KR20240071797A - Polyetherketone based resin composition, method for preparing the same and molding products comprising the same - Google Patents

Abstract

The present invention relates to a polyether ketone-based resin composition and a molded article containing the same. According to the present invention, it has excellent friction and wear resistance, surface lubricity, and dimensional stability, as well as good flowability, compatibility, and dispersibility, and has good mechanical properties and processability. It has the effect of providing a polyether ketone-based resin composition that is excellent as a material to replace metal, especially useful for sliding materials, and molded articles containing the same.

Description

Polyether ketone-based resin composition and molded product containing the same {POLYETHERKETONE BASED RESIN COMPOSITION, METHOD FOR PREPARING THE SAME AND MOLDING PRODUCTS COMPRISING THE SAME}

The present invention relates to a polyether ketone-based resin composition and a molded article containing the same, and more specifically, to a polyether ketone-based resin composition and a molded article containing the same. In more detail, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, including mechanical properties and processability. It relates to a polyether ketone-based resin composition that is excellent and can be used as a material to replace metal, and molded articles containing the same.

Recently, the demand for composite materials combining thermoplastic resins and reinforcing fibers with low weight and good mechanical properties has been increasing as materials for the automobile industry, sports equipment industry, electrical and electronic equipment parts, chemical equipment, and processing equipment parts.

These composite materials can be obtained in the form of the thermoplastic resin being melted, dissolved in a solvent, or impregnated into fibers in powder form dispersed in a fluidized bed or aqueous solution.

The impregnated fibers are then stripped of the solvent or aqueous solution in a suitable manner and then heated to melt the remaining resin and form the (semi-)product. In this case, since uniform loading of the fibers by the resin is required, a homogeneous distribution of the resin must be provided in the dispersion. As a related prior document, US Patent No. 5,236,972 states that the dispersion contains a water-soluble polymer, a wetting agent, a biocide, a plasticizer, and A technology for adding an antifoaming agent is being disclosed.

However, the high viscosity contained in composite parts manufactured using these dispersions can cause subsequent formation defects. This is because polymeric resins, which are very viscous in the molten state, can no longer flow properly. For this reason, it is difficult to achieve composite parts with the desired shape and desired surface appearance.

Accordingly, when manufacturing composite parts into sliding members, there is a trend to design molded products more complexly by taking into account the load of the parts receiving hydraulic pressure and the parts receiving torque.

Therefore, the polyether ketone-based resin composition not only secures friction resistance, surface lubricity, and dimensional stability, but also can replace metal parts without problems such as flowability, compatibility, dispersibility, processability, and deterioration of mechanical properties. Development is urgently needed.

In order to solve the problems of the prior art as described above, the present invention provides a material that replaces metal with excellent friction and wear resistance, surface lubricity, and dimensional stability, as well as good flowability, compatibility, and dispersibility, and excellent mechanical properties and processability. The purpose is to provide a usable polyether ketone-based resin composition and molded articles containing the same.

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention

polyether ketone resin; reinforcing fiber; And one or more additives selected from fluorine resin, carbon nanoplate, and inorganic filler;

The polyether ketone-based resin is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ether ketone ketone) (PEEKK), poly(ether ketone ketone) (PEKK), and poly(ether ketone). It is characterized by being at least one selected from among ketone ether ketone ketone) (PEKEKK), poly(ether ether ketone ether ketone) (PEEKEK), poly(ether ether ether ketone) (PEEEK), and poly(ether diphenyl ether ketone) (PEDEK). A polyether ketone-based resin composition is provided.

The polyether ketone-based resin may be included in an amount of 55 to 90% by weight based on 100% by weight of the polyether ketone-based resin composition.

The reinforcing fiber may be included in an amount of 5 to 50% by weight based on 100% by weight of the polyether ketone-based resin composition.

The polyether ketone-based resin may have a melt index (380°C, 5kg) of 46 to 150 cc/10min.

The polyether ketone-based resin composition may include 1 to 15% by weight of fluorine-based resin.

The polyether ketone-based resin composition may include 3 to 5% by weight of carbon nanoplates.

The polyether ketone-based resin composition may include 2 to 15% by weight of the inorganic filler.

The fluorinated resin may be a polymer obtained by polymerizing one or more monomers selected from fluorinated alkyl vinyl ether, fluorinated ethylene, fluorinated propylene, and fluorinated chloroethylene.

The reinforcing fiber may be carbon fiber or glass fiber.

The inorganic filler may be calcium carbonate.

The polyether ketone-based resin may have a melt index (380°C, 5kg) of 36 to 45 cc/10min.

The polyether ketone-based resin composition may have a melt index (380°C, 5kg) of 10 cc/10min or less.

In addition, the present invention

Provided is a molded article characterized in that it is manufactured from the above-described polyether ketone-based resin composition.

The molded article may be a gear, bearing, impeller, dispenser valve, or thrust washer.

According to the present invention, a polyether ketone-based resin composition that has excellent friction and wear resistance, surface lubricity, and dimensional stability, as well as good flowability, compatibility, and dispersibility, and thus has excellent mechanical properties and processability, and can be used as a material to replace metal; and There is an effect of providing a molded product containing this.

Therefore, the resin composition and molded article according to the present invention can be applied to sliding member fields including gears, bearings, impellers, dispenser valves, or thrust washers that require it.

Hereinafter, the polyether ketone-based resin composition of the present invention and molded articles containing the same will be described in detail.

The present inventors studied a polyether ketone-based resin composition that can satisfy market demands for improved heat resistance, mechanical properties, and friction and wear resistance that can replace metal in gears, bearings, thrust washers, etc., and found that polyether ketone Based on ketone resin and reinforcing fiber, specific fluorine resin and specific inorganic filler are applied to reinforce rigidity such as surface lubricity, friction characteristics, and dimensional stability, making it a polyether ketone resin that has excellent friction and wear resistance without significant deterioration of mechanical properties. It was confirmed that the composition was manufactured, and based on this, the present invention was completed.

The polyether ketone-based resin composition of the present invention includes a polyether ketone-based resin; reinforcing fiber; and one or more additives selected from fluorine-based resins, carbon nanoplates, and inorganic fillers, wherein the polyether ketone-based resin is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), and poly(ether ketone). Ether Ketone Ketone) (PEEKK), Poly (Ether Ketone Ketone) (PEKK), Poly (Ether Ketone Ether Ketone Ketone) (PEKEKK), Poly (Ether Ether Ketone Ether Ketone) (PEEKEK), Poly (Ether Ether Ether Ketone) ( PEEEK) and poly(etherdiphenyletherketone) (PEDEK). In this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, while also having good flowability, compatibility, and dispersibility. It has excellent mechanical properties and processability, so it can be used as a material to replace metal.

As another example, the present invention is a polyether ketone-based resin It contains 55 to 90% by weight, 1 to 15% by weight of fluorine resin, 5 to 50% by weight of reinforcing fiber, 0 to 15% by weight of carbon nanoplate, and 2 to 15% by weight of inorganic filler, and the melt of the polyether ketone resin It is characterized by an index (380°C, 5kg) of 46 to 150 cc/10min, and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, thereby improving mechanical properties and processability. It is excellent and can be used as a material to replace metal, and thus has the advantage of being particularly useful for sliding members.

As another example, the present invention is a polyether ketone-based resin It contains 55 to 90% by weight, 0 to 15% by weight of fluorine resin, 5 to 50% by weight of reinforcing fiber, 3 to 5% by weight of carbon nanoplate, and 2 to 15% by weight of inorganic filler, and the melt of the polyether ketone resin It is characterized by an index (380°C, 5kg) of 36 to 45 cc/10min, and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, thereby improving mechanical properties and processability. It is excellent and can be used as a material to replace metal, and thus has the advantage of being particularly useful for sliding members.

As another example, the present invention is a polyether ketone-based resin It contains 55 to 90% by weight, 1 to 15% by weight of fluorine resin, 5 to 50% by weight of reinforcing fiber, 0 to 15% by weight of carbon nanoplate, and 2 to 15% by weight of inorganic filler, and the melt of the polyether ketone resin It is characterized by an index (380°C, 5kg) of 46 to 150 cc/10min, and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, thereby improving mechanical properties and processability. It is excellent and can be used as a material to replace metal, and thus has the advantage of being particularly useful for sliding members.

Hereinafter, each component constituting the polyether ketone-based resin composition of the present material will be examined in detail as follows.

Polyether ketone resin

The polyether ketone-based resin of the present disclosure includes structural units represented by the following formula.

[Formula 1]

(- Ar - X -) and (- Ar1 - Y -)

In the above formula, Ar and Ar1 each represent a divalent aromatic radical, X represents an electron-withdrawing group, and Y represents an oxygen atom, a sulfur atom, or an alkylene group.

The Ar and Ar1 are, for example, 1,3-phenylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2,6-naph. tylene, which may also be optionally substituted.

The X may be selected from, for example, a carbonyl group and a sulfonyl group.

For example, Y may be selected from -CH2- and isopropylidene.

Furthermore, in the above X and Y units, at least 50%, at least 70%, especially at least 80% of the You can.

It may be preferred that 100% of the X groups represent carbonyl groups and 100% of the Y groups represent oxygen atoms.

The polyether ketone-based resin of the present substrate is preferably poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ether ketone ketone) (PEEKK), poly(ether ketone ketone) (PEKK) ), poly(etherketoneetherketoneketone) (PEKEKK), poly(etheretherketoneetherketone) (PEEKEK), poly(etheretheretherketone) (PEEEK) and poly(etherdiphenyletherketone) (PEDEK). It may be one or more types, and more preferably, poly(etherether ketone) (PEEK) containing a unit represented by the following formula 1-1, a unit represented by the following formula 1-2, and a unit represented by the following formula 1-3. It is one or more types selected from poly(etherketone ketone) (PEKK) containing units and mixtures thereof, and in this case, it has excellent anti-wear and friction properties, surface lubricity, and dimensional stability.

[Formula 1-1]

The structure of Chemical Formula 1-1 may be a meta type as shown in Chemical Formulas 1-1a to 1-1b below.

[Formula 1-1a to 1-1b]

,

Additionally, the structure of Formula 1-1 may partially or completely introduce an ortho arrangement, as shown in Formula 1-1c below.

[Formula 1-1c]

The poly(etherether ketone) (PEEK) can be obtained, for example, through the esterification reaction of butane-1,4-diol and terephthalic acid or the polymerization of butane-1,4-diol and dimethyl terephthalate. You can.

[Formula 1-2]

[Formula 1-3]

The arrangement may be of the para type, as shown in the above-mentioned Chemical Formula 1-2.

The poly(etherketone ketone) (PEKK) can be obtained, for example, through the esterification reaction of butane-1,4-diol and terephthalic acid or the polymerization of butane-1,4-diol and dimethyl terephthalate. You can.

For example, the poly(etherketone ketone) (PEKK) preferably has 35 to 100% by weight, specifically 50 to 90% by weight, especially 55% by weight, relative to the sum of terephthalic units, terephthalic and isophthalic units as repeating units. It may be a polymer comprising from 85% by weight of terephthalic units.

In the present disclosure, the weight ratio of the repeating unit in the resin or copolymer may be a value calculated by converting the repeating unit to a monomer, or may be the weight ratio of the monomer added when polymerizing the resin or copolymer.

The polyetherketone-based resin has a volume median diameter Dv50 of, for example, 1 to 300 um, specifically 5 to 100 um, especially 10 to 50 um, as measured according to standard ISO 13 320 on the Insitec equipment of Malvern for the powder type. can indicate.

The weight average molecular weight Mw of the polyether ketone-based resin measured by chromatography analysis does not increase by more than 100%, for example, by 50% or less, and especially by 20% or less after heat treatment at 375°C for 20 minutes.

In this disclosure, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze).

The polyether ketone-based resin may preferably be 55 to 90% by weight, 58 to 88% by weight, or 58 to 80% by weight based on a total of 100% by weight of the polyether ketone-based resin composition, and within this range, the friction and wear resistance , surface lubricity, dimensional stability, flowability, compatibility and dispersibility are all excellent.

The polyether ketone-based resin preferably has a melt index (380°C, 5kg) of 46 to 150 cc/10min, 46 to 120 cc/10min, 46 to 110 cc/10min, 46 to 100 cc/10min, or 50 to 100 cc/10min. It is 120 cc/10min, and within this range, it has excellent anti-wear and friction properties and dimensional stability.

The polyether ketone-based resin preferably has a melt index (380°C, 5kg) of 36 to 45 cc/10min, 36 to 43 cc/10min, 36 to 41 cc/10min, 36 to 39 cc/10min, or 40 to 40 cc/10min. 45 cc/10min, and within this range, excellent surface lubricity and formability are achieved.

The polyether ketone-based resin can preferably be used in the form of flakes, and in this case, it has excellent mechanical properties such as impact strength and bending strength, as well as excellent processability and appearance quality.

In the present description, polyphenylene oxide in the form of flakes is commercially available as long as it meets the definition of the present invention, but can be manufactured and used by a method commonly used in the technical field to which the present invention pertains, and is not particularly limited.

In this description, flake refers to a flaky shape broadly including scales and granules, and as a specific example, it may be a flake shape with a thickness of 1 to 20 μm and a length of 0.05 to 1 mm. As another example, the flakes may be in the form of thin flakes with a ratio of length to thickness (L/D) of 1.5 to 500, preferably 2 to 100, and more preferably 10 to 50.

The thickness and length of the flakes in this substrate can be measured through microscopic analysis.

The manufacturing method of the polyether ketone-based resin is not particularly limited as long as it is a manufacturing method commonly used in the technical field to which the present invention pertains, and examples include interfacial polymerization, melt polycondensation, solution polycondensation, or ester polymerization. It may be an exchange reaction, etc.

Reinforcement fiber

The reinforcing fibers of the present substrate may be selected from fibers that can form a composite material with the polyether ketone resin.

The reinforcing fibers include glass fibers, quartz fibers, carbon fibers, graphite fibers, silica fibers, metal fibers such as steel fibers, aluminum fibers, boron fibers, ceramic fibers such as silicon carbide or boron carbide fibers, synthetic organic fibers such as aramid fibers. or poly(p-phenylene benzobisoxazole) fibers, better known by the abbreviation PBO, or PAEK fibers, or mixtures of these fibers.

Preferably, the reinforcing fiber may be carbon fiber or glass fiber, more preferably carbon fiber.

When combined with other compounds, the reinforcing fiber does not significantly change the viscosity of the polyether ketone resin in the composite material.

The reinforcing fibers may be in the form of roving (a yarn made of thousands of individual filaments), a mat, or a textile obtained by weaving roving.

The reinforcing fiber may be included in an amount of 0 to 50% by weight in a total of 100% by weight of the polyether ketone-based resin composition, for example, 1 to 50% by weight, more preferably 10 to 50% by weight, even more preferably 20% by weight. to 45% by weight, and within this range, the physical property balance between mechanical properties, friction resistance, and flowability is all excellent.

For example, the carbon fiber may have a diameter of 5 to 30 um, 5 to 20 um, or 10 to 15 um, and within this range, it has excellent balance between mechanical properties, friction and wear resistance, and flowability.

In this description, the reinforcing fibers may be manufactured according to methods commonly used in the technical field to which the present invention belongs, or commercially available, as long as they comply with the definition of the present invention, and are not particularly limited.

fluorine resin

The fluorine resin of the present material can enhance surface lubrication, friction properties, and dimensional stability.

For example, the fluorinated resin may be a polymer obtained by polymerizing one or more monomers selected from fluorinated alkyl vinyl ether, fluorinated ethylene, fluorinated propylene, and fluorinated chloroethylene, preferably fluorinated ethylene, and more preferably polytetrafluoroethylene. It may be rotethylene.

The fluorine-based resin may be included, for example, in an amount of 0 to 20% by weight, 3 to 20% by weight, 5 to 20% by weight, or 1 to 15% by weight, based on a total of 100% by weight of the polyether ketone-based resin composition, within this range. It has excellent friction characteristics and formability while providing excellent dimensional stability.

The fluorine-based resin may be included in an amount of 5 to 20% by weight, or 1 to 15% by weight when, for example, a polyether ketone-based resin having a melt index (380°C, 5kg) in the range of 46 to 150 cc/10min is used.

The fluorine-based resin may be included in an amount of 3 to 20% by weight, or 1 to 15% by weight, for example, when using a polyether ketone-based resin with a melt index (380°C, 5kg) in the range of 36 to 45 cc/10min.

In this description, the fluorine resin may be manufactured according to a method commonly used in the technical field to which the present invention belongs, or commercially available, as long as it meets the definition of the present invention, and is not particularly limited.

carbon nanoplate

The carbon nanoplate of the present substrate is, for example, a plate-shaped carbon nanoplate, preferably a plate-shaped carbon nanoplate with an average thickness of 5 to 50 nm, and within this range, a polyether ketone-based carbon nanoplate is formed due to the mutual dispersion effect with the reinforcing fibers described above. It has the advantage of greatly improving the mechanical properties, moldability, and processability of the resin.

The carbon nanoplate may preferably include one or more selected from exfoliated graphite, graphene nanoplate, and exfoliated expanded graphite, and more preferably exfoliated graphite, and within this range, may be mutually dispersed with the above-described reinforcing fibers. This effect has the advantage of greatly improving the mechanical properties, moldability, and processability of the polyether ketone resin.

For example, the exfoliated graphite may be graphite obtained by processing layered graphite to a thickness of 5 to 50 nm through chemical and/or physical exfoliation methods.

The chemical and/or physical peeling method of the layered graphite is not particularly limited as long as it is a peeling method commonly used in the technical field to which the present invention pertains, and specific examples include the Brodie method, Hummers method, etc. This may be a method of reforming and expanding graphite and then exfoliating it through ultrasonic pulverization, rapid heating, etc.

The carbon nanoplate may be included, for example, in an amount of 0 to 10 wt%, 1 to 10 wt%, or 3 to 10 wt% based on a total of 100 wt% of the polyether ketone-based resin composition, and within this range, the friction properties and molding It has excellent properties and excellent dispersibility.

For example, when using a polyether ketone-based resin with a melt index (380°C, 5kg) in the range of 46 to 150 cc/10min, the carbon nanoplate may be included in an amount of 0 to 15% by weight, or 1 to 10% by weight. .

For example, when using a polyether ketone-based resin with a melt index (380°C, 5kg) in the range of 36 to 45 cc/10min, the carbon nanoplate may be included in an amount of 1 to 10% by weight, or 3 to 7% by weight. .

The carbon nanoplate may have an average thickness of more preferably 5 to 40 nm, and even more preferably 10 to 40 nm, and within this range, it has excellent friction properties and formability due to the interdispersion effect with the reinforcing fibers described above. However, it has the effect of improving dispersibility at the same time.

The carbon nanoplate may preferably have a size of 3.0 um or less in a sea and island structure.

In the present disclosure, the average thickness of the carbon nanoplate is not particularly limited when measured by a measurement method commonly used in the technical field to which the present invention pertains, and may be measured using an electron microscope analysis method as a specific example.

In this description, the carbon nanoplate may be manufactured according to a method commonly used in the technical field to which the present invention belongs, or a commercially available carbon nanoplate may be used within the scope that meets the definition of the present invention, and is not particularly limited.

inorganic filler

The inorganic filler of the present invention can provide mechanical properties, friction resistance, and physical property balance.

For example, the inorganic filler may be calcium carbonate.

The inorganic filler may be included, for example, in an amount of 0 to 15 wt%, 1 to 15 wt%, or 2 to 15 wt% based on a total of 100 wt% of the polyether ketone-based resin composition, and within this range, the friction properties and moldability It has excellent properties and has excellent dispersibility.

The inorganic filler may be included in an amount of 0 to 15% by weight, or 1 to 5% by weight, for example, when using a polyether ketone resin having a melt index (380°C, 5kg) in the range of 46 to 150 cc/10min.

The inorganic filler may be included in an amount of 1 to 5% by weight, or 3 to 5% by weight, for example, when using a polyether ketone resin having a melt index (380°C, 5kg) in the range of 36 to 45 cc/10min.

In this description, the inorganic filler may be manufactured according to a method commonly used in the technical field to which the present invention belongs, or commercially available, as long as it meets the definition of the present invention, and is not particularly limited.

Other additives

If necessary, the polyether ketone-based resin composition of the present invention may further include carbon nanotubes.

The carbon nanotubes may preferably have a BET surface area of 180 to 600 m ² /g, more preferably 180 to 400 m ² /g, even more preferably 180 to 300 m ² /g, even more preferably is 200 to 300 m ² /g, and within this range, the effect of improving processability and conductivity is significant.

In this material, the BET surface area can be measured by the nitrogen adsorption method, and as a specific example, it can be measured by the BET 6-point method by the nitrogen gas adsorption method using a pore distribution analyzer (Bell Japan Inc, Belsorp-II MRFi). And, as another example, it can be measured by the Brunauer, Emmett, and Teller method (method based on ASTM 6556).

The carbon nanotubes are preferably present in an amount of 40% by weight or less, 1 to 30% by weight, or 2 to 20% by weight, based on a total of 100% by weight of the polyether ketone resin, and within this range, the mechanical properties, processability and moldability are improved. It has excellent effects.

The carbon nanotubes include, for example, single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), and multi-walled carbon nanotubes (MWCNT). It may be one or more types selected from the group consisting of.

For example, the carbon nanotubes may be bundled (rope type) or non-bundle (entangle type).

In this description, the terms 'bundle type' and 'non-bundle type' are not particularly limited as long as they are 'bundle type' and 'non-bundle type', respectively, which are commonly approved or defined in the technical field to which the present invention belongs.

The carbon nanotubes preferably have an average diameter of 5 to 30 nm, 7 to 20 nm, or 10 to 15 nm, and within this range, conductivity and appearance quality are significantly improved.

In the present disclosure, the average diameter of the carbon nanotubes is not particularly limited when measured by a measurement method commonly used in the technical field to which the present invention pertains, and may be measured by an electron microscope analysis method as a specific example.

Polyether ketone-based resin composition

The polyether ketone-based resin composition of the present invention includes, for example, a polyether ketone-based resin; reinforcing fiber; and one or more additives selected from fluorine-based resins, carbon nanoplates, and inorganic fillers, wherein the polyether ketone-based resin is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), and poly(ether ketone). Ether Ketone Ketone) (PEEKK), Poly (Ether Ketone Ketone) (PEKK), Poly (Ether Ketone Ether Ketone Ketone) (PEKEKK), Poly (Ether Ether Ketone Ether Ketone) (PEEKEK), Poly (Ether Ether Ether Ketone) ( PEEEK) and poly(etherdiphenyletherketone) (PEDEK). In this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, while also having good flowability, compatibility, and dispersibility. It has excellent mechanical properties and processability, so it can be used as a material to replace metal.

As another example, the present invention is a polyether ketone-based resin It contains 55 to 90% by weight, 1 to 15% by weight of fluorine-based resin, 5 to 50% by weight of reinforcing fiber, 0 to 15% by weight of graphite, and 2 to 15% by weight of inorganic filler, and the melt index of the polyether ketone-based resin ( 380°C, 5kg) is 46 to 150 cc/10min, and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, leading to excellent mechanical properties and processability. Therefore, it has the effect of being able to be used as a material replacing metal, and thus has the advantage of being particularly useful for sliding members.

As another example, the present invention is a polyether ketone-based resin It contains 55 to 90% by weight, 0 to 15% by weight of fluorine-based resin, 5 to 50% by weight of reinforcing fiber, 3 to 5% by weight of graphite, and 2 to 15% by weight of inorganic filler, and the melt index of the polyether ketone-based resin ( 380°C, 5kg) is 36 to 45 cc/10min, and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, leading to excellent mechanical properties and processability. Therefore, it has the effect of being able to be used as a material replacing metal, and thus has the advantage of being particularly useful for sliding members.

As another example, the present invention is a polyether ketone-based resin It contains 55 to 90% by weight, 1 to 15% by weight of fluorine-based resin, 5 to 50% by weight of reinforcing fiber, 0 to 15% by weight of graphite, and 2 to 15% by weight of inorganic filler, and the melt index of the polyether ketone-based resin ( 380°C, 5kg) is 46 to 150 cc/10min, and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability, and has good flowability, compatibility, and dispersibility, leading to excellent mechanical properties and processability. Therefore, it has the effect of being able to be used as a material replacing metal, and thus has the advantage of being particularly useful for sliding members.

The resin composition of the present invention preferably has a melt index (380°C, 5kg) of 10 cc/10min or less, more preferably 1 to 8 cc/10min, and preferably 3 to 8 cc/10min, within this range. It has excellent physical property balance and has the advantages of excellent friction and wear resistance, formability, dispersibility, and processability.

The resin composition preferably has a coefficient of friction (contact type, 1 kg load) of 0.1 or less, 0.05 to 0.1, and has excellent physical property balance within this range, and has excellent friction resistance, moldability, dispersibility, and dimensional stability. There are outstanding benefits.

The resin composition preferably has an abrasion amount (CS17 abrasion wheel, 1 kg load, 3,000 rotations) of 70 or less, and within this range, it has excellent physical property balance and excellent friction wear resistance, formability, dispersibility, and dimensional stability. There is an advantage.

The resin composition preferably has a flowability (spiral test, barrel temperature of 310°C) of 23 cm or more, and has excellent physical property balance within this range, and has excellent friction resistance, moldability, dispersibility, and dimensional stability. There is.

The resin composition preferably has a tensile strength of 155 MPa or more, a specific example is 155 to 270 MPa, and a preferred example is 200 to 265 MPa under the conditions of a specimen thickness of 4 mm and a measurement speed of 50 mm/min based on the ISO 527 method. Within this range, it has the advantage of excellent physical property balance, friction wear resistance, formability, dispersibility, and dimensional stability.

The resin composition preferably has a notch Charpy of 40 J/m or more, more preferably 45 J/m or more under the conditions of a specimen thickness of 4 mm and a measurement temperature of 25°C based on the ISO 180A method, and specific examples are 45 to 80 J/m, and a preferred example is 45 to 75 J/m, and within this range, there is an advantage in that the physical property balance is excellent, and the friction wear resistance, moldability, dispersibility, and dimensional stability are excellent.

Method for producing resin composition

The method for producing the resin composition of the present disclosure preferably includes polyether ketone-based resin; reinforcing fiber; and at least one additive selected from fluorine-based resin, carbon nanoplate, and inorganic filler; and the step of kneading and extruding, wherein the polyether ketone-based resin is poly(ether ketone) (PEK), poly(ether ether ketone). ) (PEEK), poly(etheretherketoneketone) (PEEKK), poly(etherketoneketone) (PEKK), poly(etherketoneetherketoneketone) (PEKEKK), poly(etheretherketoneetherketone) (PEEKEK), It is characterized in that it is at least one selected from poly(etheretheretherketone) (PEEEK) and poly(etherdiphenyletherketone) (PEDEK), and in this case, it has excellent friction and wear resistance, surface lubricity, and even dimensional stability and flowability. , it has good compatibility and dispersibility, and has excellent mechanical properties and processability, so it can be used as a material to replace metal, and thus has the advantage of providing a resin composition that is particularly useful for sliding members.

As another example, the present invention is a polyether ketone-based resin Comprising 55 to 90% by weight of fluorine resin, 1 to 15% by weight of reinforcing fiber, 0 to 15% by weight of carbon nanoplate, and 2 to 15% by weight of inorganic filler, and kneading and extruding, The kneading and extrusion are performed using an extruder with 5 or more kneading blocks, and the polyether ketone resin has a melt index (380°C, 5kg) of 46 to 150 cc/10 min. In this case, the It has excellent frictional wear resistance, surface lubricity, and even dimensional stability, as well as good flowability, compatibility, and dispersibility, so it has excellent mechanical properties and processability, so it can be used as a material to replace metal, which is a particularly useful advantage for sliding members. There is.

As another example, the present invention is a polyether ketone-based resin Comprising 55 to 90% by weight of fluorine resin, 0 to 15% by weight of reinforcing fiber, 3 to 5% by weight of carbon nanoplate, and 2 to 15% by weight of inorganic filler, and kneading and extruding, The kneading and extrusion are performed using an extruder with two or more kneading blocks, and the polyether ketone resin has a melt index (380 ° C., 5 kg) of 36 to 45 cc / 10 min. In this case, the It has excellent frictional wear resistance, surface lubricity, and even dimensional stability, as well as good flowability, compatibility, and dispersibility, so it has excellent mechanical properties and processability, so it can be used as a material to replace metal, which is a particularly useful advantage for sliding members. There is.

The kneading and extrusion may be performed within a range where the barrel temperature is, for example, 250°C or more, 290 to 350°C, 290 to 340°C, 300 to 330°C, or 310 to 330°C, in which case the throughput per unit time is high and There is an advantage that sufficient melt kneading is possible and problems such as thermal decomposition of the resin component do not occur.

The kneading and extrusion may be performed under conditions where the screw rotation speed is, for example, 100 rpm or more, 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, 150 to 320 rpm, or 200 to 310 rpm, and within this range, the throughput per unit time is high. While the process efficiency is excellent, excessive cutting of carbon nanoplates is suppressed, and the final product has the advantage of superior friction wear resistance and dimensional stability.

The resin composition obtained through the kneading and extrusion may preferably be provided in pellet form.

As a specific example, reinforcing fibers impregnated with polyether ketone resin can be dried, for example, in an infrared oven to remove water.

The impregnated and dried fibers can then be heated until the resin melts.

It can then be shaped into a semi-finished product if required and shaped, for example by calendering, to provide proportions. At this time, the semi-finished product manufactured according to the method of the present invention is characterized in that the viscosity of the resin hardly changes despite the high temperature required for production to melt the resin.

In addition, the semi-finished product obtained according to the method of the invention can be used in particular for the production of composite parts.

Composite parts are obtained, for example, by first producing a preform, in particular by placing or draping a pre-impregnated semi-finished product in a mold.

The composite part is then obtained by compaction, during which the preform is heated and compressed, for example in an autoclave or press, to assemble the semi-finished product by melting.

The composite products produced according to the method of the invention are characterized in particular by little change in the viscosity of the resin despite the high temperatures required for production. An excessively high viscosity is not necessary to ensure that the semi-finished product matches the shape of the actual mold, and the viscosity of the matrix also ensures good flow during compaction, preventing surface defects such as wrinkles.

The method for manufacturing the molded article of this material is preferably a polyether ketone-based resin. Comprising 55 to 90% by weight of fluorine resin, 1 to 15% by weight of reinforcing fiber, 0 to 15% by weight of carbon nanoplate, and 2 to 15% by weight of inorganic filler, and kneading and extruding, The kneading and extrusion are performed using an extruder with two or more kneading blocks, and the polyether ketone resin has a melt index (380 ° C., 5 kg) of 46 to 150 cc / 10 min. In this case, it has an excellent appearance. , it has excellent friction and wear resistance along with rigidity and dimensional stability, which has the effect of providing molded products with minimal damage such as cracks when used as a sliding member.

The injection molding is not particularly limited as long as it follows methods and conditions commonly used in the technical field to which the present invention pertains, and can be appropriately selected and applied as needed.

In describing the resin composition, molded product, and method of manufacturing the present material, other conditions not specifically specified (e.g., configuration or specifications of the extruder and injection machine, extrusion and injection conditions, additives, etc.) are commonly used in the art. If it is within the scope, it is not particularly limited and it is specified that it can be selected and implemented as needed.

Hereinafter, the present invention will be described in detail. The type of extruder for producing the resin composition of the present base is not particularly limited, and any extruder commonly used in the industry can be appropriately selected and implemented. For example, an extruder equipped with one screw A single-screw extruder or a multi-screw extruder with a plurality of screws can be used, and when considering uniform mixing of materials, ease of processing, and economic efficiency, it may be preferable to use a twin-screw extruder with two screws.

The extruder consists of a feeder for supplying materials into the barrel, a screw for transporting and kneading the materials supplied into the barrel, and a die for extruding the kneaded materials. The screw is composed of a plurality of screw elements to provide various functions.

There may be one or more raw material suppliers, and two or more may be optionally provided as needed. For example, a main inlet and an optional auxiliary inlet may be provided, and two or more auxiliary inlets may be provided as needed.

As a specific example, polyether ketone-based resin, fluorine-based resin, reinforcing fiber, carbon nanoplate, and inorganic filler may be injected into the main inlet, and as another example, polyether ketone-based resin and reinforcing fiber may be injected into the main inlet. After that, fluorine resin, carbon nanoplates, and inorganic fillers can be added to the auxiliary inlet. In a preferred embodiment, it may be possible to add all ingredients except the polyether ketone resin into the main inlet and add the polyether ketone resin into the auxiliary inlet.

As another example, adding polyether ketone resin and reinforcing fiber into the main inlet, adding some of the fluorine resin, carbon nanoplate, and inorganic filler into auxiliary inlet 1, and then putting the remaining amount into auxiliary inlet 2. It may be possible.

In another example, polyether resin may be added to the main inlet, fluorine resin, carbon nanoplates, and inorganic fillers may be added to auxiliary inlet 1, and reinforcing fiber may be added to auxiliary inlet 2.

The kneading block of the present invention is an example of the screw element, and is specifically composed of a plurality of disks, preferably 3 to 7 disks, 5 to 7 disks, 3 to 5 disks, or 4 to 5 disks, and is usually polygonal or It has a cross-section such as an oval shape and is continuously arranged in the direction of material transport. In addition, the phase angle (meaning the movement angle between the disks) of the disks in the kneading block is preferably 45 to 90°.

In addition, the kneading block includes a forward kneading block with the ability to transport, distribute and mix materials, a neutral kneading block with only distribution and mixing capabilities without the ability to transport materials, and a neutral kneading block with the ability to transport materials in the opposite direction to the transport direction. There are backward kneading blocks that allow reverse transfer.

The polyether ketone-based resin composition according to the present invention has, for example, 2 or more, 2 or 3, 9 or more, preferably 10 or more, more preferably 12 or more, preferred examples include 9 to 9. It can be manufactured including the steps of kneading and extruding using 18 extruders, more preferably 10 to 18 extruders, more preferably 12 to 16 extruders. At this time, it can be effective to use kneading blocks in combination in the order of forward, perpendicular, and reverse with respect to the resin flow direction, and a combination of continuous or separated blocks can be used depending on the mixing method. In this case, the dispersibility of the reinforcing fiber and the inorganic filler component and the compatibility of the composition are further improved, making it possible to provide a higher quality resin composition.

For example, nine or more kneading blocks may be arranged continuously, and for another example, they may be arranged discontinuously between screws. As a specific example, 3 to 6 kneading blocks are continuously provided between the main inlet and auxiliary inlet 1, 3 to 8 kneading blocks are continuously provided between auxiliary inlet 1 and auxiliary inlet 2, and auxiliary inlet 2 2 to 5 kneading blocks may be provided between the outlet and the discharge port (not shown). When arranged in this way, local heat generation during melt kneading can be controlled to prevent thermal deformation of the raw material, and excessive cutting of nano components is prevented, which has the advantage of not deteriorating electrical conductivity and mechanical properties.

molded product

Molded articles can be manufactured from the resin composition of this base.

The molded article may be a gear, bearing, impeller, dispenser valve, or thrust washer.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the attached patent claims.

[Example]

The components used in the following examples and comparative examples are as follows.

* Polyether ketone resin 1: Polyether ketone ketone (PEKK), manufactured by Hanwha Solutions, product name (MFR 60g/10min), was used.

* Polyetherketone-based resin 2: Polyetheretherketone (PEEK) from Arkema, product name Kepstan 7003 (MFR 43g/10min, Dv50 20 ㎛) was used.

* Polyetherketone-based resin 3: VICTREX, product name PEEK450G (Melt Viscosity (400 350 Pa.s, Dv50 = 20 ㎛)) was used as polyetheretherketone (PEEK).

* Polyetherimide: PEI, product name ULTEM 1000 (Melt Volume Rate: 13 cc/10min)

* Carbon Fiber: Carbon Fiber, product name ZOLTEK PX35 (Fiber Length 6mm)

* ZRP: zirconium phosphate

* Fluorinated resin: Fluorinated ethylene (PTFE) with a diameter of 25 mm and a porosity of 0.2 μm, manufactured by GCC for Compund.

Examples 1 to 3 and Comparative Examples 1 to 5

The ingredients and contents listed in Table 1 below were mixed at a temperature of 300 to 330 using a twin-screw extruder (Uniplus TSE-32-44) with 3 to 4 mixing blocks, a screw L/D of 12:1, and a ϕ value of 32 mm. The temperature was set to ℃ and the rotation speed (rpm) was set to 300 rotations/min, and melt-kneaded and extruded to make pellets. The twin-screw extruder had a total of two or more inlets, and ingredients other than polyether ketone resin were input into the main inlet, and polyether ketone was injected into the auxiliary inlet.

After drying the manufactured pellets at 150 ℃ or higher for 4 hours or more, specimens for evaluation were manufactured using an injection machine [ENGEL, 80 tons] at an injection temperature of 390 ℃, and were incubated for 24 hours in an environment with a temperature of 23 ℃ and a relative humidity of about 50%. After standing for some time, the physical properties were measured according to ISO standards.

<Test Example 1>

The properties of the polyether ketone-based resin composition specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 1 below.

* Impact strength (J/m): Notched Charpy impact strength was measured according to the ISO 180A method using a 4mm thick specimen, and was measured at room temperature (23°C) after notching the specimen.

* Tensile strength (MPa) and tensile modulus of elasticity (MPa): A specimen with a thickness of 4 mm was used and the measurement speed was 50 mm/10 min according to the ISO 527 method.

* Flexural strength (MPa) and flexural modulus (MPa): A specimen with a thickness of 4 mm was used and the measurement speed was 50 mm/10 mn according to the ISO 527 method.

에 의거하여 측정하였다.* Melt index (380℃, 5kg, unit cc/10min): Standard measurement ASTM D1238 (380

It was measured based on .

)에서 측정하였다. *Specific gravity: Room temperature (23%) according to ASTM D792 method

) was measured.

* Surface quality (appearance): The appearance of the injection specimen was evaluated with the naked eye. Here, ◎: both excellent formability and appearance, ○: both good formability and appearance, △: good appearance (pinholes observed intermittently), observed).

** Heat distortion temperature (°C): Measured under a stress of 1.80 MPa according to the ISO 75 method using a specimen with a thickness of 4 mm.

Coefficient of friction (contact type, 1 kg load) and wear (CS17 wear wheel, 1 kg load, 3,000 revolutions, unit mg):

* Flowability (spiral test, barrel temperature 310 degrees, unit cm): Measured using the commonly used spiral test method. The maximum injection pressure (3,100 kg/cm2), injection speed (3,500 kg/cm2), holding pressure (3,000 kg/cm2), and filling amount (45 mm) in the injection machine were kept constant, and the barrel temperature during injection was 375 ℃ in the nozzle and 1 transfer unit. It was set at 380 ℃, transfer part 2 380 ℃, and inlet 385 ℃.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyether ketone resin 1 57 55 53 100 - 60 - 70 Polyether ketone resin 2 - - - - 100 - 60 - polyetherimide resin - - - - - - - 30 carbon fiber 40 40 40 - - 40 40 - ZRP 3 5 7 - - - - - Impact strength (J/m) 51.89 52.01 46.48 47.19 44.30 55.49 58.46 45.11 Tensile strength (MPa) 224.50 233.0 236.6 88.20 93.90 228.80 223.20 93.90 Tensile modulus (MPa) 28,710 28,229 28,993 3,044 3,100 26,499 25,061 3,049 Elongation_breaking point (Strain) 1.3 1.5 1.5 31.40 76.30 1.5 1.7 48.10 Elongation_yield point (Strain) 1.3 1.5 1.5 5.4 5.70 1.5 1.7 6.20 Flexural strength (MPa) 298.8 304.1 313.6 125.7 127.3 315.1 29.30 135.0 Flexural modulus (MPa) 19,630 20,674 21,152 3,172 3,185 19,994 19,919 3,199 Melt Rate (MVR) 5.60 5.60 5.60 60.12 43.47 6.58 - 42.25 importance 1.46 1.48 1.40 1.27 1.28 1.45 1.44 1/29 Surface quality (appearance) ◎ ◎ ○ X XX X XX ○

As shown in Table 1, the impact strength, tensile strength, and tensile modulus of the resin composition according to the present invention (Examples 1 to 3) are significantly improved compared to the resin composition (Comparative Examples 1 to 5) outside the scope of the present invention. It was confirmed that the flexural strength and flexural modulus were significantly superior in all examples.

In particular, polyether ketone-based resin compositions that do not appropriately contain fluorine-based resins, inorganic fillers, carbon nanoplates, etc. according to the present disclosure (Comparative Examples 1 to 4), and polyether ketone-based resin compositions containing polyetherimide (Comparative Examples 5), it was confirmed that not only the tensile strength and tensile modulus, but also the friction and wear resistance were significantly poor.

That is, the resin composition according to one embodiment of the present invention is a polyether ketone-based material that can satisfy market demands for improved heat resistance, mechanical properties, and friction and wear resistance that can replace metal in gears, bearings, thrust washers, etc. As a result of research on the resin composition, based on polyether ketone resin and reinforcing fibers, specific fluorine resin and specific inorganic fillers were applied to enhance rigidity such as surface lubricity, friction characteristics, and dimensional stability, resulting in excellent durability without significant deterioration in mechanical properties. It has the advantage of providing improvements in friction and wear resistance.

Claims (13)

polyether ketone-based resin; reinforcing fiber; and at least one additive selected from fluorine-based resin, carbon nanoplate, and inorganic filler;
The polyether ketone-based resin is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ether ketone ketone) (PEEKK), poly(ether ketone ketone) (PEKK), and poly(ether ketone). It is characterized by being at least one selected from among ketone ether ketone ketone) (PEKEKK), poly(ether ether ketone ether ketone) (PEEKEK), poly(ether ether ether ketone) (PEEEK), and poly(ether diphenyl ether ketone) (PEDEK). A polyether ketone-based resin composition. According to paragraph 1,
A polyether ketone-based resin composition, characterized in that the polyether ketone-based resin is contained in 55 to 90% by weight based on 100% by weight of the polyether ketone-based resin composition. According to paragraph 1,
The polyether ketone-based resin composition is characterized in that the reinforcing fiber is contained in an amount of 5 to 50% by weight based on 100% by weight of the polyether ketone-based resin composition. According to paragraph 1,
The polyether ketone-based resin is a polyether ketone-based resin composition, characterized in that the melt index (380°C, 5 kg) is 46 to 150 cc/10 min. According to paragraph 1,
The polyether ketone-based resin composition is characterized in that it contains 1 to 15% by weight of a fluorine-based resin. According to paragraph 1,
The polyether ketone-based resin composition is characterized in that it contains 3 to 5% by weight of carbon nanoplates and 2 to 15% by weight of the inorganic filler. According to paragraph 1,
The fluorine-based resin is a polyether ketone-based resin composition, characterized in that it is a polymer obtained by polymerizing one or more monomers selected from fluorinated alkyl vinyl ether, fluorinated ethylene, fluorinated propylene, and fluorinated chloroethylene. According to paragraph 1,
A polyether ketone-based resin composition, wherein the reinforcing fiber is carbon fiber or glass fiber. According to paragraph 1,
A polyether ketone-based resin composition, wherein the inorganic filler is calcium carbonate. According to paragraph 1,
A polyether ketone-based resin composition, characterized in that the polyether ketone-based resin has a melt index (380°C, 5 kg) of 36 to 45 cc/10 min. According to paragraph 1,
The polyether ketone-based resin composition is characterized in that the melt index (380° C., 5 kg)] is 10 cc/10 min or less. A molded article manufactured from the polyether ketone-based resin composition of any one of claims 1 to 11. According to clause 12,
The molded article is a gear, bearing, impeller, dispenser valve, or thrust washer.