. There was no problem.

The present invention has been made to solve the above problems, and an object of the present invention is to combine the organic silane-based compatibilizer and fluorinated polyolefin-based resin in polyphenylene sulfide resin and polyether sulfone resin for compatibility of the two resins. The present invention provides a polyphenylene sulfide thermoplastic resin composition which maximizes physical properties such as impact resistance, heat resistance, and elongation while maintaining original properties of polyphenylene sulfide resin such as mechanical strength and chemical resistance.

Another object of the present invention is to provide a molded article of the polyphenylene sulfide thermoplastic resin composition prepared by the polyphenylene sulfide thermoplastic resin composition improved appearance and flame retardancy.

Other objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description of the invention and the preferred embodiments.

One aspect of the present invention for achieving the above object is

(A) 0.1 to 30 parts by weight of polyphenylene sulfide resin; And

(B) To 100 parts by weight of the resin composition composed of 70 to 99.9 parts by weight of polyether sulfone resin

(C) 0.01 to 10 parts by weight of an organic silane compatibilizer;

0.01 to 10 parts by weight of (D) fluorinated polyolefin resin;

It relates to a polyphenylene sulfide thermoplastic resin composition comprising a.

Hereinafter, (A) polyphenylene sulfide resin, (B) polyether sulfone resin, (C) organic silane compatibilizer and (D) fluorinated polyolefin resin which are each component of the thermoplastic resin composition of this invention are demonstrated in detail. .

(A) polyphenylene sulfide resin

It is preferable that the polyphenylene resin used for the resin composition of this invention is a polyphenylene resin which contains 70 mol% or more of structural units represented by following [Formula 1]. When 70 mol% or more of this repeating unit is contained, it is because crystallinity which is a characteristic of a crystalline polymer is high, and it is excellent also in heat resistance, chemical resistance, and strength.

[Formula 1]

The polyphenylene sulfide resin may be a linear molecular structure having no branched or crosslinked structure or a molecular structure having a branched or crosslinked structure depending on the production method thereof, but any structure may be used in the present invention. Representative methods for producing crosslinked polyphenylene sulfide resins are disclosed in Japanese Patent Application No. 45-3368, and representative methods for producing linear polyphenylene sulfide resins are disclosed in Japanese Patent Application No. 52-12240. Such polyphenylene sulfide resin may contain less than 50 mol%, preferably less than 30 mol% of other copolymerized structural units represented by the following [Formula 2] to [Formula 9].

[Formula 2]

[Formula 3]

 [Formula 4]

 [Formula 5]

[Formula 6]

[Formula 7]

(Wherein R is an alkyl group, nitro group, phenyl group, alkoxy group, carboxyl group or metal carboxylate group)

[Formula 8]

[Formula 9]

In consideration of thermal stability and workability, the polyphenylene sulfide resin composition preferably has a melt index (MI) of 10 to 300 g / 10 min at 316 ° C. under a load of 2.16 kg. If the melt index is less than 10 g / 10 minutes, the workability during the kneading and injection process is a problem, and when the melt index exceeds 300 g / 10 minutes, a problem of strength decreases.

In the resin composition of the present invention, the polyphenylene sulfide resin is preferably used in the range of 0.1 to 30 parts by weight, more preferably in the range of 10 to 30 parts by weight. When the workability may be lowered, and if it exceeds 30 parts by weight, the heat resistance is lowered, which tends to become thermal deformation at a high temperature.

(B) polyether sulfone resin

The polyether sulfone resin used in the present invention is characterized in that it comprises a copolymer in which at least one para phenylene group is located at one place and a biphenyl group or a phenyl ether group is located at another place.

Specifically, the polyether sulfone resin is characterized in that it is any one selected from the group consisting of compounds represented by [Formula 10] to [Formula 25].

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

(In the formula, n is an integer of 10 or more, and the phenyl group can be substituted with hydrogen or an alkyl group.)

[Compound 10] is particularly preferable among the above compounds, and the polyether sulfone used in the present invention has a melt viscosity of preferably 20 to 85 g / 6 minutes at 380 ° C under 2.16 kg load, more preferably 50 to 70 g / 6 minutes.

Representative methods for producing polyether sulfone resins include 4,4'-dichlorodiphenylsulfone and 2,2'- as disclosed in Japanese Patent Application Laid-Open No. 52-38000 and the like. It can be prepared by bis (4-hydroxyphenyl) propane (2,2'-bis (4-hydroxy-phenyl) propane).

The polyether sulfone used in the present invention is preferably 70 to 99.9 parts by weight, more preferably 70 to 90 parts by weight. If it is less than 70 parts by weight, the heat resistance is low, there is a problem that tends to be thermal deformation at high temperature, if it exceeds 99.9 parts by weight there is a problem that the mechanical properties are lowered.

(C) Organosilane Compatibilizer

The organosilane-based compatibilizer used in the resin composition of the present invention is preferably a silane compound composed of an epoxy group or an amino group and a methoxy group or an ethoxy group. More preferably, it is 1 or more types chosen from the triethoxysilane represented by the following [Chemical Formula 26], or the trimethoxysilane represented by the following [Chemical Formula 27].

    [Formula 26]

A-Si (OCH ₂ CH ₃ ) ₃

[Formula 27]

A-Si (OCH ₃ ) ₃

(Wherein A is

① alkyl group such as methyl group, ethyl group,

② olefin group such as vinyl group,

③ epoxy group or amino group,

④ is a group in which a group corresponding to ① and a group corresponding to ③ are bonded, such as an aminopropyl group and a glycidoxypropyl group,

⑤ It is a methoxy group or an ethoxy group.)

The amount of the organic silane-based compatibilizer used in the resin composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably to 100 parts by weight of the resin composition composed of the polyphenylene sulfide resin and the polyether sulfone resin. 0.1 to 5 parts by weight. Less than 0.01 parts by weight or 10 When the weight part exceeds the weight part, the separation of the two resins may occur, resulting in peeling of the appearance of the injection molded article, or physical properties such as mechanical strength and impact resistance may be deteriorated.

(D) fluorinated polyolefin resin

When the fluorinated polyolefin resin is mixed and extruded together with the other component resins of the present invention, a fibrillar network is formed in the resin to lower the flow viscosity of the resin during combustion and increase the shrinkage rate to increase the shrinkage of the resin. To prevent.

Fluorinated polyolefin-based resins (D) used in the resin composition of the present invention are conventionally available resins such as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, and tetrafluoro. Ethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, and the like. These may be used independently from each other, and two or more different types may be used together.

Fluorinated polyolefin resins that can be preferably used in the preparation of the resin composition of the present invention has an average particle diameter of 0.05 to 1,000μm, specific gravity of 1.2 to 2.3 g / cm ³ Phosphorus polytetrafluoroethylene is mentioned.

The fluorinated polyolefin resin used in the preparation of the resin composition of the present invention may be prepared using a known polymerization method, for example, a pressure of 7 to 71 kg / cm 2, a temperature of 0 to 200 ℃, preferably 20 to 100 It can be prepared in an aqueous medium containing free radical forming catalysts such as sodium, potassium or ammonium peroxydisulfate at < RTI ID = 0.0 >

The fluorinated polyolefin resin may be used in an emulsion state or a powder state. However, when the fluorinated polyolefin resin in an emulsion state is used, the dispersibility in the entire resin composition is good, but the manufacturing process is complicated. Therefore, the fluorinated polyolefin resin can be properly dispersed in the whole resin composition to form a fibrous network. In this case, it is preferable to use in powder form.

The fluorinated polyolefin resin used in the resin composition of the present invention is based on 100 parts by weight of the resin composition composed of the polyphenylene sulfide resin and the polyether sulfone resin. It is preferable to use 0.01-10 weight part, More preferably, it uses it in 0.05-5 weight part. If the amount is less than 0.01 part by weight, the flame retardancy may decrease due to the increase in the combustion time and the dropping of the resin, and when the amount exceeds 10 parts by weight, the melt viscosity of the resin may be too high, thereby reducing the extrusion characteristics.

In addition to the above components, the thermoplastic resin composition of the present invention can be used for various purposes by appropriately adding an antioxidant, a mold release agent, a flame retardant, a lubricant, a colorant such as a pigment or a dye, a small amount of a multi polymer, a thermoplastic elastomer, and the like.

The resin composition of the present invention can be produced by a known method. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

Another aspect of the present invention for achieving the above object relates to a molded article greatly improved appearance and flame retardancy, characterized in that it is produced from a polyphenylene sulfide thermoplastic resin composition.

From the thermoplastic resin composition according to the present invention, the molded article may be manufactured by a method known to those skilled in the art. For example, it is possible to manufacture micro-molded products such as wire stoppers and plugs by using a plunger type injection molding machine, and more precise engineering than when using a plunger method using a screw type injection machine. It is also possible to produce small insert molded articles of plastic resin.

In addition, the composition of the present invention can be used in the molding of various products, in particular, due to the impact resistance and excellent heat resistance properties can be used in molded products such as lamp reflector (Lamp reflector), electrical and electronic components or precision parts.

Example

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention, and are not intended to limit the scope of the present invention.

Each component used to prepare the resin composition of the present invention is as follows.

(A) polyphenylene sulfide resin

Linear polyphenylene sulfide resin (trade name: KL-02) manufactured by Nippon Ink (DIC) was used.

(B) polyether sulfone resin

GAFONE PES 3500 from GHARDA was used.

(C) Organosilane Compatibilizer

A liquid gamma-glycidoxypropyltrimethoxysilane (GE: Silquest A-187) was used.

(D) fluorinated polyolefin resin

US-made Dupont Teflon 7AJ was used.

Examples 1-3 and Comparative Examples 1-7

Using the above-mentioned components were prepared resin compositions with the composition shown in Examples 1 to 3 and Comparative Examples 1 to 7 of Table 2, the extrusion properties thereof are shown in Table 1, flame retardancy is shown in Table 2 , respectively.

division Great Good failure Strand short circuit presence radish radish U Yields over 90 50-70% 30% less than

           * N.B: No Break

[Property evaluation method]

(1) specimen manufacture

After mixing each component with the composition shown in Table 2 , antioxidant and heat stabilizer were added and mixed in a conventional mixer, and the mixture was put into a twin screw extruder having L / D = 36 and ￠ = 45 mm. The mixture was prepared into a resin composition in pellet form through an extruder, and a specimen for evaluating physical properties and impact resistance and a flame retardant was prepared at an injection temperature of 310 ° C. using a 10 oz injection machine.

(2) Heat deflection temperature and non-notched Izod impact strength

After leaving the specimen for evaluation of physical properties and impact resistance for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours, the thermal deformation temperature was measured according to ASTM D648, and the non-notched Izod impact strength (1/8 ”) was determined to ASTM D256. Measured accordingly.

(3) flame retardancy and burning time

After the flame-retardant specimens were allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours, the flame retardance was measured according to the UL94 standard, and the combustion time was expressed in seconds.

(4) extrusion characteristics

Extrusion characteristics were evaluated by the presence or absence of a short circuit of the strand (yields) during extrusion for 10 minutes.

In Table 1, from the results shown in Table 2, a polyphenylene sulfide resin and a polyether resin according to the present invention further comprises an organic silane-based compound and a fluorinated polyolefin-based resin to the sulfone resin composition, than the resin compositions shown in Comparative Example It was confirmed that the heat resistance and the impact resistance, particularly UL94 flame retardancy is greatly improved.

As a result of comparing Examples 1 to 2 and Comparative Examples 4 to 5, in the case of the resin composition composed of polyphenylene sulfide resin, polyether sulfone resin, and organic silane compound alone, the extrudability was improved, but the combustion time increased during combustion and the dropping of the resin. It was confirmed that the flame retardancy is reduced by the occurrence.

In the comparative example 1, when extruded only by polyphenylene sulfide resin, it was confirmed that extrusion property was bad and heat resistance and impact resistance were very low because of the low melt viscosity of polyphenylene sulfide resin.

Further, in Comparative Examples 2 to 3, in the case of a resin composition composed only of a polyphenylene sulfide resin and an organic silane compound or a resin composition composed of only a polyether sulfone resin, the extrudability is improved, but the flame retardancy is reduced due to the dropping of the resin during flame retardation. I could confirm that.

In addition, as a result of comparing the Comparative Examples 6-7, when the organic silane compound and the fluorinated polyolefin resin was used in excess of the composition ratio of the present invention, the melt viscosity of the resin during extrusion was so high that extrusion was impossible.

The polyphenylene sulfide thermoplastic resin composition according to the present invention not only has excellent mechanical strength, heat resistance and compatibility, but also has excellent extrudability due to a reduction in combustion time and a drop in dropping of the resin, and particularly, greatly improves flame retardancy.

In addition, the molded article prepared from the polyphenylene sulfide thermoplastic resin composition according to the present invention has the characteristics of the resin, so that the flame retardancy is improved and has an excellent appearance, which is useful for electric and electronic device parts, automotive parts, or chemical device parts. Can be used.

Claims (8)

(A) 0.1 to 30 parts by weight of polyphenylene sulfide resin; And (B) Resin composition composed of 70 to 99.9 parts by weight of polyether sulfone resin     Per 100 parts by weight of water (C) 0.01 to 10 parts by weight of an organic silane compatibilizer; 0.01 to 10 parts by weight of (D) fluorinated polyolefin resin; Polyphenylene sulfide thermoplastic resin composition comprising a. The polyphenylene sulfide thermoplastic resin composition according to claim 1, wherein the polyphenylene sulfide resin is linear or crosslinked. The polyphenylene sulfide thermoplastic resin composition according to claim 1 or 2, wherein the polyphenylene sulfide resin is 10 to 30 parts by weight. The polyphenyl sulfone resin according to claim 1, wherein the polyether sulfone resin includes a copolymer in which at least one paraphenylene group is located at one place and a biphenyl group or a phenyl ether group is located at another place. Len sulfide thermoplastic resin composition. The polyphenylene sulfide thermoplastic resin composition according to claim 4, wherein the polyether sulfone resin is any one selected from the group consisting of compounds represented by the following [Formula 10] to [Formula 25]. [Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

(In the formula, n is an integer of 10 or more, and the phenyl group can be substituted with hydrogen or an alkyl group.) According to claim 1, wherein the organic silane compatibilizer is at least one selected from triethoxysilane (Triethoxysilane) represented by the following [Formula 26] or trimethoxysilane represented by the following [Formula 27] Polyphenylene sulfide thermoplastic resin composition, characterized in that. [Formula 26] A-Si (OCH ₂ CH ₃ ) ₃ [Formula 27] A-Si (OCH ₃ ) ₃ (Wherein A is ① alkyl group such as methyl group, ethyl group, ② olefin group such as vinyl group, ③ epoxy group or amino group, ④ is a group in which a group corresponding to ① and a group corresponding to ③ are bonded, such as an aminopropyl group and a glycidoxypropyl group, ⑤ It is a methoxy group or an ethoxy group.) The polyphenylene sulfide thermoplastic resin composition according to claim 1, further comprising an antioxidant, a releasing agent, a flame retardant, a lubricant, a coloring agent such as a pigment or a dye, a small amount of multiple polymers, a thermoplastic elastomer, and the like. A molded article prepared from the polyphenylene sulfide thermoplastic resin composition according to claim 1.