KR101837456B1 - Polyphenylene sulfide resin composition for thermostat housing - Google Patents

Abstract

The present invention relates to a polyphenylene sulfide resin composition for a thermostat housing, and more particularly, to a composite material composition for a vehicle, which comprises a polyphenylene sulfide resin, a glass fiber, calcium carbonate, barium sulfate, zinc oxide and a reactive compatibilizer. The polyphenylene sulfide resin composition for a thermostat housing has excellent in chemical resistance and dimensional stability.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyphenylene sulfide resin composition for a thermostat housing,

The present invention relates to a composite material composition for a vehicle, and more particularly, to a composite material composition for a vehicle, which comprises polyphenylene sulfide resin, glass fiber, calcium carbonate, barium sulfate, zinc oxide and a reactive compatibilizer, To a phenol sulfide resin composition.

The thermostat functions to control the engine coolant temperature. It prevents overheating of the engine and keeps the proper temperature so that the combustion condition of the engine is not degraded, so that it can maintain the engine output and maintain the rigidity of the engine parts. to be. During the engine operation, the hot water flows into the radiator through the thermostat. The temperature of the hot water is lowered as it passes through the radiator, and then supplied to the engine. Because indoor heaters also operate as engine coolant, metal thermostats are used in most automobiles due to environmental factors that are exposed to high temperature fluids for a long time. However, there has been a demand for improving the weight of the vehicle as well as the weight of the entire vehicle, the fuel efficiency reduction, and the light weight of the vehicle.

Meanwhile, Korean Patent Publication No. 0652968 discloses an attempt to simultaneously improve rigidity and ductility by mixing polyphenylene sulfide and polyamide (PA6). However, due to the hygroscopicity of polyamide, the dimensional stability is reduced and the thermostat housing material There are aspects that are insufficient to be used.

Further, according to Japanese Patent Publication No. 3239491, an attempt is made to react an olefin-based copolymer containing a carboxyl group or a carboxylic acid derivative group with polyphenylene sulfide and an epoxy compound in advance and to improve impact resistance and toughness through a modified elastomer However, there are limitations in achieving satisfactory physical properties in the present invention.

In the prior art including the above-mentioned patent documents, a polyphenylene sulfide composition containing barium sulfate and zinc oxide is excellent in chemical resistance, dimensional stability, and mechanical properties, and there is no example satisfying the application requirements of the thermostat housing. Material development is required.

The present invention relates to a composite resin composition for automobiles having excellent chemical resistance and dimensional stability, and more particularly, to provide a polyphenylene sulfide resin composition for a thermostat housing having improved durability and airtightness and excellent mechanical properties. .

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

One aspect of the present invention relates to a polyphenylene sulfide resin composition comprising 100 parts by weight of a polyphenylene sulfide resin; 50 to 100 parts by weight of glass fiber; 50 parts by weight to 100 parts by weight of calcium carbonate; 2 parts by weight to 20 parts by weight of barium sulfate and zinc oxide; 1 to 5 parts by weight of reactive compatibilizing agent; And 1 to 5 parts by weight of a montan based lubricant.

According to another aspect of the present invention, there is provided a method for preparing a mixture, comprising: mixing 100 parts by weight of polyphenylene sulfide with 2 parts by weight to 20 parts by weight of a mixture of barium sulfate and zinc oxide in a weight ratio of 1: 1 to 1.5: 1; A second step of adding 1 to 5 parts by weight of the reactive compatibilizing agent to the mixture of the first step; A third step of adding 1 to 5 parts by weight of a montane lubricant to the mixture of the second step; Adding 50 parts by weight to 100 parts by weight of glass fiber to the mixture of the third step and mixing 50 parts by weight to 100 parts by weight of calcium carbonate; A fifth step of extruding the mixture of the fourth step while heating; And a sixth step of cooling the extrudate in the fifth step. The present invention also provides a method for producing a polyphenylene sulfide resin composition.

Another aspect of the present invention provides a molded article made of a polyphenylene sulfide resin composition.

The thermostat housing made of the polyphenylene sulfide resin composition of the present invention has characteristics of high heat resistance, high rigidity and light weight due to the manifestation of the rigidity and light weight of the polyphenylene sulfide resin, and is excellent in heat resistance, impact resistance, Excellent mechanical properties including stability, engine room characteristics, and chemical resistance, and excellent extrudability.

In addition, by replacing the metal with a resin, the step of processing the metal material is omitted, thereby simplifying the production process and reducing the time and manufacturing cost. And has advantages as an eco-friendly composite material having effects of reduction of automobile exhaust gas and improvement of fuel economy through high heat resistance, high stiffness and light weight.

1 is a block diagram of a thermostat housing.
Fig. 2 is an air-tightness evaluation image of a specimen injection-molded with the polyphenylene sulfide resin composition according to the present invention.
3 is a graph showing the results of evaluating the anti-freeze solution of the specimen injection-molded with the polyphenylene sulfide resin composition according to the present invention.
4 is a graph of thermal expansion coefficient measurement of a specimen injection-molded with a polyphenylene sulfide composition according to the present invention.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly explain the present invention in the drawings, parts not related to the description are omitted.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Throughout this specification, the phrase " step "or" step "does not mean" step for.

Hereinafter, embodiments and examples of the present invention have been described in detail, but the present invention is not limited thereto.

One aspect of the present invention relates to a polyphenylene sulfide resin composition comprising 100 parts by weight of a polyphenylene sulfide resin; 50 to 100 parts by weight of glass fiber; 50 parts by weight to 100 parts by weight of calcium carbonate; 2 parts by weight to 20 parts by weight of barium sulfate and zinc oxide; 1 to 5 parts by weight of reactive compatibilizing agent; And 1 to 5 parts by weight of a montan based lubricant. Wherein the polyphenylene sulfide resin composition comprises 100 parts by weight of a polyphenylene sulfide resin as a thermoplastic resin, 50 to 100 parts by weight of glass fiber and 50 to 100 parts by weight of calcium carbonate based on polyphenylene sulfide resin, Characterized in that it contains barium sulfate and zinc oxide in order to impart chemical stability and dimensional stability to the resin, glass fiber and calcium carbonate composite composition. About 65% of a mixture of glass fiber, calcium carbonate, zinc oxide and barium sulfate can be added based on the total amount of the polyphenylene sulfide resin composition. In order to improve the wettability, impregnation property and mechanical strength of the resin composition, Or two species. In addition, a filler or an additive may be further included within the range in which the effect of the present invention is not impaired.

[0033] The binder of two or more fillers (reinforcing agents) in the polyphenylene sulfide resin composition of the present invention, that is, calcium carbonate having an average particle size of 1 to 10 mu m, barium sulfate having a specific gravity of 4 to 4.5 and grains having a specific gravity of 5.4 to 5.7 The bonding of zinc oxide improves the chemical stability and dimensional stability and serves to provide a resin composition suitable for thermostat housing.

In one embodiment herein, the additional filler is selected from the group consisting of talc, calcium sulfate, kaolin, clay, pyroferrite, bentonite, cerilite, nephelinesycnite, Gypsum, ferrite, calcium silicate, magnesium silicate, dolomite, antimony trioxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass But are not limited to, at least one selected from the group consisting of balloons, glass powder, silica, and combinations thereof.

In one embodiment of the invention, the additive additive may include one or more conventional additives such as thermal stabilizers, antioxidants, ultraviolet absorbers, nucleating agents, corrosion inhibitors, colorants (dyes or pigments) But is not limited thereto.

In one embodiment of the invention, the weight ratio of barium sulfate to zinc oxide may be from 1: 1 to 1.5: 1. The content of the glass fiber and the calcium carbonate is 100 parts by weight to 150 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. The mixing ratio of 2 to 20 parts by weight of barium sulfate and zinc oxide is 1: 1 to 1.5: 1.

In one embodiment of the invention, the barium sulphate may have a specific gravity of 4 to 4.5. Barium sulphate can increase the specific gravity of the product due to its high specific gravity, contribute to soundproofing and dustproofing properties, and can be chemically stable, thus acting as an inert filler for chemical resistance. In addition, it has a low oil absorption and a high refractive index (1.67) to impart luster or reflect light, and can improve frictional resistance performance.

In one embodiment of the invention, the zinc oxide may have a specific gravity of 5.4 to 5.7. Zinc oxide is used as a promoter in many types of synthetic rubbers as well as natural rubbers. In the case of mixing a large amount of zinc oxide, heat resistance can be imparted to rubber due to its excellent thermal conductivity in addition to being used as a filler.

In one embodiment of the invention, the glass fiber may have an average particle diameter of 10 mu m or more and an average length of 4000 mu m or more. The average particle diameter of the glass fibers may be, for example, 10 탆 to 15 탆, 10 탆 to 14 탆, 10 탆 to 13 탆, 10 탆 to 12 탆, or 10 탆 to 11 탆, Preferably, 10 [mu] m to 12 [mu] m. The average length of the glass fibers is, for example, from 4000 탆 to 5000 탆, from 4000 탆 to 4800 탆, from 4000 탆 to 4600 탆, from 4000 탆 to 4400 탆, from 4000 탆 to 4200 탆, from 4200 탆 to 5000 탆, To 5000 m, from 4600 m to 5000 m, or from 4800 m to 5000 m, but is not limited thereto, preferably 4500 m.

In one embodiment herein, the reactive compatibilizing agent is an epoxy or amino-based reactive compatibilizing agent selected from 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane], 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, [N-glycidoxypropyl triethoxysilane] Aminoethyl) -3-aminopropylmethyldimethoxysilane], N-2- (aminoethyl) -3-aminopropyltrimethoxysilane [N-2 - (aminoethyl) -3-aminopropyltrimethoxysilane], 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- 3 dimethyl-butylidene) propylamine [3-triethoxysilyl-N- (1,3 dimethyl-butylidene) propylamine], N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl) -3-aminopropyltrimethoxysilane hydrochloride [N - (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride], N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- aminopropyltrimethoxysilane hydrochloride], and combinations thereof. However, the present invention is not limited thereto.

In one embodiment of the present invention, the montane lubricant may include at least one member selected from the group consisting of polyethylene wax, ester wax, metal montmate, silicone oil, metal stearate, and combinations thereof. But is not limited thereto.

In one embodiment of the present invention, the polyphenylene sulfide resin may have a flow index of 200 g / min or more at a temperature of 310 캜 under a load of 5 kg. The flow index can be, for example, from 200 g / min to 1500 g / min, from 200 g / min to 1200 g / min, from 200 g / min to 900 g / min, or from 200 g / min to 600 g / min But is not limited thereto, preferably 200 g / min to 900 g / min. Polyphenylene sulfide resin is a high-performance thermoplastic engineering resin that maintains its stiffness at room temperature even at high temperatures, and can improve heat resistance and chemical resistance through the addition of glass fibers and fillers. The polyphenylene sulfide resin can be molded by a common injection molding method, but it is thick and hard, and the chains of the molecules are partially bundled, which requires higher temperature conditions than general-purpose plastics. The melting characteristics of the polymer resin are directly related to the processability of the product and are important factors affecting the physical properties of the product. In addition, the larger the flow index, the higher the injection pressure can be achieved in a large-sized component or a dense structure. The large flow index means that the flowability during molding is good. In order to overcome the problem of forced extraction after injection rather than the cross-linked type, the present invention is characterized by high toughness and wet condition ), It is preferable to use a resin having a flow index of from 200 g / min to 900 g / min.

In one embodiment of the present invention, the polyphenylene sulfide resin composition may have a flow index of 14 g / 10 min or more at a temperature of 310 ° C under a load of 5 kg. The flow index is, for example, from 14 g / 10 min to 20 g / 10 min, from 14 g / 10 min to 18 g / 10 min, from 14 g / 10 min to 16 g / 10 min, from 16 g / 10 min to 20 g / 16 g / 10 min to 18 g / 10 min, but is not limited thereto.

According to another aspect of the present invention, there is provided a method for preparing a mixture, comprising: mixing 100 parts by weight of polyphenylene sulfide with 2 parts by weight to 20 parts by weight of a mixture of barium sulfate and zinc oxide in a weight ratio of 1: 1 to 1.5: 1; A second step of adding 1 to 5 parts by weight of the reactive compatibilizing agent to the mixture of the first step; A third step of adding 1 to 5 parts by weight of a montane lubricant to the mixture of the second step; Adding 50 parts by weight to 100 parts by weight of glass fiber to the mixture of the third step and mixing 50 parts by weight to 100 parts by weight of calcium carbonate; A fifth step of extruding the mixture of the fourth step while heating; And a sixth step of cooling the extrudate in the fifth step. The present invention also provides a method for producing a polyphenylene sulfide resin composition. The filler comprising the barium sulfate and zinc oxide is contained in an amount of 2 to 20 parts by weight based on 100 parts by weight of the polyphenylene sulfide, and the mixing of the polyphenylene sulfide, calcium carbonate, barium sulfate and zinc oxide is effective From 1 to 5 parts by weight of reactive compatibilizing agent. The polyphenylene sulfide resin composition containing the filler is advantageous in chemical resistance and numerical stability compared to a composition containing no barium sulfate or zinc oxide filler. In addition, the reactive compatibilizing agent can improve the thermal expansion coefficient and the anti-freezing effect of the resin composition.

Another aspect of the present invention provides a molded article made of a polyphenylene sulfide resin composition. The molded article is injection-molded using the polyphenylene sulfide resin composition according to the present invention at an injection temperature of 320 ° C or higher and a mold temperature of 120 ° C or higher. The mold temperature during molding is an important factor that affects the physical properties of the molded article and can be from room temperature to a high temperature of 150 ° C or higher. However, since the characteristics of the polyphenylene sulfide resin are influenced by the mold temperature, High temperature molds over 120 ℃ are required. Since the excellent heat resistance of the polyphenylene sulfide resin depends on the degree of crystallization, it is possible to obtain a molded article having high crystallinity and gloss on the surface when the mold temperature is at a high temperature of 120 캜 or higher.

In one embodiment of the present invention, the polyphenylene sulfide resin composition may have a flexural strength of 185 MPa or more measured according to ASTM D790 standard, and a heat distortion temperature (HDT) of 270 DEG C or more measured according to ASTM D648 standard.

In one embodiment of the present invention, the polyphenylene sulfide resin composition may have a thermal expansion coefficient measured according to the ASTM E831 standard of 20.0 x 10 ^-6 in / (in.

In one embodiment of the present invention, the molded article made of the polyphenylene sulfide resin composition may include a thermostat housing. In the present invention, by using not only calcium carbonate but also a high-boiling inorganic filler, barium sulfate and zinc oxide reinforced polyphenylene sulfide and inorganic filler and a reactive compatibilizer for excellent dispersibility, A resin composition excellent in chemical and airtightness is provided. The polyphenylene sulfide resin composition is excellent in heat resistance, chemical resistance, dimensional stability, and is non-toxic, so that it can be applied to various fields. The application field of the molded article is suitable for a thermostat housing which requires airtightness based on various chemical resistance and dimensional stability in an engine system, and is excellent in heat resistance, and can be used for electric and electronic parts such as a motor case, a lamp socket, Automobile parts, precision machine parts, and the like, but is not limited thereto.

The polyphenylene sulfide resin composition for a thermostat housing includes a polyphenylene sulfide resin composition for a thermostat housing which has a high heat resistance and a high rigidity and is lightweight and is similar to the claims and embodiments / Can be applied.

[Example]

A polyphenylene sulfide resin composition for a thermostat housing was prepared with the composition shown in Table 1 below. Based on 100 parts by weight of polyphenylene sulfide resin, 50 parts by weight to 100 parts by weight of glass fiber as a reinforcing agent, 50 parts by weight to 100 parts by weight of calcium carbonate, 2 parts by weight to 20 parts by weight of barium sulfate and zinc oxide, 1 to 5 parts by weight of 3-glycidoxypropyl trimethoxysilane, and 1 to 5 parts by weight of a polyethylene wax as a montane-based lubricant are fed into a twin-screw extruder and subjected to a series of melting and kneading processes Respectively. Examples 1 to 3 were prepared with specific compositions and contents shown in Table 1 below. To compare measured values of physical properties according to barium sulfate and zinc oxide, compositions without barium sulfate or zinc oxide were compared with Comparative Examples 1 to 3 . The filler or additive which is not described in the following Table 1 may further be included.

[Experimental Example]

(ASTM D638, ASTM D790, and ASTM D256) of the polyphenylene sulfide resin composition prepared in the composition of Table 1 were measured according to the above Examples. The thermal properties (ASTM D648, ASTM E831), the flow index D1238), the antifouling evaluation (MS211-19) and the airtightness evaluation (test method ES 25600-01) of the sealing test section. The results of the experiment are shown in Table 2 below.

The mechanical properties of the polyphenylene sulfide resin composition measured by the above Experimental Examples were elongation, flexural strength, flexural modulus and impact strength, and heat distortion temperature and thermal expansion coefficient were measured to evaluate the thermal properties. Also, flow index, internal antifreeze evaluation, and airtightness evaluation were performed (FIGS. 2 and 3).

Fig. 3 shows the results of evaluation of the antifouling solution of the specimen injection-molded with the polyphenylene sulfide composition according to the present invention. The tensile strength and the flexural strength of the specimen made of the polyphenylene sulfide composition were measured after immersing the specimen in an antifreeze solution of 120 ° C for 3000 hours. The tensile strength and the flexural strength before and after immersion were 10% Respectively. Specifically, the tensile strength before immersion in the antifreeze solution was from 150 MPa to 160 MPa, and the change value from 140 MPa to 150 MPa after immersion in the antifreeze liquid was about 4.5%. The flexural strength measurement value also ranged from 240 MPa to 245 MPa In MPa, the change of mechanical properties was about 7.5% after immersion of the antifreeze solution at about 230 MPa.

Fig. 4 shows the expansion coefficient according to the temperature as a result of thermomechanical analysis of the specimen. The dimensional stability can be confirmed by the dimensional change, and it can be confirmed from the graph that the dimensional change of the test piece (molded product) is not large in accordance with the temperature change within the range of -50 ° C to 50 ° C. The thermal expansion coefficient at 50 ° C was small, about 17.1 × 10 ^-6 in / (in · ° C).

The elongation showed a result of 1.9% in Experimental Example 1, and the flexural modulus was in the range of 17,500 MPa to 18,000 MPa, and in particular, 18,379 MPa in Experimental Example 1. The impact strength showed the maximum value of 71 kg cm / cm in the composition of Example 3, and the flow index showed the composition of Example 1 at 19.7 g / min. In the airtightness evaluation, no leakage occurred in all of Experimental Examples 1 to 3.

From the above results, it was confirmed that Examples 1 to 3 have excellent chemical resistance and dimensional stability and are capable of exhibiting airtightness, and have physical properties applicable to parts of automobile engine system parts and components of electric and electronic fields. However, in the compositions such as the comparative example, the thermal expansion coefficient and the property of the anti-freezing agent were deteriorated when evaluated.

1: Housing assembly - thermostat (housing assy-thermostat)
2: Housing thermostat (housing-thermostat)
3: insert
4: Gasket-housing (gasket-housing)
5: thermostat
6: Gasket-cover
7: cover-thermostat
8: Bolt

Claims (9)

100 parts by weight of polyphenylene sulfide resin;
50 to 100 parts by weight of glass fiber;
50 parts by weight to 100 parts by weight of calcium carbonate;
2 parts by weight to 20 parts by weight of barium sulfate and zinc oxide;
1 to 5 parts by weight of reactive compatibilizing agent; And
1 to 5 parts by weight of a montan lubricant
Lt; / RTI >
Wherein the weight ratio of the barium sulfate and the zinc oxide is 1: 1 to 1.5: 1,
A flexural strength of 185 MPa or more measured according to ASTM D790 standard, a heat distortion temperature (HDT) measured according to ASTM D648 standard of 270 DEG C or more,
The thermal expansion coefficient measured according to the ASTM E831 standard is 20.0 x 10 < ^-6 > in / (in.
In the measurement of mechanical properties after immersing in an antifreeze solution at 120 占 폚 for 3,000 hours, the change in mechanical properties before and after measurement was 10% or less,
Polyphenylene sulfide resin composition. delete The method according to claim 1,
The reactive compatibilizing agent may be epoxy or amino-based and may include 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane [3 3-glycidoxypropyl methyldimethoxysilane], 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, N-2- (aminoethyl) -3- N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane], N-2- (aminoethyl) -3-aminopropyltrimethoxysilane [ , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine [3-triethoxysilyl-N- (1,3 dimethyl-butylidene) propylamine], N-phenyl- N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- [vinylbenzyl] -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride], and combinations thereof. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition is a polyphenylene sulfide resin composition. A first step of mixing 100 parts by weight of polyphenylene sulfide with 2 to 20 parts by weight of a mixture of barium sulfate and zinc oxide in a weight ratio of 1: 1 to 1.5: 1;
A second step of adding 1 to 5 parts by weight of the reactive compatibilizing agent to the mixture of the first step;
A third step of adding 1 to 5 parts by weight of a montane lubricant to the mixture of the second step;
Adding 50 parts by weight to 100 parts by weight of glass fiber to the mixture of the third step and mixing 50 parts by weight to 100 parts by weight of calcium carbonate;
A fifth step of extruding the mixture of the fourth step while heating; And
A sixth step of cooling the extrudate in the fifth step
Wherein the polyphenylene sulfide resin composition is a polyphenylene sulfide resin. A molded article comprising the polyphenylene sulfide resin composition of claim 1. delete delete delete 6. The method of claim 5,
Wherein the molded article comprising the polyphenylene sulfide resin composition comprises a thermostat housing.

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