WO2018047794A1 - Procédé de production de particules expansées de polyuréthane thermoplastique - Google Patents

Procédé de production de particules expansées de polyuréthane thermoplastique Download PDF

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Publication number
WO2018047794A1
WO2018047794A1 PCT/JP2017/031875 JP2017031875W WO2018047794A1 WO 2018047794 A1 WO2018047794 A1 WO 2018047794A1 JP 2017031875 W JP2017031875 W JP 2017031875W WO 2018047794 A1 WO2018047794 A1 WO 2018047794A1
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Prior art keywords
thermoplastic polyurethane
particles
tpu
producing
foaming agent
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PCT/JP2017/031875
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English (en)
Japanese (ja)
Inventor
展允 越田
政春 及川
林　達也
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株式会社ジェイエスピー
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Priority to CN201780054362.0A priority Critical patent/CN109689752B/zh
Publication of WO2018047794A1 publication Critical patent/WO2018047794A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a method for producing thermoplastic polyurethane (Thermoplastic Polythane; hereinafter sometimes abbreviated as TPU) foamed particles.
  • thermoplastic polyurethane Thermoplastic Polythane; hereinafter sometimes abbreviated as TPU
  • TPU is a kind of thermoplastic elastomer, but exhibits properties close to vulcanized rubber, and is excellent in wear resistance, cold resistance, and resilience. In addition, since it has high mechanical strength, it is positioned as an engineering elastomer and is used in various applications such as cushioning materials, vibration-proof materials, sporting goods, and automobile members.
  • Patent Document 1 describes a method of producing TPU foamed particles by foaming TPU particles impregnated with carbon dioxide in a supercritical state. Specifically, first, TPU particles and water are added to the reaction kettle, and carbon dioxide is further added. Next, after controlling the temperature and pressure in the reaction kettle to bring the carbon dioxide into a supercritical state, the temperature in the reaction kettle is raised to 90 to 140 ° C. and maintained at that temperature.
  • TPU particles impregnated with carbon dioxide in a supercritical state are released into the pressure tank held from the inside of the reaction kettle, the temperature is lowered to 70 ° C. or lower, and first-stage foaming is performed to obtain TPU primary foamed particles. . Thereafter, a method of producing TPU expanded particles by performing second-stage normal pressure expansion on the TPU primary expanded particles is described.
  • TPU particles mixed with 0.1 to 5 phr of cell nucleating agent are added to a pressure vessel together with a blowing agent and water, and the inside of the vessel is 110 to 135 ° C., 10 to 25 bar (1.0 to 2).
  • a method of producing TPU foamed particles by foaming the TPU particles impregnated with the foaming agent by releasing the contents in the container to the atmosphere after the temperature is raised to 5 MPa) Has been.
  • TPU particles are foamed under a certain pressure to produce TPU foam particles with a low expansion ratio, and then foamed in a separate process, followed by two-stage foaming (two-stage foaming). Yes.
  • two-stage foaming method has a problem that the productivity is inferior and a problem that the uniformity of bubbles of the TPU foamed particles is lowered.
  • the present invention has been made in order to solve the above-described problems, and an object of the present invention is to provide a method for producing TPU foamed particles, which is capable of obtaining a molded article having excellent in-mold moldability and excellent surface properties. .
  • thermoplastic polyurethane particle dispersed in an aqueous medium in a sealed container is impregnated with a foaming agent under heating, and the thermoplastic polyurethane particles containing the foaming agent are discharged together with the aqueous dispersion medium from the sealed container and foamed.
  • thermoplastic polyurethane foam particles having an apparent density of 100 to 300 kg / m 3 comprising:
  • the foaming agent is a physical foaming agent mainly composed of carbon dioxide,
  • the thermoplastic polyurethane particles contain 300 to 2000 mass ppm of inorganic powder,
  • the method for producing thermoplastic polyurethane foam particles, wherein the pressure in the container at the time of release is more than 2.5 MPa (G) and not more than 4.0 MPa (G).
  • the temperature of the aqueous medium when impregnated with the blowing agent is 80 ° C. or more and the melting temperature of the thermoplastic polyurethane particles is Tm ⁇ 20 ° C. or less, and the pressure in the sealed container is 2.5 MPa (G ) To 7.0 MPa (G) or less until the physical foaming agent is impregnated into the thermoplastic polyurethane particles by press-fitting the physical foaming agent into a sealed container [1] or [2] The method for producing thermoplastic polyurethane foam particles according to [2]. [4] The temperature of the aqueous medium at the time of release is not lower than the melting temperature Tm-60 ° C.
  • thermoplastic polyurethane foam particles according to any one of [3].
  • thermoplastic polyurethane foam particles according to any one of [1] to [6], wherein the thermoplastic polyurethane particles contain 300 to 950 mass ppm of inorganic powder.
  • expanded particles capable of obtaining a molded article having excellent in-moldability and excellent surface properties can be obtained.
  • a to B indicating a numerical range represents a numerical range including A and B as end points, and “A or more and B or less” (when A ⁇ B) or “A or less and B or more” (when A> B).
  • a mass part and mass% are synonymous with a weight part and weight%, respectively.
  • the TPU constituting the TPU expanded particles produced in the present invention is a hard segment obtained by polymerizing a diisocyanate and a chain extender (a diol compound such as a short-chain glycol) via a urethane bond, and an ether.
  • a soft segment composed of a polymer chain containing a group, an ester group, a carbonate group or the like has a structure in which they are bonded to each other. In the normal temperature region, the soft segment exhibits elasticity, and the hard segment generates a strong hydrogen bond and acts as a physical crosslinking point, thereby exhibiting elasticity close to rubber.
  • the type of soft segment has a great influence on the characteristics of TPU.
  • the ester-based TPU is particularly excellent in mechanical strength, heat resistance, and the like, while the ether-based TPU is particularly excellent in cold resistance, hydrolysis resistance, bacteria resistance, and the like. Therefore, the type of TPU to be used can be appropriately selected according to the characteristics required for the TPU expanded particle molded body.
  • the constituent elements of the TPU are not particularly limited, and are appropriately selected according to physical properties required for a TPU foamed particle molded body (hereinafter also simply referred to as a foamed molded body) obtained by in-mold molding of foamed particles. can do. Since ether-based TPU is superior in hydrolysis resistance compared to ester-based TPU, by using ether-based TPU as a raw material, hydrolysis can be performed even in a foaming method using an aqueous medium as in the production method of the present invention. The molecular weight is not easily lowered by foaming, bubbles are hard to break during foaming, and a good cell structure is maintained, so that it is easy to obtain expanded particles having good moldability.
  • polymers such as polyolefin resins, polystyrene resins, and styrene elastomers may be used by mixing with the TPU within a range that does not impair the purpose of the present invention, depending on the use and purpose of the foam molded article. You can also.
  • the usage-amount of these other polymers is 30 mass parts or less with respect to 100 mass parts of TPU, More preferably, it is 20 mass parts or less, More preferably, it is 10 mass parts or less. It is particularly preferable that the expanded particles do not contain any polymer other than TPU.
  • the melting temperature of TPU used for producing the expanded particles is preferably 140 to 170 ° C. If the melting temperature of TPU is within the above range, expanded particles with better moldability can be obtained. From the above viewpoint, the melting temperature is more preferably 150 to 170 ° C.
  • the melting temperature is based on JIS K7121-1987, and the condition of the test piece is “when the melting temperature is measured after performing a certain heat treatment” (both the heating rate and the cooling rate in the condition adjustment of the test piece are 10 This is a value obtained as a peak apex temperature of a melting peak of a DSC curve obtained by a heat flux differential scanning calorimetry method at a heating rate of 10 ° C./min. When the DSC curve has a plurality of melting peaks, the peak apex temperature of the melting peak with the highest temperature is adopted as the melting temperature.
  • the TPU type A durometer hardness is preferably A90 or less. If the hardness is A90 or less, a good foamed molded article can be obtained without excessively increasing the steam pressure (molding pressure) during molding. On the other hand, if the hardness is too low, depending on the molding conditions and the shape of the foamed molded product, after the foamed molded product has been released from the mold, the foamed molded product tends to shrink and deform so that a so-called sink is likely to occur. Become. Therefore, the type A durometer hardness is preferably A70 to A90, more preferably A80 to A88. The type A durometer hardness means a durometer hardness measured using a type A durometer based on JIS K6253-3: 2012. The measurement time is 3 seconds.
  • TPU particles dispersed in an aqueous medium in a sealed container are impregnated with a foaming agent under heating, and TPU particles containing the foaming agent are discharged from the sealed container together with the aqueous dispersion medium to foam.
  • a TPU foamed particle having an apparent density of 100 to 300 kg / m 3 wherein the foaming agent is a physical foaming agent mainly composed of carbon dioxide, and the TPU particle is an inorganic material having a mass of 300 to 2000 ppm by mass.
  • the pressure in the container at the time of discharge exceeds 2.5 MPa (G: gauge pressure) and is 4.0 MPa (G) or less.
  • the aqueous medium in which the TPU particles are dispersed is not particularly limited, but water or the like can be used.
  • the foaming agent impregnated into the TPU particles is a physical foaming agent mainly composed of carbon dioxide. Carbon dioxide is used as a blowing agent. By controlling the pressure in the pressure vessel so that carbon dioxide does not enter a supercritical state, TPU expanded particles can be obtained without excessively miniaturizing the bubbles.
  • other physical foaming agents and chemical foaming agents can be used in combination as the foaming agent.
  • Other physical blowing agents include aliphatic hydrocarbons such as propane, butane, hexane, pentane, heptane, chlorofluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, Examples include halogenated hydrocarbons such as methyl chloride, ethyl chloride, and methylene chloride, and organic physical foaming agents such as dialkyl ethers such as dimethyl ether and diethyl ether. Moreover, inorganic physical foaming agents, such as nitrogen, argon, air, and water, are mentioned. In this case, the blending ratio of carbon dioxide in the foaming agent is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.
  • Carbon dioxide used as a foaming agent is press-fitted into the sealed container so that the pressure in the sealed container is 7.0 MPa (G) or less from the viewpoint of not excessively reducing the bubble diameter of the obtained foamed particles.
  • the impregnation pressure is preferably 7.0 MPa (G) or less, more preferably 5.0 MPa (G) or less, and still more preferably 4.0 MPa (G) or less.
  • the impregnation pressure is 3.4 MPa (G) or less from the viewpoint that the pressure at the time of foaming described later can be easily controlled.
  • the impregnation pressure is preferably 0.5 MPa (G) or more, more preferably 1.0 MPa (G) or more. From the viewpoint of easy control of the pressure at the time, it is more preferably more than 2.5 MPa (G), particularly preferably 2.6 MPa (G) or more. Further, from the viewpoint of the impregnation property of the foaming agent to the TPU particles, the impregnation is preferably performed under heating.
  • the temperature at the time of impregnation performed under heating (hereinafter referred to as the impregnation temperature) is preferably 20 ° C. or higher and the TPU particle melting temperature Tm ° C.
  • the impregnation time is appropriately set according to the pressure in the sealed container, the type and mass of the TPU particles, etc., but is set as a time during which the TPU particles can be sufficiently impregnated with the foaming agent. Therefore, it is preferably 0.05 to 3 hours, more preferably 0.1 to 1 hour.
  • the temperature of the aqueous medium is set to 80 ° C. or higher and the TPU particle melting temperature Tm ⁇ 20 ° C. or lower, and the pressure in the sealed container exceeds 2.5 MPa (G) and 7.0 MPa (G ) It is preferable to impregnate the TPU particles with the physical foaming agent by press-fitting a physical foaming agent mainly composed of carbon dioxide into the hermetic container until the following is achieved.
  • the melting temperature is “when measuring the melting temperature after performing a certain heat treatment” as a condition adjustment of the test piece based on JIS K7121-1987 (the heating rate and the cooling rate in the condition adjustment of the test piece are These are values obtained as the peak apex temperature of the melting peak of the DSC curve obtained at a heating rate of 10 ° C./min by a heat flux differential scanning calorimetry method.
  • the peak apex temperature of the melting peak with the highest temperature is adopted as the melting temperature.
  • the TPU particles contain 300 to 2000 ppm by mass of inorganic powder. If the content of the inorganic powder in the TPU particles is too small, wrinkles are likely to occur on the surface of the expanded particles, and the bubbles are likely to be non-uniform, which may make it impossible to form a good molded product. From this viewpoint, the lower limit of the content of the inorganic powder in the TPU particles is preferably 400 mass ppm. Moreover, when there is too much content of inorganic powder, there exists a possibility that the bubble of an expanded particle may become too fine and the foaming speed may become too fast, or in-mold shaping
  • the upper limit of the content of the inorganic powder in the TPU particles is preferably 1500 ppm by mass, more preferably 1000 ppm by mass, and even more preferably 950 ppm by mass.
  • the inorganic powder is not particularly limited, but talc is preferably used, and talc having a 50% volume average particle diameter (d50) of 1 to 15 ⁇ m is more preferable. If d50 of talc is 1 ⁇ m or more, the bubble diameter of the foamed particles will not be excessively refined, so that foamed particles having excellent in-mold moldability can be obtained, and the obtained molded foam can be permanently compressed. There is no deterioration of physical properties such as strain. On the other hand, if d50 of talc is 15 ⁇ m or less, bubbles are not excessively coarsened, and thus expanded particles having excellent in-mold moldability can be obtained.
  • the pressure in the container (hereinafter referred to as foaming pressure) at the time of releasing the TPU particles exceeds 2.5 MPa (G) and is 4.0 MPa (G) or less.
  • the foaming pressure is 2.5 MPa (G) or less, wrinkles are generated on the surface of the foamed particles, and the bubble diameter is not uniform.
  • the foaming pressure exceeds 4.0 MPa (G)
  • the foaming speed of the TPU particles becomes too high, and as a result, the TPU crystals are easily oriented in the foamed particles. Therefore, in order to obtain such a molded article by molding such expanded particles in the mold, the pressure of the forming steam must be increased. From such a viewpoint, the foaming pressure is preferably 2.6 to 3.4 MPa (G).
  • the temperature of the aqueous medium at the time of release (hereinafter referred to as foaming temperature) is preferably (Tm-60) ° C. or higher and (Tm-20) ° C. or lower.
  • foaming temperature By setting the foaming temperature in the range of (Tm ⁇ 60) ° C. or more and (Tm ⁇ 20) ° C. or less, it is possible to obtain expanded particles having better in-mold moldability.
  • the temperature (foaming temperature) of the aqueous medium at the time of release is more preferably (Tm-40) ° C. or more and (Tm-25) ° C. or less.
  • the mass of one TPU particle is appropriately set according to the size of the target expanded particle and the expansion ratio, but is preferably 0.5 to 30 mg.
  • the TPU particles can be sufficiently impregnated with the foaming agent, and the foamed particles have an excellent balance between the filling ability in the mold and the moldability in the mold.
  • the lower limit of the mass of the TPU particles is more preferably 1 mg, and even more preferably 3 mg.
  • the upper limit is more preferably 20 mg, further preferably 15 mg, and particularly preferably 12 mg.
  • grains is not specifically limited, It can obtain by a well-known method.
  • the raw material TPU is melted in an extruder, the melt of TPU is extruded into a strand form from a small hole in a die attached to the tip of the extruder, and this is cut into a predetermined mass,
  • UWC method underwater cut method
  • hot cut method that extrudes and cuts TPU melt from small holes into the bubble phase.
  • the mass of the TPU particles can be adjusted by adjusting the hole diameter of the small holes, the extrusion amount, and the cutting speed.
  • TPU particles include commonly used antistatic agents, conductivity imparting agents, lubricants, antioxidants, ultraviolet absorbers, flame retardants, metal deactivators, Various additives such as a crystal nucleating agent, a filler, and a colorant can be appropriately blended as necessary.
  • the addition amount of these various additives varies depending on the purpose of use of the foamed particle molded body, but is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass relative to 100 parts by mass of the raw material TPU. It is 5 parts by mass or less, particularly preferably 5 parts by mass or less.
  • the apparent density of the expanded particles obtained by the production method of the present invention is 100 to 300 kg / m 3 .
  • foamed particles having uniform bubbles and excellent in-mold moldability and an apparent density of 100 to 300 kg / m 3 can be produced by one-stage foaming. If the apparent density of the expanded particles is too low, the obtained molded product is likely to be greatly deformed and contracted when the expanded particles are molded in the mold. From this viewpoint, the apparent density of the expanded particles is preferably 150 kg / m 3 or more, more preferably 200 kg / m 3 or more.
  • the apparent density of the expanded particles is a value obtained by dividing the weight of the expanded particles by the volume of the expanded particles.
  • the volume of the expanded particles can be determined by a submersion method.
  • the average cell diameter of the expanded particles is preferably 100 to 500 ⁇ m.
  • the average cell diameter is 100 ⁇ m or more, it is difficult for bubbles to break during molding in the mold, and a foamed molded product having particularly excellent surface properties is easily obtained.
  • the average cell diameter is 500 ⁇ m or less, steam easily penetrates into the inside of the foamed particles at the time of molding in the mold, so that the foamed particles are sufficiently secondary foamed to obtain a foamed molded product having particularly excellent surface properties.
  • the average cell diameter of the expanded particles is more preferably 150 to 400 ⁇ m.
  • the average cell diameter of the expanded particles is a value measured as follows in accordance with ASTM D3576-77.
  • the expanded particle is cut so as to pass through the central portion thereof and divided into two.
  • four line segments are drawn at equal angles from the outermost surface of the expanded particle to the outermost surface on the opposite side. Measure the number of bubbles intersecting each line segment and divide the total length of the four line segments by the total number of bubbles intersecting the line segment to obtain the average chord length of the bubbles, and further divide by 0.616 By doing this, the average cell diameter of the expanded particles is obtained.
  • the melt flow rate (MFR) at 190 ° C. and a load of 10 kg is preferably 10 to 50 g / 10 min.
  • the MFR is 10 g / 10 min or more, the secondary foaming property at the time of in-mold molding becomes good, and a foamed particle molded body having a particularly good surface can be obtained.
  • the lower limit of the MFR is more preferably 15 g / 10 minutes, and further preferably 20 g / 10 minutes.
  • MFR is 50 g / 10min or less, the obtained foaming molding will be excellent in recoverability.
  • the upper limit of MFR is more preferably 45 g / 10 minutes, and further preferably 40 g / 10 minutes.
  • This MFR is a value measured under conditions of a temperature of 190 ° C. and a load of 10 kg based on JIS K7210-2: 2014.
  • a foam-molded article can be obtained by in-mold molding of the foamed particles obtained by the production method of the present invention.
  • a conventionally known method can be adopted as the in-mold molding method.
  • the pressure was maintained until the pressure reached, and the pressure was maintained for 15 minutes while maintaining the pressure. Thereafter, back pressure is applied with carbon dioxide, and the pressure in the container is adjusted to be constant at the pressure (foaming pressure) shown in Table 1, while foaming is performed at the temperature of the dispersion medium (foaming temperature) shown in Table 1.
  • the TPU particles impregnated with the agent were discharged together with the dispersion medium under atmospheric pressure to obtain expanded particles.
  • the obtained foamed particles were put in a sealed container, pressurized at 30 ° C. with compressed air of 0.3 MPa (G) for 12 hours, then released and left at 40 ° C. under atmospheric pressure for 48 hours.
  • Average cell diameter of expanded particles 50 expanded particles were randomly selected from the obtained expanded particle group.
  • the expanded particles were cut into two parts by passing through the center.
  • four line segments were drawn at equal angles from the outermost surface of the expanded particles through the central portion to the outermost surface on the opposite side. Measure the number of bubbles intersecting each line segment and divide the total length of the four line segments by the total number of bubbles intersecting the line segment to obtain the average chord length of the bubbles, and further divide by 0.616 By doing this, the average cell diameter of each expanded particle was determined. Then, the average cell diameter of the expanded particles was obtained by arithmetically averaging these values.
  • MFR of expanded particles Based on JIS K7210-2: 2014, measurement was performed under conditions of a temperature of 190 ° C. and a load of 10 kg. As a sample for measurement, a foamed particle was dried at a temperature of 80 ° C. for 4 hours, and then the water content was 500 mass ppm or less.
  • the fusing rate is measured. When the fusing rate is 90% or more, “ ⁇ ”, and when the fusing rate is less than 90%, “ ⁇ ”. It was evaluated.
  • the fusion rate of the foamed molded product was measured by the following method. A test piece was cut out from the foamed molded product with the length of 170 mm, the width of 30 mm, and the thickness as they were. On one surface of the test piece, a cut with a depth of about 10 mm is made in the thickness direction at a position where the vertical length of the test piece is bisected with a cutter knife, and the molded body is bent and broken from the cut portion. It was.
  • a ratio (m / n ⁇ 100 [%]) of the number m of the foam particles whose material was broken on the fracture surface and the number n of all the foam particles present on the fracture surface was calculated.
  • the fusion rate was set to 100%. The above measurement was performed 5 times using different test pieces, the respective material destruction rates were obtained, and the arithmetic average of them was used as the fusion rate.
  • the apparent density of the obtained foamed molded product was measured. The results are shown in Table 1. The method for measuring the apparent density is shown below. These measurements were carried out after the foamed molded product thus obtained was left for 2 days under conditions of 50% relative humidity, 23 ° C. and 1 atm.
  • the foamed molded product was submerged in ethanol, and the apparent volume of the molded product was determined from the rise in the water level.
  • the apparent density [kg / m 3 ] of the foamed molded product was determined by dividing the mass of the foamed molded product by the apparent volume.
  • the foam diameter of the foamed particles is non-uniform
  • the resulting foam-molded product also has a non-uniform cell diameter, white portions of the excessively fine cell diameter are whitened, and the foam molded product is inferior in marble appearance. Only obtained.

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Abstract

La présente invention concerne un procédé de production de particules expansées comprenant l'imprégnation d'un agent d'expansion sous chauffage dans des particules de polyuréthane thermoplastique dispersées dans un milieu aqueux dans un récipient hermétiquement fermé, et l'évacuation des particules de polyuréthane thermoplastique contenant l'agent d'expansion du récipient hermétiquement fermé conjointement au milieu aqueux afin de provoquer l'expansion des particules, produisant de là des particules expansées de polyuréthane thermoplastique ayant une densité apparente de 100 à 300 kg/m3, l'agent d'expansion étant un agent d'expansion physique comprenant principalement du dioxyde de carbone, les particules de polyuréthane thermoplastique contenant 300 à 2 000 ppm en masse d'une poudre inorganique, et la pression à l'intérieur du récipient au moment de l'évacuation étant supérieure à 2,5 MPa(G) mais non supérieure à 4,0 MPa(G).
PCT/JP2017/031875 2016-09-08 2017-09-05 Procédé de production de particules expansées de polyuréthane thermoplastique WO2018047794A1 (fr)

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JP2016175429A JP6346919B2 (ja) 2016-09-08 2016-09-08 熱可塑性ポリウレタン発泡粒子の製造方法
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CN114456433A (zh) * 2022-01-29 2022-05-10 中山大学南昌研究院 一种高硬度热塑性聚氨酯发泡卷材及其半连续制备方法

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JP7326023B2 (ja) * 2019-05-17 2023-08-15 株式会社ジェイエスピー 熱可塑性エラストマー発泡粒子及びその成形体
CN112795174A (zh) * 2020-12-31 2021-05-14 平湖华申汽车内饰件有限公司 一种汽车内饰聚氨酯自动发泡一体化工艺

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