WO2016060511A2 - Polyketone resin composition having excellent conductivity - Google Patents

Abstract

The present invention relates to a polyketone resin composition having excellent electrical conductivity, which is prepared by blending conductive carbon black, elastic polyurethane, and carbon fibers, with a polyketone terpolymer composed of repeat units represented by general formulas (1) and (2), and the polyketone resin composition has excellent electrical conductivity, impact resistance, and wear resistance, and thus can be applied to vehicle components, such as a gear, a belt, and a fuel filter, and industrial components such as cams. -[-CH2CH2-CO]x- (1) -[-CH2-CH(CH3)-CO]y- (2) In addition, the present invention provides a highly thermally conductive composite material, which has improved thermal conductivity, by, while containing a polyketone resin and a filler, adjusting the content of the filler. In addition, the present invention relates to a highly thermally conductive composite material for an outdoor housing and an outdoor housing comprising the same and, more specifically, to a highly thermally conductive composite material and an outdoor housing comprising the same, wherein the highly thermally conductive composite material realizes high thermal conductivity and has excellent hygroscopic resistance, by, while containing a polyketone resin and a filler, adjusting the content of the filler.

Description

Polyketone resin composition with excellent conductivity

The present invention relates to a polyketone resin composition having excellent conductivity. More specifically, the present invention is manufactured by blending conductive carbon black, elastic polyurethane, carbon fiber, and the like with polyketone resin, such as automobile parts such as gears, belts, fuel filters, and cams. The present invention relates to a polyketone resin composition applicable to industrial parts.

The present invention also relates to a high thermal conductive composite material, and more particularly, to a high thermal conductive composite material including a polyketone resin and a filler.

In addition, the present invention relates to a high thermal conductivity composite material for an outdoor housing and an outdoor housing including the same, and more particularly, a high thermal conductivity composite material that can be applied to an outdoor or outdoor housing because of high thermal conductivity and excellent moisture resistance. And it relates to an outdoor housing comprising the same.

Polyketone (PK) is a material that has lower raw materials and polymerization process costs than general engineering plastic materials such as polyamide, polyester, and polycarbonate. Polyketone (PK) has excellent properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance. It is widely applied to. There is a growing interest in a group of linear alternating polymers, consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide and ethylene and other olefinically unsaturated hydrocarbons, such as propylene.

The process for preparing polyketone polymers is usually a compound of a Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used. U.S. Pat.No. 4,843,144 describes a process for preparing polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid with a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus. It is starting.

In recent years, many fillers have been used in polyketones for the high value of plastics, the desire for high performance, and the development of high-tech industries. The role of the filler can be seen as cost reduction, improvement of physical properties or properties, functionalization and processability improvement.

Accordingly, the mechanical properties of the polyketone blends are diversified in the application fields of thermoplastics, and demands of industries that require more excellent properties are required to study polyketone blends having improved electrical conductivity, impact resistance, and wear resistance.

On the other hand, light emitting diodes (LEDs) consume less thermal energy and are used in numerous electronic products due to their advantages of high lifespan.

As the LEDs have high brightness and high functionality, the amount of heat emitted from a product rapidly increases, and the heat of heat not only degrades the function of the device, but also causes malfunctions of peripheral devices and substrate degradation. However, the ultra-light weight / thinning of the LED is rapidly progressed, the heat dissipation space constraint is emerging as a problem. In order to prevent this, there is an increasing demand for the use of a high-temperature conductive high-molecular material that is lightweight and has excellent moldability.

In addition, aluminum is mainly used for indoor, outdoor, and outdoor heat conduction materials. However, aluminum, which is widely used as a heat-conducting material, is easy to obtain than other metals and has high thermal conductivity, and thus has great strength in realizing heat-conducting properties.However, the manufacturing process such as post-processing after making a die casting during product manufacturing is complicated. There is a disadvantage in that it is difficult, and when applied to heavy products of the 10kg level (street lights, industrial, etc.), there is a safety risk when falling. In addition, aluminum is also a high heat dissipation material, but at the same time, the heat capacity is large, so that the operating temperature increases when it is used.In order to solve the high heat dissipation properties, the inside of the product is composed of a complicated structural design, which increases the processing cost. There is a problem that causes.

However, the high thermal conductivity of the polymer itself is limited. In order to improve this, high heat radiation composite materials have been developed by compounding high thermal conductivity fillers such as graphite, carbon fiber, and boron nitride, but many fillers are required to realize high thermal conductivity. have. In addition, the high filling composite material has a problem that has a low mechanical properties.

Accordingly, in the art, there is a demand for development of related technologies to utilize high thermal conductivity compared to filler content, and to utilize a thermally conductive composite material and high injection molding freedom thereof to meet the weight reduction while securing mechanical properties. In addition, it can be expected that a high physical property retention rate is required for the thermally conductive composite material so that it can be applied to various applications in which the existing aluminum is applied.

The present invention is to provide a polyketone composition excellent in electrical conductivity, impact resistance and wear resistance compared to the existing polyketone composition to solve the above problems.

In addition, the present invention comprises a polyketone resin and a filler, by adjusting the content of the filler, high thermal conductivity composite material with improved thermal conductivity and excellent hygroscopic resistance can be applied to outdoor or outdoor housings and high thermal conductivity composite material comprising the same An object of the present invention is to provide an outdoor housing.

The present invention to solve the above problems

A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), which has excellent electrical conductivity, comprising a linear alternating polyketone having y / x of 0.03 to 0.3 and conductive carbon black The polyketone resin composition is provided as a means for solving the problem.

-[-CH2CH2-CO] x- (1)

-[-CH2-CH (CH3) -CO] y- (2)

(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)

The polyketone resin composition may include an elastic polyurethane and / or carbon fiber, the polyketone resin composition is 10 to 30 parts by weight of conductive carbon black, elastic polyurethane, carbon fiber compared to 100 parts by weight of polyketone terpolymer It is characterized by including as much.

In another aspect, the present invention provides a gear, a belt, an automobile fuel filter, a cam excellent in electrical conductivity, impact resistance, and wear resistance, which are made of the polyketone resin composition as a means for solving the problem.

Polyketone is 60 to 85% by weight, conductive carbon black is 5 to 20% by weight and elastic polyurethane is 10 to 20% by weight, polyketone polyketone having an impact strength of 10 KJ / m2 or more It provides a polyketone molded article comprising the composition.

A polyketone copolymer composed of repeating units represented by formulas (1) and (2), having an intrinsic viscosity (LVN) of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and y / x of 0.03 Linear alternating polyketone and carbon fiber, wherein the polyketone is 60 to 99% by weight, the carbon fiber is 1 to 40% by weight, and the polyketone composition is Taber wear based on the total weight of the polyketone composition. Using a tester (DAITO ELECTRON CO., LTD.), There is provided a polyketone molded article made of a polyketone composition, characterized in that the wear amount measured in accordance with JIS K-7311 is 2.0 mg or less.

The content of carbon nanotubes or conductive carbon black is 1 to 30% by weight based on the total blend weight, and the surface resistance of the polyketone molded article is preferably 10 ² to 10 ⁴ Ω / cm 2, and the impact strength of the polyketone molded article is 70 It provides a conductive fuel filter made of a polyketone molded article characterized in that the J / m or more.

In addition, the present invention also provides a high thermal conductivity composite material including a polyketone resin and a filler.

At this time, the polyketone resin is 30 to 70% by weight based on the total weight of the high thermal conductivity composite material; And it is preferable that the filler contains 30 to 70% by weight.

In addition, the filler is preferably at least one member selected from the group consisting of carbon-based, nitride-based and metal oxides.

In addition, the high thermal conductivity composite material is preferably a high thermal conductivity composite material for the outdoor housing.

In addition, the present invention also provides an outdoor housing including the high thermal conductivity composite material.

Here, the outdoor housing is preferably used for street lights or transformers.

Polyketone resin composition of the present invention is excellent in electrical conductivity, impact resistance, wear resistance has the advantage that can be used as industrial parts such as automobile parts, such as gears, belts and cams.

In addition, the high thermal conductivity composite material of the present invention includes a polyketone resin and a high content of filler, and thus can be lighter than conventional thermally conductive resins, have excellent light resistance and hygroscopicity, and improve thermal conductivity and impact strength. Can be. For this reason, the high thermal conductivity composite material of the present invention can be easily applied as an outdoor or outdoor housing.

In addition, the thermally conductive composite material used in the present invention can realize the same level of thermal conductivity by applying a smaller amount of filler than the composite material made of polyamide, which is used as a conventional thermally conductive composite material. It can be implemented to reduce manufacturing costs.

The polyketone polymer of the present invention is a linear alternating structure and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons are ethene and α-olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene Aryl aliphatic groups containing aryl substituents on aliphatic or other aliphatic molecules, such as aryl substituents on ethylenically unsaturated carbon atoms. Examples of the aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene. The polyketone polymers preferably used in the present invention are copolymers of carbon monoxide and ethene or second ethylenically unsaturated hydrocarbons having at least three carbon atoms with carbon monoxide and ethene, in particular α-olefins such as propene. Terpolymers.

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.

The intrinsic viscosity (LVN) of the polymer of the polyketone resin of the present invention is preferably 0.5 to 10, more preferably 0.8 to 4.0, and particularly preferably 1.0 to 2.0.

Preferred methods of preparing polyketone polymers are disclosed in US Pat. No. 4,843,144. Carbon monoxide and hydrocarbon monomers in the presence of a palladium compound and a catalyst composition suitably produced from anionic and phosphorus bidentate ligands of less than 6 pKa or preferably less than pKa 2 and preferably less than pKa 2. Is contacted under polymerization conditions to prepare a polyketone polymer.

Preferred methods for preparing polyketone polymers are disclosed in US Pat. No. 4,843,144. Polyketone polymers are prepared by contacting carbon monoxide with hydrocarbon monomers under polymerization conditions in the presence of a palladium compound, a catalyst composition suitably produced from anionic and phosphorus bidentate ligands of less than pKa 6 or preferably less than pKa 2.

As a method for producing a polyketone resin, a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition composed of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus. The polymerization reaction temperature is preferably 50 ~ 100 ℃ and the reaction pressure is 40 ~ 60bar. The polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone. As the palladium compound, palladium acetate is preferable, and the amount of use thereof is preferably 10 ^-3 to 10 ^-1 1 mole. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium. Moreover, 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.

Hereinafter, the polymerization process of the polyketone resin will be described in detail.

The process for producing polyketones is characterized by the presence of an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15. In the method for producing polyketone by terpolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg methanol) and water to form a linear terpolymer, the mixture As a solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.

The catalyst is composed of a ligand having an element of (a) Group 9, Group 10 or Group 11 transition metal compound (b) Group 15 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, 1989).

Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, trifluoromethane sulfonate ruthenium and the like.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel, acetylacetate, palladium acetate and trifluoroacetic acid. Palladium, palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate and the like.

Examples of the Group 11 transition metal compound include a complex of copper or silver, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, Silver trifluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) are palladium compounds in terms of yield and molecular weight of polyketones, and in terms of improving catalytic activity and intrinsic viscosity. Most preferably, palladium acetate is used in the process.

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,3-bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (Diphenylphosphino) benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, 1,2- Bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino] methyl] benzene, 1,1'-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Spinosyns; there may be mentioned a ligand, such as propane.

Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonate-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane. Preferred ligand (b) having an atom of group 15 is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane, most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2 Methoxyphenyl) phosphine).

[Formula 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) of Formula 1 is a polyketone introduced to date Activity equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to exhibit the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention is able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost. The method for preparing a ligand for a polyketone polymerization catalyst is as follows. Using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventionally 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially mass synthesized.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature. Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding and stirring methanol after completion of the reaction; (d) adding toluene and water, washing the oil layer with water after separating the layers, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue is recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) It can be performed through;

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies uniformly since the appropriate value varies depending on the type of the ethylenic and propylene unsaturated compounds selected or other polymerization conditions. Although not limited, it is usually 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the capacity of the reaction zone. The capacity of the reaction zone means the capacity of the liquid phase of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per mol of the transition metal compound (a).

In addition, the addition of benzophenone during the polymerization of polyketones is another feature.

In the present invention, it is possible to achieve the effect of improving the intrinsic viscosity of the polyketone by adding benzophenone during the polymerization of the polyketone. The molar ratio of the (a) Group 9, Group 10 or Group 11 transition metal compound and benzophenone is 1: 5 to 100, preferably 1:40 to 60. If the molar ratio of the transition metal and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of the transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity produced is rather It is not desirable because it tends to decrease.

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Preferred ethylenically unsaturated compounds among these are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

Ternary copolymerization of carbon monoxide, the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex comprising a Group 9, Group 10 or Group 11 transition metal compound (a) and a ligand (b) having an element of Group 15 As a result of the catalyst, the catalyst is produced by contacting the two components. Arbitrary methods can be employ | adopted as a method of making it contact. That is, you may make and use the solution which mixed two components previously in a suitable solvent, and may respectively supply two components separately to a polymerization system, and may contact them in a polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration of a catalyst solution are used. The polymerization may be either batchwise or continuous. The reactor used for superposition | polymerization can use a well-known thing as it is or processing it. There is no restriction | limiting in particular about polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ | adopted. Although there is no restriction | limiting also about the pressure at the time of superposition | polymerization, Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.

Linear alternating polyketones are formed by the polymerization method as described above.

The polymer ring of the polyketone polymer preferred in the present invention may be represented by the following formula (2).

[Formula 2]

-[CO-(-CH2-CH2-)-] x- [CO- (G)] y-

In the formula (2), G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer composed of repeating units represented by General Formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit inferior in meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. And y / x is more preferably 0.03 to 0.1.

-[-CH2CH2-CO] x- (1)

-[-CH2-CH (CH3) -CO] y- (2)

In addition, the melting point of the polymer may be controlled by controlling the ratio of ethylene and propylene of the polyketone polymer. For example, the melting point is about 220 ° C. when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, but the melting point is adjusted to 235 ° C. when the molar ratio is adjusted to 47.3: 2.7: 50.

Particularly preferred are polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer depend on the molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of terpolymers, on the nature of the second hydrocarbon moiety present. Melting | fusing point of the conversion of the polymer used by this invention is 175 degreeC-300 degreeC, and is 210 degreeC-270 degreeC generally. The ultimate viscosity number (LVN) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl / g to 10 dl / g, more preferably 0.8 dl / g to 4 dl / g, More preferably, they are 1.0 dl / g-2.0 dl / g. At this time, if the intrinsic viscosity number is less than 0.5dl / g, the mechanical properties are inferior, and if it exceeds 10dl / g, there is a problem of poor workability.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. Less than 1.5 had a poor polymerization yield, and more than 2.5 had a problem of poor moldability. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of palladium catalyst and polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100 ° C. or more, the molecular weight distribution is increased.

The conductive carbon black and the elastic polyurethane which are subcomponents of the present invention will be described. Polyurethane (POLYURETHANE) is a generic term for high-molecular compounds having URETHANE bond (-NH-COO) in the molecule. Generally, it is obtained by addition reaction using Polyisocyanate and Polyol as the main raw materials. According to their combination method, the synthesis of polyurethanhane material with various molecular structure and physical properties is made, and is typically divided into polyester type and polyether type.

Specifically, the polyketone composition of the present invention is composed of a blend made of a combination of polyketone, conductive carbon black, and an elastic polyurethane, and is characterized by improving electrical conductivity and rebound elasticity.

The weight of the carbon nanotubes or the conductive carbon black or the elastic polyurethane is 1 to 30% by weight based on the total weight. Preferably it is 5 to 20% by weight for carbon black, 10 to 20% by weight for elastic polyurethane. If the content of the polyketone resin is less than 700% by weight, the mechanical strength, dimensional stability, and molding properties of the polyketone resin may be degraded, thereby decreasing practicality. If the content is more than 85%, the relative content of the elastic polyurethane and the conductive carbon black Reduction can make it difficult to impart the desired level of electrical conductivity and resilience.

If the carbon nanotube content is less than 1% by weight, sufficient electrical conductivity to be obtained by adding carbon nanotubes cannot be obtained. If the carbon nanotube content is more than 30% by weight, the thermal stability of the polyketone molded article is not good, and the workability Since there exists a problem of falling, it is preferable to add in the said range.

In addition, carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties. In addition, antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.

The carbon fiber which is a subcomponent of the present invention will be described. Carbon fiber was first known about 100 years ago when T. A. Edison carbonized bamboo fiber and used it as a filament for the bulb. The industrial production began on the basis of cellulose-based fibers in 1959, and in 1990, Taekwang was first produced in Korea. As the raw material, cellulose, acrylic fiber, vinylon, pitch, etc. are used, and molecular arrangements and crystals change depending on the raw material or the processing temperature. In general, hexagonal rings of carbon form a layered lattice successively, and have a metallic luster and black or grey. Excellent heat resistance and impact resistance, resistant to chemicals and high resistance to pests. Molecular weights such as oxygen, hydrogen, nitrogen, etc. are lost during the heating process, and thus the weight is reduced. Therefore, they are lighter than metals (aluminum), and are superior to metals (iron). Due to these characteristics, sporting goods (fishing rods, golf clubs, tennis rackets), aerospace industry (heat-resistant materials, aircraft fuselage), automobiles, civil construction (light materials, interior materials), electrical and electronics, telecommunications (antenna), environmental industry (air purifier) It is widely used as a high performance industrial material in each field.

In Korea, a research team from Chungbuk National University in 1996 began developing an odor removal device using activated carbon fiber. Adsorption capacity is much better than using activated carbon as an adsorbent, which has the advantage of being able to process a large amount at a time, which can greatly improve the work environment of the workplace by reducing facility costs and effectively removing harmful substances.

Specifically, the polyketone composition of the present invention consists of a blend consisting of a combination of polyketone and carbon fiber.

The weight of the carbon fiber is contained by 1 to 40% by weight based on the weight of the polyketone, preferably 5 to 20% by weight, more preferably 10 to 15% by weight. When the content of the carbon fiber exceeds 40% by weight, the mechanical strength, dimensional stability and molding properties of the composition may be lowered, thereby causing a lack of practicality. If it is less than 1%, the problem that the electrical conductivity of the final composition is lowered occurs.

In addition, the present invention can reinforce the mechanical properties by adding carbon fibers, mica and talc as a reinforcing material to the composition. In addition, antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.

Hereinafter, a manufacturing method for producing the polyketone composition is as follows.

Method for producing a polyketone resin composition having excellent conductivity of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And mixing and extruding the polyketone resin with conductive carbon black or elastic polyurethane or carbon fiber.

Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of the palladium compound is preferably 10 ^-3 to 10 ^-1 mole.

As the acid having a pKa value of 6 or less constituting the catalyst composition, one or more selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid may be used, and preferably trifluoroacetic acid is used. 6-20 (molar) equivalents to the compound are appropriate.

Examples of the phosphorus double ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (eg, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis ( Methylene)) bis (bis (2-methoxyphenyl) phosphine) may be used at least one selected from the group consisting of, the amount is preferably 1 ~ 1.2 (mole) equivalent to the palladium compound.

The carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer. The mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.

In addition, the polymerization temperature is 50 ~ 100 ℃, the reaction pressure is suitable for the range of 40 ~ 60bar. The resulting polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone resin is mixed with carbon nanotubes and then extruded with an extruder to finally obtain a blend composition. The blend is prepared by melt kneading and extrusion into a twin screw extruder.

At this time, the extrusion temperature is 230 ~ 260 ℃, screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃ kneading may not occur properly, if it exceeds 260 ℃ may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm it may not be a smooth kneading, if it exceeds 300rpm conductive carbon black or elastic polyurethane or carbon fiber may be destroyed and mechanical properties may be reduced.

The conductive carbon black, elastic polyurethane, and carbon fibers may be blended alone or in combination, and the added amount may be 1 to 30 parts by weight, preferably 5 to 10 parts by weight, relative to 100 parts by weight of the polyketone terpolymer. . If the added content is less than 1 part by weight, it is difficult to impart a desired level of conductivity, and if it exceeds 30 parts by weight, mechanical strength, dimensional stability, and molding properties may be lowered, thereby causing a lack of practicality.

Polyketone resin composition according to the production method of the present invention is excellent in electrical conductivity with low surface resistance, excellent flexural modulus, impact strength and wear resistance can be applied to industrial parts such as automotive parts, such as gears, belts, fuel filters and cams Do.

On the other hand, the present invention provides a high thermal conductivity composite material comprising a polyketone resin and a filler.

In this case, the high thermal conductivity composite material is preferably a high thermal conductivity composite material for the outdoor housing.

The high thermal conductivity composite material includes a polyketone resin.

The polyketone refers to a compound containing a ketone unit of ethylene-carbon monoxide represented by the following formula (1) as a main repeating unit, propylene, butene, hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene Alpha olefins such as these may be polymerized into small comonomers.

[Formula 3]

The content of the polyketone resin as described above is not particularly limited, but is preferably 30 to 70% by weight based on the total weight of the high thermal conductivity composite material.

On the other hand, the high thermal conductivity composite material includes a filler.

The type of the filler is not particularly limited, but may be carbon-based, nitride-based, and metal oxide, and these fillers may be used alone or in combination of two or more thereof.

In this case, the carbon-based is preferably graphite, carbon fiber, and the like, the nitride is preferably boron nitride, aluminum nitride, and the like, and the metal oxide is preferably alumina or the like, but is not limited thereto.

The content of the filler is not particularly limited, but is preferably 30 to 70% by weight based on the total weight of the high thermal conductivity composite material.

In particular, when the content of the filler is less than 30% by weight, it is difficult to fully implement the filler-resin thermal conductive network in the existing composite material, the thermal conductivity improvement effect may be insignificant. In addition, when the content of the filler is 70% by weight or more, the interfacial resistance of the filler itself is increased, which hinders the heat transfer flow and tends to lower the thermal conductivity.

As described above, the manufacturing method of the high thermal conductivity composite material including the polyketone resin and the filler is not particularly limited, but the polyketone resin and the filler may be manufactured from the high thermal conductivity composite material by melt mixing.

At this time, by using an extruder or the like to disperse the filler evenly into the polyketone resin at high temperature and high shear force to prepare a high thermal conductivity composite material, compared to In-situ Polymerization and Solution Mixing (Solution Mixing) High capacity can be achieved and manufacturing cost can be reduced.

The high thermal conductivity composite material according to the present invention includes a polyketone resin and a filler, and is a polymer material having improved thermal conductivity and excellent electrical properties, and is useful as a basic material for electrical, electronic, and communication devices requiring electrical properties. In particular, it can be effectively applied to products that require electromagnetic shielding or electrostatic dispersion.

In addition, the high thermal conductivity composite material according to the present invention includes a polyketone resin and a filler, thereby making it possible to reduce the weight of the conventional thermal conductive resin. Specifically, while the aluminum used in the prior art has a density of 2.7 g / cm 3 at room temperature, in the case of the composite material of the present invention, 1.2 ~ 2.0 g / cm 3 in the range of at least 30% lighter than aluminum when forming the same standard product Is possible. In addition, while manufacturing a molded article made of conventional aluminum, the composite material of the present invention may have a variety of forms according to the mold design, there is an advantage that the processing time and process can be shortened.

In addition, it is excellent in light resistance and hygroscopicity compared to the conventional polyamide resin can be applied to outdoor or outdoor articles, and can be applied in summer weather conditions. In addition, it is excellent in dimensional stability even in the humidity conditions that occur in outdoor or outdoor conditions when applied to electrical and electronic products.

Hereinafter, the present invention will be described in detail through examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples. The invention is illustrated in detail by the following non-limiting examples.

Example  One

Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexafluoroisopropano) at 1.3 dl / g, and a MI (Melt index) of 48 g / 10 min. Blended 30 parts by weight of conductive carbon black to 100 parts by weight of the polyketone terpolymer prepared above was made into pellets on an extruder using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. It was.

Example  2

15 parts by weight of conductive carbon black and 15 parts by weight of elastic polyurethane were mixed with 100 parts by weight of the polyketone terpolymer prepared according to Example 1, using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. To pellets on an extruder.

Example  3

10 parts by weight of conductive carbon black, 10 parts by weight of elastic polyurethane, and 10 parts by weight of carbon fiber were mixed with 100 parts by weight of the polyketone terpolymer prepared according to Example 1, and the diameter was 2.5 cm operating at 250 rpm, and L / D = 32 The pellets were prepared on an extruder using a phosphorous biaxial screw.

Comparative example  One

30 parts by weight of conductive carbon black was blended to 100 parts by weight of polyoxymethylene (POM) and melt kneaded with a screw speed of 250 rpm and a discharge rate of 30 kg / h using a 40Φ, L / D = 32 twin screw extruder, and melted from the extruder die. Was cooled through a cooling bath to prepare pellets.

Comparative example  2

15 parts by weight of conductive carbon black and 15 parts by weight of elastic polyurethane were blended with 100 parts by weight of polyoxymethylene (POM) and melt kneaded with a screw speed of 250 rpm and a discharge rate of 30 kg / h using a 40Φ, L / D = 32 twin screw extruder. The melt from the extruder die was cooled through a cooling bath to prepare pellets.

Comparative example  3

Blend 100 parts by weight of conductive carbon black, 10 parts by weight of elastic polyurethane, and 10 parts by weight of carbon fiber to 100 parts by weight of polyoxymethylene (POM), and use a twin screw extruder with 40Φ and L / D = 32. Kg / h melt kneading, and the melt from the extruder die was cooled through a cooling bath to prepare pellets.

Property evaluation

After injection molding the prepared pellet of the Example to prepare a conductive fuel filter specimen, and compared to the product of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 1 below.

1. Surface resistance evaluation: Surface resistivity was measured by the IEC 60093 method. Higher values mean lower conductivity.

2. Flexural modulus evaluation: Flexural strength was evaluated according to the ISO 178 method.

3. Impact strength evaluation: Charpy impact strength (Notched) was evaluated according to the ISO 179 method.

4. Wear resistance evaluation: After molding the molded products prepared in Examples and Comparative Examples (diameter 120 mm, thickness 2 mm) and left at 25 ℃ for 2 days, Taber wear tester (DAITO ELECTRON CO., LTD., Preparation, Conditions: The amount of wear was measured according to JIS K-7311 using a load of 1 kg and a wear wheel H-22).

Item	Surface resistance (Ω / sq)	Flexural modulus (MPa)	Impact strength (J / m)	Abrasion Resistance (mg)
Example 1	103.5	6800	80	18
Example 2	103	6700	85	20
Example 3	103.2	6500	85	19
Comparative Example 1	105.2	6000	40	44
Comparative Example 2	105.6	5500	45	46
Comparative Example 3	105.8	5800	38	48

Through the table 1, the polyketone resin composition of the present invention has a low surface resistance and is excellent in electrical conductivity, and has excellent flexural modulus, impact strength, and abrasion resistance, and is applied to industrial parts such as automobile parts such as gears, belts, fuel filters, and cams. It turned out to be possible.

Example  4

Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized at 70 to 90 ° C. with a mixed solvent of 5 parts by weight of water to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. Meanwhile, the melting point of the prepared polyketone terpolymer was 220 ° C., and the intrinsic viscosity (LVN) measured at 1,1,1,3,3,3-HFIP was 1.5 dl / g.

A polyketone composition was prepared by blending the prepared polyketone terpolymer, 20 wt% of conductive carbon black, and 10 wt% of elastic polyurethane.

Example  5

A polyketone composition was prepared by blending 60% by weight polyketone terpolymer prepared by the method of Example 4, 20% by weight conductive carbon black and 20% by weight elastic polyurethane.

Example  6

A polyketone composition was prepared by blending 80% by weight of the polyketone terpolymer prepared by the method of Example 4, 10% by weight of conductive carbon black and 10% by weight of elastic polyurethane.

Example  7

A polyketone composition was prepared by blending 70% by weight of the polyketone terpolymer prepared by the method of Example 4 and 30% by weight of conductive carbon black.

Comparative example  4

A PA66 composition was prepared by blending 70% by weight of Rhodda PA66 (manufactured by A218V30), 15% by weight of conductive carbon black, and 15% by weight of elastic polyurethane.

Property evaluation

The polyketone composition prepared by the method of Examples 4 to 7 and the PA66 composition of Comparative Example 4 were prepared as specimens, and the physical properties were evaluated by the following method, and the results are shown in Table 2 below.

1. Surface resistance evaluation: Surface resistivity was measured by the IEC 60093 method. Higher value means insulation and lower value means better conductivity.

2. Impact strength evaluation (notched Izod): It was carried out according to ASTM D638.

	Example 4	Example 5	Example 6	Example 7	Comparative Example 4
Surface resistance (Ω / sq)	1.25 6	1.43 6	3.52 6	0.58 6	1.2 7
Impact Strength (KJ / m 2 )	12.5	11.4	12.0	11.8	5.2

As shown in Table 1, in Examples 4 to 7, the surface resistance is lower than that of Comparative Example 4, which is excellent in electrical conductivity and excellent in impact strength (impact strength of 10 KJ / m 2 or more). It was evaluated as suitable for use as a plastic.

Example  8

Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent at 70 to 90 ° C. with 5 parts by weight of water relative to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. Meanwhile, the melting point of the prepared polyketone terpolymer was 220 ° C., and the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.4 dl / g.

A polyketone composition was prepared by blending 99% by weight of the prepared polyketone terpolymer and 1% by weight of carbon fiber.

Example  9

A polyketone composition was prepared by blending 90% by weight of the polyketone terpolymer prepared in Example 8 and 10% by weight of carbon fiber.

Example  10

A polyketone composition was prepared by blending 70% by weight of the polyketone terpolymer prepared in Example 8 and 30% by weight of carbon fiber.

Example  11

The polyketone terpolymer prepared according to Example 8 was used.

Example  12

A polyketone composition was prepared by blending 65% by weight of the polyketone terpolymer prepared in Example 8 and 35% by weight of carbon fiber.

Comparative example  5

Specimens were prepared in the same manner as in Example 8 except that 90% by weight of Rhodda polycarbonate (PC) was used instead of polyketone.

Property evaluation

The prepared polyketone compositions of Examples 8 to 12 and Comparative Example 5 were prepared as specimens, and then compared with the products of Comparative Examples to evaluate physical properties in the following manner, and the results are shown in Table 3 below.

1. Surface resistance evaluation: Surface resistivity was measured by the IEC 60093 method. Higher value means insulation and lower value means better conductivity.

2. Impact strength evaluation (notched Izod): It was carried out according to ASTM D638.

3. Abrasion resistance evaluation: The specimens prepared in Examples and Comparative Examples were processed into disc shapes (120 mm in diameter and 2 mm in thickness) and left at 25 ° C. for 2 days, followed by a Taber wear tester (DAITO ELECTRON CO., LTD., Preparation, Conditions: The amount of wear was measured according to JIS K-7311 using a load of 1 kg and a wear wheel H-22).

 The polyketone composition of the present invention was measured using a Taber wear tester (DAITO ELECTRON CO., LTD.), The wear amount measured according to JIS K-7311 is 2.0 mg or less.

	Example 8	Example 9	Example 10	Example 11	Example 12	Comparative Example 5
Surface Resistance (Ω / sq)	1.44 6	1.32 6	0.75 6	1.48 6	0.55 6	2.54 6
Impact Strength (KJ / m 2 )	12	11.8	11.8	12.4	11.6	4.5
Wear resistance (wear amount mg)	1.4	1.2	1.3	1.6	1.2	5.5

As shown in Table 3, the polyketone composition of the present invention according to Examples 8 to 12 was found to be superior in electrical conductivity, impact resistance, and wear resistance (wear amount of less than 2mg) compared to polycarbonate, and is used in industries including automobiles. Seems to be very suitable.

Example  13

Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.3 dl / g, and a MI (Melt index) of 48 g / 10 min. 70% by weight of the polyketone terpolymer prepared above and 30% by weight of carbon nanotubes were prepared in pellet form on an extruder using a biaxial screw having a diameter of 2.5cm and L / D = 32 operating at 250 rpm. .

Example  14

Except for 70% by weight of polyketone terpolymer and 30% by weight of conductive carbon black, pellets were prepared in the same manner as in Example 13.

Comparative example  6

Polyoxymethylene (POM) and carbon nanotube 30% content using a 40Φ, L / D = 32 twin screw extruder melt kneading screw speed 250rpm, discharge amount 30kg / h, the melt from the extruder die Cooled through to prepare pellets.

Property evaluation

After injection molding the prepared pellet of the Example to prepare a conductive fuel filter specimen, and compared to the product of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 4 below.

1. Surface resistance evaluation: Surface resistivity was measured by the IEC 60093 method. Higher value means insulation and lower value means better conductivity.

2. Flexural modulus evaluation: Flexural strength was evaluated according to the ISO 178 method.

3. Impact strength evaluation: Charpy impact strength (Notched) was evaluated according to the ISO 179 method.

4. Fuel deposition evaluation: Specimens prepared according to ASTM D638 at 82 ° C in a solution consisting of toluene (46.25% by weight), isooctane (46.25% by weight), ethanol (5.0% by weight) and methanol (2.5% by weight). Immersion was performed to evaluate the tensile strength after 1,000 hours.

Item	Required property	Comparative Example 6	Example 13	Example 14
Surface resistance (Ω / sq)	10 2 to 10 4	10 5	10 3.5	10 3
Flexural modulus (MPa)	6,000-7,000	6,000	6,800	6,700
Impact strength (J / m)	50 or more	40	80	75
Longitudinal strength retention of fuel deposited	1,000hr rating	80%	95%	93%

As shown in Table 4, in the case of Examples 13 and 14 it was evaluated that the electrical conductivity is better than Comparative Example 6, the flexural modulus is high and the impact strength and fuel deposition is excellent. Thus, the polyketone produced through the embodiment of the present invention Molded articles were very suitable for application as conductive fuel filters because of their excellent electrical conductivity and impact strength.

Example  15

The polyketone resin was put into the main hopper of an extruder, and the filler was put into the side feeder. At this time, the content of the filler was to be 30% by weight in the composite.

Thereafter, the extrusion process was performed at 150 RPM, and the extrusion temperature was set at 240 ° C. to prepare a thermally conductive composite material.

Example  16

A thermally conductive composite was prepared in the same manner as in Example 15, except that 60 wt% of the filler content was added to the composite.

Example  17

A thermally conductive composite was prepared in the same manner as in Example 15, except that the filler content was 70 wt% in the composite.

Comparative example  7 to 13

In place of the polyketone resin was added to the resin shown in Table 5, except that the filler content was adjusted to the content shown in Table 5, to prepare a thermally conductive composite material in the same process as in Example 15.

Property evaluation

The physical properties of the thermally conductive composites prepared in Examples 15 to 17 and Comparative Examples 7 to 13, respectively, were evaluated using the following method, and the results are shown in Table 5 below.

(1) Thermal conductivity: Thermal conductivity was measured using a laser flash, and the in-plane thermal conductivity was measured based on the method of ASTM E1461.

(2) Tensile strength and tensile modulus: measured according to ASTM D 638, the test piece was Type 1, the test speed was 5mm / min.

(3) Flexural strength and flexural modulus: measured at room temperature according to ASTM D 790, and the test speed was 2.7 mm / min.

(4) Impact strength: measured at room temperature according to ASTM D 256, notched specimens were used.

	Suzy	filler	Thermal Conductivity (W / mK, In-plane)	Tensile Strength (MPa)	Tensile Modulus (GPa)	Flexural Strength (MPa)	Flexural Modulus (GPa)	Impact Strength (J / m)
Example 15	PK	BN 30wt%	2.3	48.1	9.5	87.0	10.5	25.3
Example 16	PK	BN 60wt%	9.2	46.5	18.7	68	9.2	37.5
Example 17	PK	BN 70wt%	12.8	32.3	26.1	51.7	10.3	35.5
Comparative Example 7	PA	BN 30wt%	1.7	63.3	10.2	125.3	13.7	17.8
Comparative Example 8	PA	BN 60wt%	6.7	61.3	13	117.4	8.7	25.1
Comparative Example 9	PA12		8.1	47	2	78	10.5	48.4
Comparative Example 10	PA46		3.8	63.2	2.2	88.2	13	33.9
Comparative Example 11	PA4T		5.5	57.9	20.9	93.9	16.8	35.1
Comparative Example 12	PA10T		2.3	10.2	16.5	165	14.4	32.6
Comparative Example 13	PA	BN 70wt%	8.5	57.6	26	82.6	14	23.3

As can be seen in Table 5, the composite material containing a polyketone resin (Example 16) according to the present invention shows a higher thermal conductivity than the composite material containing a polyamide resin (Comparative Example 8) Could. It was confirmed that PK thermally conductive composites had 37% higher thermal conductivity values than PA thermally conductive composites when the same content filler was applied. This can solve the high cost and low mechanical properties, which are a problem in the commercialization of the thermally conductive composite material. When the same thermal conductivity is realized, the cost of the filler is reduced by reducing the amount of filler added, and also the mechanical properties are reduced by the amount of filler added. The improvement effect can be secured at the same time.

It can be seen that the composite material according to the present invention (Example 16) is about 14% improved in thermal conductivity compared to the composite material containing polyamide 12 (Comparative Example 9), and the composite material containing the general polyamide (Comparative Example) Compared with 8), the impact strength is about 50% improved.

In addition, the composite material according to the present invention includes a polyketone resin, which is less expensive than a special polyamide resin, thereby achieving a higher level of thermal conductivity, and having about 30% higher than that of the composite material containing a polyamide resin. It can have a cost-saving effect.

Example  18

Polyketone resin was put into the main hopper of an extruder, and boron nitride which is a filler was put into the side feeder. At this time, the content of the filler was 60% by weight in the composite.

Thereafter, the extrusion process was performed at 150 RPM, and the extrusion temperature was set at 240 ° C. to produce a high thermal conductivity composite material.

Example  19

A high thermal conductivity composite material was manufactured in the same manner as in Example 18, except that 50 wt% of graphite instead of 60 wt% of boron nitride was used as the filler.

Comparative example  14

Polyketone resin was added to the main hopper of the extruder. Thereafter, the extrusion process was performed at 150 RPM, and the extrusion temperature was set at 240 ° C. to produce a high thermal conductivity composite material.

Comparative example  15

The polyamide resin was put into the main hopper of the extruder. Thereafter, the extrusion process was performed at 150 RPM, and the extrusion temperature was set at 240 ° C. to produce a high thermal conductivity composite material.

Comparative example  16

A composite material was manufactured in the same manner as in Example 18, except that the polyamide resin was added to the main hopper instead of the polyketone resin.

Comparative example  17

A composite material was manufactured in the same manner as in Example 19, except that a polyamide resin was added to the main hopper instead of a polyketone resin.

Experimental Example  One : Hygroscopic  Assessment Methods

Properties of the composite materials prepared in Examples 18, 19 and Comparative Examples 14 to 17, respectively, for 120 hours at a temperature of 50 ° C. and a humidity of 90% RH were evaluated using the following methods. The results are shown in Table 6 below.

Experimental Example  2 : Light fast  Assessment Methods

The composite materials prepared in Example 19 and Comparative Example 17 were evaluated for 80 days in the UV-B lamp of the Accelerated Weathering Tester (QUV) and the properties before leaving, using the following method. The results are shown in Table 7 below.

(1) Tensile strength: measured according to ASTM D 638, the test piece was Type 1, the test speed was 5mm / min.

(2) Flexural strength: measured according to ASTM D 790, the test speed was 2.7mm / min.

(3) Thermal conductivity: Thermal conductivity was measured using a laser flash, and in-plane thermal conductivity was measured based on the method of ASTM E1461.

	Suzy	filler	Tensile Strength Retention Rate (%)	Flexural Strength Retention Rate (%)	Thermal Conductivity (W / mK)
Example 18	PK	BN 60wt%	98.3	95.1	10.5
Example 19	PK	50wt% graphite	85.4	83.1	3.4
Comparative Example 14	PK	-	97	95.8	0.38
Comparative Example 15	PA	-	65.5	45	0.37
Comparative Example 16	PA	BN 60wt%	97.6	93.4	8.8
Comparative Example 17	PA	50wt% graphite	80.7	75.6	2.7

		1 day later	5 days later	12 days later	After 20 days	30 days later	80 days later
Example 19	Tensile Strength Retention Rate (%)	100.4	100.3	102.3	99.7	99.5	99.6
	Flexural Strength Retention Rate (%)	104.1	100.6	100.8	101.7	98.7	97.3
Comparative Example 17	Tensile Strength Retention Rate (%)	99.9	99.5	98.3	97.6	96.3	95.5
	Flexural Strength Retention Rate (%)	100.1	99.7	97.7	95.7	94.3	93.2

As can be seen in Table 6, the composite material containing a polyketone resin according to the present invention (Example 18) is compared to the composite material containing a polyamide resin (Comparative Example 16) and the tensile strength in the moisture absorption conditions and The flexural strength retention was shown to be high, and the hygroscopicity was excellent. In addition, according to the present invention, it was found that the composite material containing the polyketone resin exhibited higher thermal conductivity than the composite material (Comparative Examples 14 and 15) containing no fillers. This can solve the high cost and mechanical low properties that are highlighted as a problem in the commercialization of the thermally conductive composite material, when implementing the same thermal conductivity, it can have a reduction in manufacturing cost by reducing the amount of expensive resin addition.

In addition, as can be seen in Table 7, the composite material containing a polyketone resin according to the present invention (Example 19) is a tension after irradiating UV compared to the composite material containing a polyamide resin (Comparative Example 17) The strength and flexural strength retention were high, indicating that the light resistance was excellent.

For this reason, the high thermal conductivity composite material of the present invention can be easily applied as an outdoor or outdoor housing.

Claims (24)

1. A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), which has excellent electrical conductivity, comprising a linear alternating polyketone having y / x of 0.03 to 0.3 and conductive carbon black Polyketone resin composition.

   -[-CH2CH2-CO] x- (1)

   -[-CH2-CH (CH3) -CO] y- (2)

   (x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
2. The method of claim 1,

   The polyketone resin composition is excellent polyketone resin composition, characterized in that it further comprises an elastic polyurethane.
3. The method according to claim 1 or 2,

   The polyketone resin composition is excellent polyketone resin composition characterized in that it comprises a carbon fiber.
4. The method of claim 3, wherein

   The polyketone resin composition is a polyketone resin composition having excellent electrical conductivity, characterized in that it comprises 10 to 30 parts by weight of conductive carbon black, elastic polyurethane, carbon fibers relative to 100 parts by weight of the polyketone terpolymer.
5. A gear, a belt, an automobile fuel filter, and a cam, which are made of the polyketone resin composition according to claim 1.
6. A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), wherein the polyketone comprises a linear alternating polyketone having y / x of 0.03 to 0.3, conductive carbon black and an elastic polyurethane Ketone composition.

   -[-CH2CH2-CO] x- (1)

   -[-CH2-CH (CH3) -CO] y- (2)

   (x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
7. The method of claim 6,

   The polyketone is 60 to 85% by weight, the conductive carbon black is 5 to 20% by weight and the elastic polyurethane is a polyketone composition, characterized in that 10 to 20% by weight.
8. The method of claim 6,

   Polyketone composition, characterized in that the impact strength of the polyketone composition is 10 KJ / m 2 or more.
9. A polyketone molded article comprising the polyketone composition according to any one of claims 6 to 8.
10. A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having an intrinsic viscosity (LVN) of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and y / x of 0.03 Polyketone composition characterized in that it comprises a linear alternating polyketone and carbon fiber of 0.3 to 0.3.

    -[-CH2CH2-CO] x- (1)

    -[-CH2-CH (CH3) -CO] y- (2)

    (x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
11. The method of claim 10,

    The polyketone composition is characterized in that the polyketone is 60 to 99% by weight, and the carbon fiber is 1 to 40% by weight relative to the total weight of the polyketone composition.
12. The method of claim 10,

    The polyketone composition is a polyketone composition, characterized in that the wear amount measured in accordance with JIS K-7311 using a Taber wear tester (DAITO ELECTRON CO., LTD.) Is 2.0 mg or less
13. A polyketone molded article made of the polyketone composition according to any one of claims 10 to 12.
14. A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the polyketone copolymer having y / x of 0.03 to 0.3; And at least one or more of carbon nanotubes and conductive carbon blacks.

    -(CH2-CH2-CO) x- (1)

    -(CH2-CH (CH3) -CO) y- (2)

    (x, y are mole% of each of the general formulas (1) and (2) in the polymer)
15. The method of claim 14,

    The content of the carbon nanotubes or conductive carbon black is a polyketone molded article, characterized in that 1 to 30% by weight relative to the total blend weight.
16. The method of claim 14,

    Polyketone molded article, characterized in that the surface resistance of the polyketone molded article is 10 ² to 10 ⁴ Ω / cm2.
17. The method of claim 14,

    Impact strength of the polyketone molded article is a polyketone molded article, characterized in that more than 70 J / m.
18. A conductive fuel filter made of the polyketone molded article of claim 14.
19. High thermal conductivity composite material comprising polyketone resin and filler.
20. The method of claim 19,

    Based on the total weight of the high thermal conductivity composite material,

    The polyketone resin is 30 to 70% by weight; And

    The filler is a high thermal conductivity composite material comprising 30 to 70% by weight.
21. The method of claim 19,

    The filler is a high thermal conductivity composite material, characterized in that at least one selected from the group consisting of carbon-based, nitride-based and metal oxides.
22. The method according to any one of claims 19 to 21,

    The high thermal conductivity composite material is a high thermal conductivity composite material, characterized in that the high thermal conductivity composite material for the outdoor housing.
23. An outdoor housing comprising the high thermal conductivity composite material of claim 22.
24. The method of claim 23,

    And the outdoor housing is used for a street lamp or a transformer.