KR20030027479A - Intelligent heat absorb-release engineering plastics - Google Patents

Abstract

PURPOSE: An artificial intelligence heat absorbing/radiating engineering plastic composition is provided, which can absorb or radiate the heat in the form of latent heat at a desired temperature by itself and is applied to the interior of vehicle or the housing of electric home appliances. CONSTITUTION: The engineering plastic composition comprises 100 parts by weight of a mixture of a thermoplastic or thermosetting resin, and an inorganic or organic material whose melt-crystallization temperature or adsorption-desorption temperature is lower than that of the thermoplastic or thermosetting resin; a compatibilizer selected from maleic anhydride-olefin copolymer, vinyl acetate-olefin copolymer, styrene-ethylene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, and polyolefin copolymerized with amide group; optionally 5-90 parts by weight of a ceramic or solid metal thermal conductive additive whose thermal conductivity is 5 W/m·K; and optionally 1-30 parts by weight of at least one reinforcing agent selected from the group consisting of glass fiber, carbon fiber, talc, glass flake, mica, carbon black and carbon nanotube. The thermal conductivity of the engineering plastic composition satisfies the mathematical equation (h·d/k) < 1, wherein h is a heat transfer coefficient of the composition (W/m2·K), d is a thickness of the composition (m) and k is a thermal conductivity (W/m·K).

Description

INTELLIGENT HEAT ABSORB-RELEASE ENGINEERING PLASTICS}

The present invention relates to engineering plastics, and more particularly, to an artificial heat-absorbing heat-dissipating engineering plastics resin composition capable of absorbing heat or releasing heat as latent heat by sensing a temperature at a desired temperature.

[Private Technology]

Engineering plastics are widely used for interior and exterior materials of automobiles or housings of home appliances due to their excellent heat resistance and mechanical properties. Conventional engineering plastics are used in the form of blending two or more polymers or adding organic or inorganic fillers, depending on price and required properties. In particular, engineering plastics used for automotive interiors, home appliances, and the like require very high heat deflection temperatures of 70 to 300 ° C. due to heat rise.

U.S. Patent No. 4,797,160 and U.S. Patent No. 5,053,446 disclose compositions that exhibit endothermic and heat dissipation properties due to melting or crystallization of phase change materials. These are limited to polyolefins, and there is a limit not to show the physical properties of the material balanced according to the use environment. They are also intended to be used for the purpose of energy storage materials but do not give them the ability to sense temperature.

Conventional temperature control system is composed of temperature sensor, coat roller, heating device, cooling device, and to produce artificial heat-absorbing and heat-dissipating plastic having the performance of such temperature control system, temperature sensing ability, heat-absorbing and heat-dissipating performance, and mechanical You must have all the physical properties. However, conventionally, there have been no attempts to impart these properties to plastic materials so that they have a temperature control capability.

In view of the problems of the prior art, an object of the present invention is to provide an artificial heat-absorbing heat-resistant engineering plastic having a function capable of sensing heat by self-heating.

Another object of the present invention is to provide an artificial heat-absorbing heat dissipation engineering plastic having an endothermic and heat dissipation function by phase transition or adsorption and desorption.

Another object of the present invention is to provide an artificial heat dissipation engineering plastic that can be used as a structural material can maintain a certain form even under the conditions of use of temperature or stress.

The present invention, in order to achieve the above object, in the engineering plastic resin composition,

a) thermoplastic, or thermosetting resin; And

b) inorganic or organic material having a melt-crystallization temperature or an adsorption-desorption temperature lower than the melting temperature of the thermoplastic or thermosetting resin of a).

To include, the thermal conductivity of the composition to satisfy the following equation

Artificial Intelligence Radiation Engineering Plastic Resin Composition

[Equation 4]

In formula (4), h is the heat transfer coefficient of the composition (W / m ² K), d is the thickness of the composition (m), k is the thermal conductivity (W / mK) of the composition.

In addition, the composition may further comprise c) one or more compatibilizers to perform the function of preventing the dispersed phase from exiting the interface of the composition.

In addition, the composition may further include a thermally conductive additive of at least one ceramic or metal solid having d) thermal conductivity of 5 W / m-K or more, which serves to speed up the endothermic or exothermic rate of the composition.

In addition, the composition may further include e) one or more organic or inorganic reinforcing additives for enhancing mechanical properties and performing a function of viscosity control.

Hereinafter, the present invention will be described in detail.

The present invention provides the artificial heat-absorbing heat-dissipating engineering plastic resin composition that absorbs heat at a desired temperature in latent heat, so the temperature rise of the material is small even when it is subjected to heat, and the heat can be released at a desired temperature when the surrounding environment becomes cold. It is.

The engineering plastics defined in the present invention mean plastics that can be used as structural materials because the plastics can maintain a certain shape under conditions of use (temperature, stress, etc.), and artificial intelligence means that plastics can sense temperature by themselves. Performance. Therefore, the artificial heat absorbing engineering plastic refers to a plastic that can be used as a structural material capable of absorbing or dissipating heat by sensing a specific temperature by itself.

There has been no prior attempt to impart the heat dissipation properties of artificial intelligence to engineering plastics, and the present invention provides a resin composition having the heat dissipation performance of artificial intelligence.

Since the heat absorbing plastic of artificial intelligence absorbs heat at a specific temperature, the temperature rise is small, and thus it can be used in a heat-receiving environment even though it has a relatively low heat deflection temperature as compared with the conventional engineering plastics. In addition, the artificial heat absorbing plastic can be used for the purpose of maintaining a specific temperature. A specific example is that the interior of the car has a problem that heat in the summer due to solar heat. When the artificial heat absorbing plastic is applied to the interior materials of automobiles, it can absorb heat and provide a comfortable environment for the user, and can exhibit heat dissipation performance when the temperature falls at night. Still other uses can be applied to plastics such as housings or accessories of home appliances, cooling or heating devices, textiles, building materials and flooring materials.

The thermoplastic or thermosetting resin of a) used in the present invention is polybutylene terephthalate, polyethylene terephthalate, aromatic polyamide, polyamide, polycarbonate, polystyrene, polyphenylene sulfide, thermotropic liquid crystal polymer, polysulfone, Polyethersulfone, polyetherimide, polyetheretherketone, polyarylate, polymethylmethylacrylate, polyvinyl alcohol, polypropylene, polyethylene, polyacrylonitrile butadiene styrene copolymer and polytetramethylene oxide-1,4 Butanediol copolymer (polybutylene terephthalate elastomer), styrene-containing copolymer (SBR, SBS, ASA, etc.), fluorine resin (PVDF, PTFE, FEP, etc.), polyvinyl chloride, polyacrylonitrile One or more types can be selected and used from a group. In addition, all kinds of thermoplastic or thermosetting resins are applicable. This resin preferably contains 10 to 95% by weight in the composition. If it is less than 10% by weight, there is a problem in that it cannot be maintained as a matrix, and if it exceeds 95% by weight, there is a problem in that the endothermic and heat-dissipating performance is not effectively exhibited.

In addition, the inorganic or organic material having a melting-crystallization temperature or an adsorption-desorption temperature of b) lower than the melting temperature of the thermoplastic or thermosetting resin of a) used in the present invention may be zeolite powder, polytriphenylphosphate, crystalline paraffin. Wax, polyethylene glycol, fatty acid, naphthalene, calcium dichloride, polyepsiloncaprolactone, polyethylene oxide, polyisobutylene, polycyclopentene, polycyclooctene, polycyclododecene, polyisoprene, polyoxypreeylene, polyoxytetrake Preference is given to using at least one selected from the group consisting of styrene, polyoxyoctamethylene, polyoxypropylene, polybutyrolactone, polyvalolalactone, polyethylene adipide, polyethylene suverate, and polydecamethyl azilide Do. Even if such an organic-inorganic material is selected, if their melt-crystallization temperature or adsorption-desorption temperature is higher than the melting temperature of the thermoplastic or thermosetting resin of a), there is a problem in that absorption and heat dissipation are not possible at the use temperature. In addition, it is preferable that this inorganic substance or organic substance contains 5 to 95 weight% in a composition. If less than 5% by weight, there is a problem that the amount of heat absorption and heat dissipation is not effective, and if it exceeds 90% by weight, there is a problem that the form cannot be maintained at the use temperature.

In addition, the compatibilizer of c) used in the present invention is at least from polyolefin copolymerized with maleic hydride or vinyl acetate, styrene-ethylene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, polyolefin copolymerized with amide group It is preferable to select and use 1 or more types. The compatibilizer is preferably added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the resin component of a) and the inorganic or organic materials of b). If it is less than 0.1 part by weight, there is a problem in that it does not play a role of a compatibilizer, and if it exceeds 30 parts by weight, there is a problem that the amount of heat absorption and heat dissipation does not appear effectively.

In addition, the thermally conductive additive of a ceramic or metal solid having a thermal conductivity of 5 W / mK or more of d) used in the present invention may be copper, silver, gold, steel, nickel, silicon carbide, boron nitride, diamond, beryllium oxide, or boron. At least one selected from the group consisting of phosphide, aluminum nitride, beryllium sulfide, boron azenide, silicon, gallium nitride, aluminum phosphide, and gallium phosphide can be used. The thermally conductive additive is preferably added in an amount of 5 to 90 parts by weight based on 100 parts by weight of the sum of the amounts of the resin component of a) and the inorganic or organic substance of b). If it is less than 5 parts by weight, there is a problem that the thermal conductivity synergistic effect is weak, and if it exceeds 90 parts by weight, there is a problem that the amount of heat absorption and heat dissipation is weak.

In addition, the reinforcing additive of e) used in the present invention is preferably at least one organic or inorganic material selected from the group consisting of glass fibers, carbon fibers, talc, glass flakes, mica, carbon black, and carbon nanotubes. Do. These additives are preferably added in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total amount of the resin component of a) and the inorganic or organic materials of b). If it is less than 1 part by weight, there is a problem in that the effect of reinforcing mechanical strength does not appear. If it exceeds 30 parts by weight, the amount of heat absorption and heat dissipation is reduced, and the work of the material becomes difficult.

Hereinafter, the heat absorption of the artificial intelligence of the present invention will be described.

The heat capacity is defined as Equation 1 below as the energy required to change the temperature of 1 g by 1 ° K at a constant pressure.

[Equation 1]

In Equation 1, C _p is a heat capacity at a constant pressure P, H is enthalpy, and T is temperature.

The heat gained or lost by the material according to the change in temperature is shown in Equation 2 below, and when the heat is applied, the change in temperature depending on the heat capacity is caused by sensible heat. Equation 2 shows the amount of heat (Q ₁ ) obtained by the raw material when the temperature rises when the raw material is composed of n components. Conventional engineering plastics have a relationship between energy and temperature in the form of Equation 2 below.

[Equation 2]

In formula (2), w is the weight of the component.

However, the artificial heat dissipation engineering plastic of the present invention includes a component that absorbs or releases heat in the form of latent heat at a specific temperature, such as the second term on the right side of Equation 3 below.

[Equation 3]

In the above Equation 3, w is the weight ratio of the components

When raising the temperature, the artificial heat dissipation heat dissipation is smaller than the conventional engineering plastic even if the same amount of heat.

The second term in Equation 3 can use the exothermic or endothermic energy that appears when adsorption or desorption. Alternatively, the second term in Equation 3 may utilize endotherms or exotherms that appear when the dispersed phase melts or crystallizes. Since adsorption-desorption or melt-crystallization occurs at a specific temperature depending on the type of the dispersed phase, the plastic material containing such a dispersed phase exhibits heat absorption or heat dissipation at a specific temperature.

However, in order for the material to detect the temperature change of the surrounding environment on its own, the material must have sufficient sensitivity. This sensing capability requires sufficient heat transfer inside the material as compared to the rate of conduction, convection, radiation, etc. That is, the thermal resistance (d / k; d is the material due to the thermal conductivity k ([W / mK]) of the material rather than the thermal resistance (1 / h) due to the heat transfer coefficient h; [W / m ² K]). The thickness of the molded part) should be small. If the material's thermal conductivity is too low to detect the ambient temperature, it will not be able to effectively exhibit absorption and heat dissipation performance. Therefore, the thermal conductivity of the material satisfying the following equation (4) is essential.

[Equation 4]

In formula (4), h is the heat transfer coefficient (W / m ² K), d is the thickness (m) of the material molded article, k is the thermal conductivity (W / mK) of the material.

More preferably, the thermal conductivity of the material satisfying the following equation (5) is required.

[Equation 5]

In the formula (5), h is the heat transfer coefficient, d is the thickness of the material molded article, k is the thermal conductivity of the material.

In the present invention, by using the latent heat accompanying the phase transition (melting, crystallization) of the material endotherm or heat radiation at a specific temperature, in order to sense the specific temperature of the material itself to satisfy the equation (4) or (5) It is to provide an artificial heat absorbing heat engineering plastic having thermal conductivity.

Based on this, the thermal conductivity of the matrix material is 0.3 W / mK, preferably 0.7 W / mK, and more preferably 5 W / mK when the artificial heat-absorbing plastic of the present invention is used as a tube material of a heat exchanger. The above thermal conductivity is required.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Injection molded specimens of engineering plastics prepared in the following Examples were measured for physical properties using the following method.

Heat Deflection Temperature: ASTM D638

Impact Strength: ASTM D256

Flexural Modulus: ASTM D790

Endothermic and Calorific Values: Differential Scanning Calorimeter

Thermal Conductivity: Data within 10% error in Plate Method (LG Chem Tech Center) and Haake Thermoflixer

Example 1

A resin composition comprising 60% by weight of polypropylene and 40% by weight of polyepsilon caprolactone was prepared using a twin screw extruder.

The absorption and heat dissipation of the injection molded specimen was 31 J / g at 48 ° C., depending on the melting or crystallization of the polycaractone. The thermal deformation temperature was 74 ℃, the impact strength was 10 kg.cm / cm, the flexural modulus was 4048 kg / cm ² , the thermal conductivity was 0.17 W / mK at room temperature.

The composition exhibits artificial intelligence absorption and heat dissipation performance in a molded article having a thickness of 1.7 mm or less in an environment having a heat transfer coefficient of 10 W / m ² K, and exhibits the best performance according to the condition of Equation 5, more preferably.

Example 2

A resin composition comprising 74.7% by weight of polystyrene-co-acrylonitrile, 18.7% by weight of paraffin wax, 2% by weight of carbon black, and 4.6% by weight of polystyrene ethylene-butadiene styrene copolymer was prepared using a twin screw extruder.

Paraffin wax is endothermic or dissipated at a phase transition temperature of 40 ° C., and carbon black mixes well with paraffin wax and increases the viscosity of paraffin to maintain the shape of the dispersed phase. The polystyrene ethylene budadiene styrene copolymer serves to prevent the paraffin wax melt from flowing at the interface between the paraffin wax and the polystyrene-co-acrylonitrile. The absorption and heat dissipation of the injection molded specimen was about 20 J / g depending on the melting or crystallization of paraffin wax at around 55 ° C. The thermal deformation temperature was 65 ℃, the impact strength was 4 kg.cm / cm, the flexural modulus was 5000 kg / cm ² , the thermal conductivity was 0.19 W / mK at room temperature.

Example 3

A resin composition comprising 56 wt% polypropylene, 15 wt% ethylene vinyl acetate, 25 wt% paraffin wax, and 4 wt% talc was prepared using a twin screw extruder.

The absorption and heat dissipation amount of the injection molded specimen was 40 J / g depending on the melting or crystallization of paraffin wax at around 55 ° C. The thermal deformation temperature was 60 ℃, the impact strength was 3 kg.cm/cm, the flexural modulus was 3200 kg / cm ² , and the thermal conductivity was 0.17 W / mK at room temperature.

Example 4

A resin composition comprising 55% by weight of polypropylene, 13.5% by weight of ethylene vinyl acetate, 18% by weight of paraffin wax, 3.5% by weight of talc, and 10% by weight of glass fiber was prepared using a twin screw extruder.

The absorption and heat dissipation of the injection molded specimen was about 20 J / g depending on the melting or crystallization of paraffin wax at around 55 ° C. The thermal deformation temperature was 90 ℃, the impact strength was 7 kg.cm / cm, the flexural modulus was 16512 kg / cm ² , the thermal conductivity was 0.2 W / mK at room temperature.

Example 5

A resin composition comprising 38% by weight of polypropylene, 15% by weight of paraffin wax, 12% by weight of ethylene vinyl acetate, and 35% by weight of silicon carbide was prepared using a twin screw extruder.

The absorption and heat dissipation amount of the injection molded specimen was 16 J / g at 55 ° C. depending on the melting or crystallization of paraffin wax. The heat deflection temperature was 80 ℃, the impact strength was 3 kg.cm/cm, the flexural modulus was 17000 kg / cm ² , and the thermal conductivity at room temperature was 0.6 W / mK.

Example 6

A resin composition comprising 35% by weight of polybutylene terephthalate, 15% by weight of stearic acid, 10% by weight of a copolymer of maleic hydride and ethylene, and 40% by weight of silicon carbide was prepared using a twin screw extruder.

The heat dissipation amount of the injection molded specimen was about 14 J / g depending on the melting or crystallization of paraffin wax at about 40 ° C. The heat deflection temperature was 85 ℃, the impact strength was 3 kg.cm/cm, the flexural modulus was 23000 kg / cm ² , and the thermal conductivity was 1.0 W / mK at room temperature.

Example 7

A resin composition comprising 56% by weight of polypropylene, 15% by weight of ethylene vinyl acetate, 25% by weight of polyethylene glycol, and 4% by weight of talc was prepared using a twin screw extruder.

The heat dissipation amount of the injection molded specimen was 35 J / g due to melting or crystallization of polyethylene glycol at around 50 ° C. The heat deflection temperature was 55 ℃, the impact strength was 3 kg.cm/cm, the flexural modulus was 3000 kg / cm ² , and the thermal conductivity was 0.18 W / mK at room temperature.

Artificial heat absorbing engineering plastic according to the present invention can be used as a structural material can be maintained in a certain form under the use conditions (temperature, stress, etc.), by controlling the thermal conductivity of the material, the temperature sensing ability of the material itself detects a specific temperature And it has the property of absorbing or releasing heat, so it can be used for applications requiring little heat rise even when heat is received and heat releasing property becomes cold.

Claims (8)

In the engineering plastic resin composition, a) thermoplastic, or thermosetting resin; And b) inorganic or organic material having a melt-crystallization temperature or an adsorption-desorption temperature lower than the melting temperature of the thermoplastic or thermosetting resin of a). To include, the thermal conductivity of the composition to satisfy the following equation AI endothermic engineering plastic resin composition: [Equation 4] In formula (4), h is the heat transfer coefficient of the composition (W / m ² K), d is the thickness of the composition (m), k is the thermal conductivity (W / mK) of the composition. The method of claim 1, c) at least one member selected from the group consisting of maleic hydride-olefin copolymers, vinyl acetate-olefin copolymers, styrene-ethylene-butadiene-styrene copolymers, styrene-butadiene-styrene copolymers, and polyolefins copolymerized with amide groups Comprising a compatibilizer to be added to the artificial component of 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the resin component of a) and the inorganic or organic matter of b). The method according to claim 1 or 2, d) thermally conductive additives in ceramic or metal solids with a thermal conductivity of at least 5 W / m-K The artificial heat-absorbing heat-dissipating engineering plastic resin composition comprising 5 to 90 parts by weight based on 100 parts by weight of the total amount of the resin component of a) and the inorganic or organic matter of b). The method according to claim 1 or 2, e) reinforcing additives selected from the group consisting of glass fibers, carbon fibers, talc, glass flakes, mica, carbon black, and carbon nanotubes Further comprising: 1 to 30 parts by weight based on 100 parts by weight of the total amount of the resin component of a) and the inorganic or organic matter of b), the artificial heat-absorbing engineering plastic resin composition. The method of claim 1, The thermoplastic resin of a) is polybutylene terephthalate, polyethylene terephthalate, aromatic polyamide, polyamide, polycarbonate, polystyrene, polyphenylene sulfide, thermotropic liquid crystal polymer, polysulfone, polyether sulfone, polyetherimide, Polyether ether ketone, polyarylate, polymethylmethacrylate, polyvinyl alcohol, polypropylene, polyethylene, polyacrylonitrile-butadiene-styrene copolymer, polytetramethylene oxide-1,4-butanediol copolymer (polybutyl Lene terephthalate elastomer), a copolymer comprising styrene, a fluorine resin, polyvinyl chloride, polyacrylonitrile. The method of claim 1, The inorganic or organic substance of b) may be zeolite powder, polytriphenylphosphate, crystalline paraffin wax, polyethylene glycol, fatty acid, naphthalene, calcium dichloride, poly epsilon caprolactone, polyethylene oxide, polyisobutylene, polycyclopentene, Polycyclooctene, polycyclododecene, polyisoprene, polyoxypreeylene, polyoxytetraketylene, polyoxyoctamethylene, polyoxypropylene, polybutyrolactone, polyvalolalactone, polyethylene adipide, polyethylene suverate And at least one selected from the group consisting of polydecamethyl azide. The method of claim 1, a) 10 to 95% by weight of a thermoplastic, or thermosetting resin; And b) 5 to 90% by weight of an inorganic or organic substance having a melt-crystallization temperature or an adsorption-desorption temperature lower than the melting temperature of the thermoplastic or thermosetting resin of a). Artificial heat absorption engineering plastic resin composition comprising a. The method of claim 1, Artificial heat absorbing heat-resistant engineering plastic resin composition of the thermal conductivity of the composition satisfies Equation 5 below: [Equation 5] In formula (5), h is the heat transfer coefficient of the composition (W / m ² K), d is the thickness of the composition (m), k is the thermal conductivity (W / mK) of the composition.