WO2021060255A1 - 液晶ポリマーパウダーおよびその製造方法 - Google Patents

液晶ポリマーパウダーおよびその製造方法 Download PDF

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WO2021060255A1
WO2021060255A1 PCT/JP2020/035732 JP2020035732W WO2021060255A1 WO 2021060255 A1 WO2021060255 A1 WO 2021060255A1 JP 2020035732 W JP2020035732 W JP 2020035732W WO 2021060255 A1 WO2021060255 A1 WO 2021060255A1
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Prior art keywords
liquid crystal
crystal polymer
polymer powder
pulverized
finely pulverized
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French (fr)
Japanese (ja)
Inventor
裕之 大幡
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to EP20869800.1A priority Critical patent/EP4036156A4/en
Priority to JP2021548919A priority patent/JP7405146B2/ja
Priority to CN202080066956.5A priority patent/CN114450328B/zh
Publication of WO2021060255A1 publication Critical patent/WO2021060255A1/ja
Priority to US17/698,314 priority patent/US11939507B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/523—Organic solid particles

Definitions

  • the present invention relates to a liquid crystal polymer powder and a method for producing the same.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-193387
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2005-501760
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2008-50715
  • Patent Document 4 There is Patent No. 5904307
  • Patent Document 1 a pellet-shaped rigid linear aromatic synthetic polymer is mechanically treated in a water-suspended state until the weight average fiber length of the rigid linear aromatic synthetic polymer is 1.6 mm or less.
  • a method for producing a microfibrillated polymer of a rigid linear aromatic synthetic polymer, which comprises a homogenizer treatment after pre-beating, is described.
  • the rigid linear aromatic synthetic polymer include aromatic polyamides typified by poly (p-phenylene terephthalamide) and aromatic polyesters of liquid crystal polymers typified by poly (p-hydroxybenzoic acid). Has been described.
  • Patent Document 2 describes a pulverization method for forming small particles of an anisotropic thermotropic liquid crystal polymer from larger particles.
  • the pulverization method includes (a) a first pulverization step of pulverizing an anisotropic thermotropic liquid crystal polymer with a first pulverizer, and (b) taking out the anisotropic thermotropic liquid crystal polymer from the first pulverizer. And (c) a second pulverization step in which the anisotropic thermotropic liquid crystal polymer from (b) is pulverized by a second pulverizer, and (d) an anisotropic thermotropic liquid crystal polymer is pulverized from the second pulverizer. It is stated that it includes taking out.
  • LCP Liquid Crystal Polymer
  • Patent Document 3 contains a solvent in a proportion of 0.1 to 20% by weight based on the entire fiber, (1) the average fiber length (L) is 0.01 to 1 mm, and (2) the average fiber diameter.
  • a method for producing fine fibers wherein (D) is 0.001 to 1 ⁇ m, and (3) the ratio (L / D) of the average fiber length (L) to the average fiber diameter (D) is 1000 to 10000.
  • a method for producing fine fibers is described in which the fibers are dispersed in a solvent, microfibrillated by a mechanical shearing force, and then dried. It is described that the fiber is selected from the group consisting of aromatic polyamide fibers and polyarylate fibers.
  • Patent Document 4 describes a method for producing a fibrillated liquid crystal polymer powder containing fibrillated liquid crystal polymer particles.
  • the manufacturing method includes a pulverization step and a fibrillation step in this order.
  • a biaxially oriented liquid crystal polymer film is pulverized to obtain a liquid crystal polymer powder.
  • the fibrillation step the fibrillated liquid crystal polymer powder is obtained by crushing the liquid crystal polymer powder with a wet high pressure crusher.
  • pulverization using a freeze pulverization method is carried out. The pulverization using the freeze pulverization method is described as pulverizing an LCP film or the like in a frozen state.
  • a tape-shaped film made of the liquid crystal polymer may be roughly pulverized and then fed into a pulverizer in order while pouring liquid nitrogen. ..
  • the fine fiber is, for example, a fiber having a fiber diameter of 3 ⁇ m to 5 ⁇ m.
  • Cellulose is mainly mentioned as a material constituting fine fibers.
  • Cellulose for example, forms the cell wall of a plant as an aggregate.
  • Fine fibers made of cellulose can be obtained relatively easily by physically or chemically destroying an aggregate of cellulose and defibrating it.
  • cellulose is a polysaccharide and contains a large number of hydroxyl groups, it has extremely high hygroscopicity. This causes a problem when fine fibers made of cellulose are used as an electronic material such as a material forming a part of a circuit board. Specifically, there arises a problem that the electrical characteristics change due to the absorption of moisture by the fine fibers, and a problem that the dimensions of the member composed of the fine fibers change due to the absorption or drying of the fine fibers.
  • the inventor of the present application examined a liquid crystal polymer as a material constituting fine fibers that can be suitably used as an electronic material. This is because the liquid crystal polymer has low hygroscopicity.
  • the inventor of the present application has examined the use of a non-fibrous liquid crystal polymer as a raw material to form fine fibers from the viewpoint of manufacturing cost and the like.
  • the electric field spinning method which is one of the methods for producing fine fibers, it is necessary to dissolve the raw material to be made into fine fibers in a solvent.
  • the material to be made into fine fibers is melted, and the melted material can be discharged from the nozzle.
  • the molten material discharged from the nozzle By applying hot air to the molten material discharged from the nozzle, the material is stretched.
  • the liquid crystal polymer has a low melt tension. Therefore, when the liquid crystal polymer is made into fine fibers by the melt blow method, the liquid crystal polymer is cut before it is sufficiently stretched. Therefore, in the melt blow method, the average diameter of the fiber portion cannot be reduced to about 3 ⁇ m or less.
  • a pellet-shaped liquid crystal polymer is used as a raw material.
  • the pellet-shaped liquid crystal polymer is uniaxially oriented and has a very strong anisotropy.
  • pulverization in a mode in which it is divided along the orientation axis of the molecule occurs preferentially.
  • a fibrous raw material powder having a large aspect ratio is obtained.
  • Patent Document 1 does not describe the fiber diameter of the obtained fibril-like product of the liquid crystal polymer.
  • Patent Document 2 does not describe that the obtained LCP is a fine fiber having an average diameter of 1 ⁇ m or less.
  • Patent Document 3 it is necessary to use a fibrous raw material in order to obtain fine fibers.
  • the content of the lumpy liquid crystal polymer in the entire fiber described in Patent Document 3 is not specified.
  • the present invention has been made in view of the above problems, and is a fine fibrous liquid crystal polymer powder that does not use a fibrous raw material and has a low content of lumps or does not contain lumps.
  • the purpose is to get.
  • the liquid crystal polymer powder based on the present invention contains a fiber part.
  • the fiber portion is composed of fibrous particles having an aspect ratio of 10 times or more, which is the ratio of the length in the longitudinal direction to the fiber diameter.
  • the average diameter of the fiber portion is 1 ⁇ m or less.
  • the content of the lumpy portion that is not substantially fibrous is 20% or less.
  • the method for producing a liquid crystal polymer powder based on the present invention includes a fine pulverization step and a fibrosis step.
  • the fine pulverization step the liquid crystal polymer is pulverized in a state of being dispersed in liquid nitrogen to obtain a granular finely pulverized liquid crystal polymer.
  • the fibrosis step the granular finely pulverized liquid crystal polymer is crushed by a wet high pressure crusher to obtain a liquid crystal polymer powder.
  • it is an image which shows an example of the particle of the liquid crystal polymer powder which was taken in order to measure the average diameter of a fiber part.
  • This is an example of a 3D analysis image of the aggregated portion of the liquid crystal polymer powder according to Example 1.
  • This is an example of a 3D analysis image of the aggregated portion of the liquid crystal polymer powder according to Comparative Example 2.
  • it is a graph which shows the change of D50 of the liquid crystal polymer powder with respect to the number of times of crushing in a fibrosis step.
  • the liquid crystal polymer powder according to one embodiment of the present invention contains a fiber portion and a lump portion.
  • the fibrous portion may be contained in the liquid crystal polymer powder as an agglomerated portion in which fibrous particles are aggregated, or the agglomerated portion may be contained in the liquid crystal polymer as an agglomerated portion in which agglomerated particles are contained.
  • the liquid crystal polymer powder according to this embodiment does not have to contain a lumpy portion.
  • the fiber part is composed of fibrous particles.
  • the fibrous particles are liquid crystal polymer particles having an aspect ratio of 10 times or more, which is the ratio of the length in the longitudinal direction to the fiber diameter.
  • the longitudinal length and fiber diameter of the fibrous particles can be measured from the image data of the fibrous particles obtained when the fibrous particles are observed with a scanning electron microscope.
  • the average diameter of the fiber portion is 1 ⁇ m or less.
  • the value of the average diameter of the fiber portion is the average value of the fiber diameters of the plurality of fibrous particles constituting the fiber portion.
  • the liquid crystal polymer powder according to the present embodiment contains fine fibrous particles.
  • the lumpy part is a liquid crystal polymer powder that is not substantially fibrous.
  • the lumpy portion may have a flat outer shape.
  • the content of the lumpy portion is 20% or less. That is, in the liquid crystal polymer powder according to the present embodiment, the content of the lumpy portion is relatively low, or the liquid crystal polymer powder according to the present embodiment does not contain the lumpy portion.
  • the content of the lumps is evaluated by the number of lumps relative to the number of agglomerates contained in the liquid crystal polymer powder.
  • the agglomerated portion having a maximum height of more than 10 ⁇ m is the agglomerated portion, and the agglomerated portion having a maximum height of 10 ⁇ m or less is the fiber portion.
  • the average diameter of the fiber portion in the liquid crystal polymer powder is 1 ⁇ m or less, the content of the lump portion is 20% or less, and no fibrous raw material is used. , A fine fibrous liquid crystal polymer powder having a low content of lumpy portions has been obtained. Further, the liquid crystal polymer powder having an average diameter of the fiber portion of 1 ⁇ m or less and a content of the lump portion of 20% or less has a high tensile elastic modulus and a large surface area. Therefore, the liquid crystal polymer powder according to the present embodiment is easy to obtain adhesion to other members, and is suitable as a filler to be added to the coating film for reinforcement.
  • the liquid crystal polymer powder according to the present embodiment is made of a thermotropic liquid crystal polymer.
  • the liquid crystal polymer powder according to the present embodiment is heated to 400 ° C. in an inert atmosphere, cooled to room temperature at a temperature lowering rate of 40 ° C./min or more, and then heated again at a temperature rising rate of 40 ° C./min.
  • the endothermic peak temperature measured using a scanning calorimeter exceeds 330 ° C.
  • the liquid crystal polymer powder according to the present embodiment has high heat resistance and can be used as an electronic material.
  • the endothermic peak temperature measured as described above may be simply referred to as "melting point".
  • the liquid crystal polymer powder according to the present embodiment preferably has a D50 value of 13 ⁇ m or less measured by particle size measurement using a particle size distribution measuring device by a laser diffraction / scattering method.
  • the method for producing a liquid crystal polymer powder according to an embodiment of the present invention includes a coarse pulverization step, a fine pulverization step, a coarse grain removal step, and a fibrosis step in this order.
  • a molded product of a liquid crystal polymer is prepared as a raw material.
  • the molded product of the liquid crystal polymer include uniaxially oriented pellets, biaxially oriented films, and powders of liquid crystal polymers.
  • a pellet-shaped or powder-shaped liquid crystal polymer is preferable, and a pellet-shaped liquid crystal polymer is more preferable, from the viewpoint of manufacturing cost and the like.
  • the molded product of the liquid crystal polymer does not include the fibrous liquid crystal polymer directly molded by the electrolytic spinning method, the melt blow method, or the like.
  • the molded product of the liquid crystal polymer may contain a pellet-shaped liquid crystal polymer or a liquid crystal polymer processed into a fibrous form by crushing a powder-like liquid crystal polymer.
  • the melting point of the molded product of the liquid crystal polymer is preferably larger than 330 ° C, more preferably 350 ° C or higher. As a result, a liquid crystal polymer powder having high heat resistance suitable as a material for electronic parts can be obtained.
  • the film-shaped liquid crystal polymer is usually molded by the melt extrusion method.
  • a melt extrusion method for a liquid crystal polymer having a melting point higher than 330 ° C. a large amount of fish eyes of the liquid crystal polymer are generated or deterioration due to decomposition occurs.
  • the liquid crystal polymer needs to be heated to near the decomposition temperature and continuously kneaded. Therefore, a film-shaped liquid crystal polymer having a melting point higher than 330 ° C. cannot be used as a molded product of the liquid crystal polymer.
  • a coarsely pulverized liquid crystal polymer is obtained by coarsely pulverizing a molded product of the liquid crystal polymer.
  • a molded product of a liquid crystal polymer is roughly pulverized with a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the particle size of the coarsely pulverized liquid crystal polymer is not particularly limited as long as it can be used as a raw material for the fine pulverization step described later.
  • the maximum particle size of the coarsely pulverized liquid crystal polymer is, for example, 3 mm or less.
  • the method for producing the liquid crystal polymer powder in the present embodiment does not necessarily have to include a coarse pulverization step.
  • the molded product of the liquid crystal polymer can be used as a raw material for the fine pulverization step, the molded product of the liquid crystal polymer may be directly used as a raw material for the fine pulverization step.
  • a coarsely pulverized liquid crystal polymer is pulverized in a state of being dispersed in liquid nitrogen to obtain a granular finely pulverized liquid crystal polymer.
  • a medium is used to pulverize the coarsely pulverized liquid crystal polymer dispersed in liquid nitrogen.
  • the media is, for example, beads.
  • the pulverization method in which the liquid crystal polymer is dispersed in liquid nitrogen is different from the conventional freeze pulverization method.
  • the conventional freeze-grinding method is a method of crushing the raw material to be crushed while pouring liquid nitrogen onto the raw material to be crushed and the main body of the crushing device.
  • the liquid nitrogen is vaporized when the raw material to be crushed is crushed. That is, in the conventional freeze-grinding method, the raw material to be crushed is not dispersed in liquid nitrogen at the time when the raw material to be crushed is crushed.
  • the heat of the raw material to be crushed, the heat generated from the crushing device, and the heat generated by crushing the raw material to be crushed vaporize liquid nitrogen in an extremely short time. Therefore, in the conventional freeze pulverization method, the raw material during pulverization located inside the pulverizer has a temperature much higher than the boiling point of liquid nitrogen, which is -196 ° C. That is, in the conventional freeze pulverization method, pulverization is carried out under the condition that the temperature inside the pulverizer is usually about 0 ° C. to 100 ° C. In the conventional freeze pulverization method, even when liquid nitrogen is supplied as much as possible, the temperature inside the pulverizer is about ⁇ 150 ° C. at the lowest case.
  • a plane substantially parallel to the axial direction of the molecular axis of the liquid crystal polymer is used. Since the pulverization proceeds along the above, a fibrous liquid crystal polymer having a large aspect ratio and a fiber diameter much larger than 1 ⁇ m can be obtained. That is, even if a uniaxially oriented pellet-shaped liquid crystal polymer or a coarsely pulverized pellet-shaped liquid crystal polymer is crushed in the conventional freeze-crushing direction, a granular finely crushed liquid crystal polymer cannot be obtained.
  • the raw material to be crushed since the raw material to be crushed is crushed in a state of being dispersed in liquid nitrogen, the raw material in a further cooled state can be crushed as compared with the conventional freeze crushing method.
  • the raw material to be pulverized can be pulverized at a temperature lower than -196 ° C., which is the boiling point of liquid nitrogen.
  • the brittle fracture of the raw material to be pulverized is repeated, so that the pulverization of the raw material proceeds.
  • the liquid crystal polymer that has become granular due to brittle fracture in liquid nitrogen is continuously impacted with a medium or the like in a brittle state.
  • a plurality of fine cracks are formed from the outer surface to the inside of the liquid crystal polymer obtained in the fine pulverization step of the present embodiment.
  • the granular finely pulverized liquid crystal polymer obtained by the pulverization step preferably has a D50 of 50 ⁇ m or less as measured by a particle size distribution measuring device by a laser diffraction / scattering method. As a result, it is possible to prevent the granular finely pulverized liquid crystal polymer from being clogged with the nozzle in the fibrosis step shown below.
  • the coarse grain removing step coarse grains are removed from the granular finely pulverized liquid crystal polymer obtained in the above fine pulverization step.
  • coarse grains are removed from the granular finely pulverized liquid crystal polymer obtained in the above fine pulverization step.
  • a granular finely pulverized liquid crystal polymer under the sieve is obtained, and by removing the granular liquid crystal polymer on the sieve, a granular finely pulverized liquid crystal polymer is obtained.
  • the coarse particles contained can be removed.
  • the type of mesh may be appropriately selected, and examples of the mesh include those having a mesh opening of 53 ⁇ m.
  • the method for producing the liquid crystal polymer powder according to the present embodiment does not necessarily have to include a coarse grain removing step.
  • the granular liquid crystal polymer is crushed by a wet high pressure fracturing device to obtain a liquid crystal polymer powder.
  • the finely pulverized liquid crystal polymer is dispersed in a dispersion medium.
  • the finely pulverized liquid crystal polymer to be dispersed does not have to have coarse particles removed, but it is preferable that coarse particles have been removed.
  • the dispersion medium include water, ethanol, methanol, isopropyl alcohol, toluene, benzene, xylene, phenol, acetone, methyl ethyl ketone, diethyl ether, dimethyl ether, hexane, or a mixture thereof.
  • the finely pulverized liquid crystal polymer dispersed in the dispersion medium that is, the slurry-like finely pulverized liquid crystal polymer is passed through the nozzle in a state of being pressurized at a high pressure.
  • the shearing force or collision energy due to the high-speed flow at the nozzle acts on the liquid crystal polymer to crush the granular finely crushed liquid crystal polymer, and the fibrosis of the liquid crystal polymer progresses.
  • the liquid crystal polymer powder according to the embodiment can be obtained.
  • the nozzle diameter of the nozzle is preferably made as small as possible within a range in which clogging of the finely pulverized liquid crystal polymer does not occur in the nozzle. Since the granular finely pulverized liquid crystal polymer in the present embodiment has a relatively small particle size, the nozzle diameter in the wet high-pressure crusher used in the fibrosis step can be reduced.
  • the nozzle diameter is, for example, 0.2 mm or less.
  • a plurality of fine cracks are formed in the granular finely pulverized liquid crystal polymer powder. Therefore, by pressurizing with a wet high-pressure disperser, the dispersion medium penetrates into the finely pulverized liquid crystal polymer through fine cracks. Then, when the slurry-like finely pulverized liquid crystal polymer passes through the nozzle and is located under normal pressure, the dispersion medium that has penetrated into the finely pulverized liquid crystal polymer expands in a short time. As the dispersion medium that has penetrated into the finely pulverized liquid crystal polymer expands, destruction proceeds from the inside of the finely pulverized liquid crystal polymer.
  • the granular liquid crystal obtained by the conventional freeze pulverization method is obtained by defibrating the granular finely pulverized liquid crystal polymer obtained in the fine pulverization step in the present embodiment. It is possible to obtain the liquid crystal polymer powder according to the present embodiment, which has a lower content of a lump portion and is in the form of fine fibers than the liquid crystal polymer powder obtained by crushing the polymer.
  • the finely pulverized liquid crystal polymer may be crushed a plurality of times with a wet high pressure crusher to obtain a liquid crystal polymer powder. It is preferable that the number of times of crushing by the wet high pressure crusher is small. The number of times of crushing by the wet high-pressure crushing device may be, for example, 5 times or less.
  • the method for producing a liquid crystal polymer powder according to an embodiment of the present invention includes a fine pulverization step and a fibrosis step.
  • the fine pulverization step the liquid crystal polymer is pulverized in a state of being dispersed in liquid nitrogen to obtain a granular finely pulverized liquid crystal polymer.
  • the fibrosis step the finely pulverized liquid crystal polymer is crushed by a wet high pressure crusher to obtain a liquid crystal polymer powder.
  • the liquid crystal polymer dispersed in liquid nitrogen is pulverized by using a medium in the fine pulverization step.
  • the raw material dispersed in liquid nitrogen can be pulverized with a simple structure.
  • Example 1 In Example 1, first, a film-like liquid crystal polymer having a thickness of 250 ⁇ m and having molecules biaxially oriented in the plane direction was roughly pulverized by being charged into a cutter mill device.
  • the melting point of the liquid crystal polymer used in Example 1 is 315 ° C.
  • a coarsely pulverized film-like liquid crystal polymer was discharged from a discharge hole having a diameter of 3 mm provided in a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the coarsely pulverized liquid crystal polymer was finely pulverized with a liquid nitrogen bead mill (LNM-08 manufactured by IMEX).
  • a liquid nitrogen bead mill In pulverization with a liquid nitrogen bead mill, a vessel volume of 0.8 L is used, zirconia beads having a diameter of 5 mm are used as media, the amount of media charged is 500 mL, 30 g of coarsely pulverized liquid crystal polymer is charged, and rotation is performed.
  • the pulverization treatment was carried out at several 2000 rpm for 120 minutes.
  • a coarsely pulverized liquid crystal polymer is dispersed in liquid nitrogen to perform a wet pulverization treatment.
  • FIG. 1 is a photograph of a pulverized liquid crystal polymer after being pulverized by the pulverization step in Example 1. As shown in FIG. 1, the coarsely pulverized liquid crystal polymer was pulverized with a liquid nitrogen bead mill to obtain a granular finely pulverized liquid crystal polymer. The photographs in FIG. 1 and FIGS. 2 to 12 shown below were taken with a scanning electron microscope.
  • the finely pulverized liquid crystal polymer was sieved with a mesh having an opening of 53 ⁇ m to remove coarse particles contained in the finely pulverized liquid crystal polymer, and the finely pulverized liquid crystal polymer that had passed through the mesh was recovered.
  • the yield of the finely pulverized liquid crystal polymer by removing the coarse particles was 85% by mass.
  • the finely pulverized liquid crystal polymer from which the coarse particles had been removed was dispersed in a 20 wt% ethanol aqueous solution.
  • the ethanol slurry in which the finely pulverized liquid crystal polymer was dispersed was pulverized a plurality of times using a wet high pressure crusher under the conditions of a nozzle diameter of 0.2 mm and a pressure of 200 MPa to form fibers.
  • a wet high-pressure crusher NanoVita (registered trademark) C-ES008 manufactured by Yoshida Kikai Kogyo Co., Ltd. was used.
  • FIG. 2 is a photograph of the liquid crystal polymer powder after being repeatedly crushed 5 times by the fibrosis step in Example 1. As shown in FIG. 2, by crushing the finely pulverized liquid crystal polymer, a fine fibrous liquid crystal polymer powder was obtained.
  • Example 2 In Example 2, instead of the film-shaped liquid crystal polymer charged into the cutter mill device in Example 1, a uniaxially oriented pellet-shaped liquid crystal polymer was charged into the cutter mill device to obtain a coarsely pulverized liquid crystal polymer. .. In Example 2, a liquid crystal polymer having a melting point of 315 ° C. was used. Then, in the same manner as in Example 1, fine pulverization was performed with a liquid nitrogen bead mill.
  • FIG. 3 is a photograph of a pulverized liquid crystal polymer after being pulverized by the pulverization step in Example 2. As shown in FIG. 3, also in Example 2, a finely pulverized liquid crystal polymer was obtained by pulverizing the coarsely pulverized liquid crystal polymer with a liquid nitrogen bead mill.
  • FIG. 4 is a photograph of the internal cross section of the pulverized liquid crystal polymer after being pulverized by the pulverization step in Example 2. As shown in FIG. 4, it was confirmed that a large number of cracks were formed inside the finely pulverized liquid crystal polymer in Example 2.
  • the coarse particles contained in the finely pulverized liquid crystal polymer were removed in the same manner as in Example 1, and the finely pulverized liquid crystal polymer from which the coarse particles had been removed was crushed a plurality of times with a wet high pressure crusher to form fibers.
  • FIG. 5 is a photograph of the liquid crystal polymer powder after being repeatedly crushed 5 times by the fibrosis step in Example 2. As shown in FIG. 5, in Example 2, by crushing the finely pulverized liquid crystal polymer, a fine fibrous liquid crystal polymer powder was obtained without clogging the nozzle of the wet high pressure crusher with the liquid crystal polymer.
  • Example 3 a coarsely pulverized liquid crystal polymer was obtained by charging a uniaxially oriented pellet-shaped liquid crystal polymer into the cutter mill device instead of the film-shaped liquid crystal polymer charged into the cutter mill device in Example 1. It was. In Example 3, unlike Examples 1 and 2, a liquid crystal polymer having a melting point of 350 ° C. was used. Then, fine pulverization was performed with a liquid nitrogen bead mill in the same manner as in Examples 1 and 2.
  • FIG. 6 is a photograph of a pulverized liquid crystal polymer after being pulverized by the pulverization step in Example 3. As shown in FIG. 6, also in Example 3, the coarsely pulverized liquid crystal polymer was pulverized with a liquid nitrogen bead mill to obtain a granular finely pulverized liquid crystal polymer.
  • the coarse particles contained in the finely pulverized liquid crystal polymer were removed in the same manner as in Examples 1 and 2, and the finely pulverized liquid crystal polymer from which the coarse particles were removed was crushed by a wet high-pressure crusher to form fibers.
  • FIG. 7 is a photograph of the liquid crystal polymer powder after being repeatedly crushed 5 times by the fibrosis step in Example 3. As shown in FIG. 7, also in Example 3, by crushing the finely pulverized liquid crystal polymer, a fine fibrous liquid crystal polymer powder was obtained without clogging the nozzle of the wet high pressure crusher with the liquid crystal polymer. Further, in Example 3, since the liquid crystal polymer powder in the form of pellets is used as the raw material instead of the film, it is possible to use a liquid crystal polymer having a relatively high melting point, and by extension, a fine fibrous liquid crystal having a high melting point. I was able to obtain a polymer powder.
  • Comparative Example 1 In Comparative Example 1, first, in the same manner as in Example 2, a uniaxially oriented pellet-shaped liquid crystal polymer was coarsely pulverized with a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the coarsely pulverized liquid crystal polymer was finely pulverized using a dry freeze pulverizer (Hosokawa Micron Co., Ltd., Linlex Mill (registered trademark)).
  • a dry freeze pulverizer Hosokawa Micron Co., Ltd., Linlex Mill (registered trademark)
  • liquid nitrogen is supplied to the inside of the apparatus together with the coarsely pulverized liquid crystal polymer.
  • the nitrogen supplied to the inside of the device is vaporized instantaneously, the nitrogen exists as a gas inside the device.
  • FIG. 8 is a photograph of a pulverized liquid crystal polymer after being pulverized by the pulverization step in Comparative Example 1.
  • the finely pulverized liquid crystal polymer obtained by pulverizing the coarsely pulverized liquid crystal polymer with a dry freeze pulverizer became a fibrous liquid crystal polymer having a fiber diameter of several tens of ⁇ m to several hundreds of ⁇ m.
  • the following can be considered as the cause of the finely pulverized liquid crystal polymer becoming a fibrous liquid crystal polymer.
  • the pellet-shaped liquid crystal polymer used in this comparative example first, the molten liquid crystal polymer is extruded from a die to prepare a strand. Due to the strong shearing force associated with extrusion from the die, the molecules constituting the liquid crystal polymer are strongly uniaxially oriented in the direction parallel to the extrusion direction. Then, by cutting the strands to a predetermined length, a pellet-shaped liquid crystal polymer can be obtained.
  • the pellet-shaped liquid crystal polymer and the coarsely crushed liquid crystal polymer obtained by coarsely pulverizing the pellet-like liquid crystal polymer also have strong anisotropy because the molecules are uniaxially oriented. Therefore, in the conventional dry freeze pulverization apparatus, it is considered that the fibrous liquid crystal polymer was obtained by pulverizing the coarsely pulverized liquid crystal polymer along the uniaxial orientation.
  • a fibrous finely pulverized liquid crystal polymer having a size of several tens of ⁇ m to several hundreds of ⁇ m was sieved with a mesh of 53 ⁇ m to remove coarse particles, and the finely pulverized liquid crystal polymer that had passed through the mesh was recovered.
  • the yield of the finely pulverized liquid crystal polymer by removing the coarse particles was 3% by mass.
  • the finely pulverized liquid crystal polymer after removing the coarse particles was also fibrous.
  • FIG. 9 is a photograph of the internal cross section of the pulverized liquid crystal polymer after being pulverized by the pulverization step in Comparative Example 1. As shown in FIG. 9, it was confirmed that the number of cracks inside the finely pulverized liquid crystal polymer in Comparative Example 1 was extremely small as compared with the number of cracks inside the finely pulverized liquid crystal polymer in Example 2.
  • the fibrous finely pulverized liquid crystal polymer from which the coarse particles have been removed is further fiber of the finely pulverized liquid crystal polymer by crushing with a wet high pressure fracturing device in the same manner as in Example 2, that is, under the same conditions as in Example 1. I tried to change it. However, since the fibrous finely pulverized liquid crystal polymer was clogged in the nozzle in the wet high pressure crusher, the liquid crystal polymer powder could not be obtained in Comparative Example 1.
  • Comparative Example 2 In Comparative Example 2, first, in the same manner as in Example 1, a biaxially oriented film-shaped liquid crystal polymer was roughly pulverized with a cutter mill device to obtain a coarsely pulverized liquid crystal polymer. Then, the coarsely pulverized liquid crystal polymer was finely pulverized using the dry freeze pulverizer used in Comparative Example 1.
  • FIG. 10 is a photograph of a finely pulverized liquid crystal polymer after being pulverized by the pulverization step in Comparative Example 2. As shown in FIG. 10, in Comparative Example 2, a finely pulverized liquid crystal polymer was obtained by finely pulverizing the coarsely pulverized liquid crystal polymer using a dry freeze pulverizer.
  • FIG. 11 is a photograph of the liquid crystal polymer powder after being repeatedly crushed seven times by the fibrosis step in Comparative Example 2.
  • a liquid crystal polymer powder was obtained by crushing a finely pulverized liquid crystal polymer.
  • the surface of the finely pulverized liquid crystal polymer could be fibrillated by crushing only once or twice, but the entire finely pulverized liquid crystal polymer could not be made into fine fibers.
  • the liquid crystal polymer powder to be measured was dispersed in ethanol to prepare a slurry containing 0.01 wt% liquid crystal polymer powder. At this time, the slurry was prepared so that the water content in the slurry was 1 wt% or less. Then, after dropping 5 ⁇ L to 10 ⁇ L or less of this slurry onto the slide glass, the slurry on the slide glass was naturally dried. The liquid crystal polymer powder was placed on the slide glass by allowing the slurry to air dry.
  • FIG. 12 is an image showing an example of particles of the liquid crystal polymer powder taken to measure the average diameter of the fiber portion in this embodiment. As shown in FIG. 12, the particles of the liquid crystal polymer powder are shown in white.
  • the above region was set according to the size of each particle of the liquid crystal polymer so that the number of image data would be 100 or more. Further, for each particle of the liquid crystal polymer, in order to suppress omission of image data collection and occurrence of measurement error, the magnification of the scanning electron microscope is appropriately changed to 500 times, 3000 times, or 10000 times, and the above is described. Image data was collected.
  • the longitudinal dimension and the width dimension of each particle of the liquid crystal polymer powder were measured.
  • a path that can be taken on one particle of the liquid crystal polymer powder photographed in each of the above image data that is, from one end of the particle through substantially the center of the particle to the opposite end of the one end.
  • the direction along the longest route was defined as the longitudinal direction.
  • the dimension of the length of the longest path was measured as the dimension in the longitudinal direction.
  • the dimensions of one particle of the liquid crystal polymer powder in the direction orthogonal to the longitudinal direction were measured at three points different from each other in the longitudinal direction. The average value of the dimensions measured at these three points was taken as the widthwise dimension per particle of the liquid crystal polymer powder.
  • one particle of the liquid crystal polymer powder whose longitudinal dimension is 10 times or more of the width direction dimension is defined as a fibrous particle constituting the fiber portion. That is, the fiber diameter of the particles constituting the liquid crystal polymer powder in the fiber portion is the width direction dimension of the liquid crystal polymer powder. Then, with respect to the fibrous particles constituting the fiber portion, the fiber diameters of 100 fibrous particles were measured. The value obtained by averaging the measurement results of these fiber diameters was taken as the average diameter of the fiber portion.
  • the liquid crystal polymer powder to be evaluated was collected in the state of a slurry immediately after crushing by a wet high pressure crusher. Ethanol was additionally mixed with the collected slurry-like liquid crystal polymer powder to further dilute the slurry-like liquid crystal polymer powder. Ethanol was additionally mixed until the content of the liquid crystal polymer powder in the slurry was diluted to 0.01 wt% or less. The diluted slurry was dropped onto a slide glass and then left at room temperature to vaporize ethanol, which is a dispersion medium of the slurry. In this way, the liquid crystal polymer powder was placed on the slide glass.
  • the liquid crystal polymer powder placed on the slide glass was observed with a laser microscope (manufactured by KEYENCE, VK-8700) at a magnification of 100 times. From the observation, it was confirmed that the liquid crystal polymer powder contained a plurality of agglutinating portions in Examples 1 to 3 and Comparative Example 2. For example, the agglomerated portion can be confirmed by a scanning electron microscope. For example, as shown in FIGS. 5 and 11, in Examples 1 to 3 and Comparative Example 2, the liquid crystal polymer powder is an agglomerated portion. Includes.
  • FIG. 13 is an example of a 3D analysis image of the aggregated portion of the liquid crystal polymer powder according to Example 1.
  • Example 14 is an example of a 3D analysis image of the aggregated portion of the liquid crystal polymer powder according to Comparative Example 2. As shown in FIGS. 13 and 14, the overall heights of the agglomerated portion in Example 1 and the agglomerated portion in Comparative Example 2 are significantly different.
  • the liquid crystal polymer powder to be measured 30 agglomerates were selected by the above microscopic observation, and the maximum height of each of these agglutinates was measured.
  • the average diameter of the fiber portions was 1 ⁇ m, so that the agglomerated portion having the maximum height of 10 ⁇ m was determined to be a lump portion in which the liquid crystal polymer was not fibrous. ..
  • the ratio of the number of lumpy portions to the number of agglomerated portions whose maximum height was measured was evaluated as the content of the lumpy portions contained in the liquid crystal polymer powder.
  • Example 1 The details of the evaluation results of the content of the lumpy portion in Example 1 and Comparative Example 2 are shown in Table 1 below.
  • Table 1 For each of Example 1 and Comparative Example 2, each of the 30 selected agglutinating portions is numbered, and the results of measuring the maximum height of the agglutinating portions related to each number are shown. There is.
  • Example 2 the content rate of the lumpy portion was evaluated in the same manner as in Example 1 and Comparative Example 2.
  • the evaluation results of the content of the lumpy portion in Examples 1 to 3 and Comparative Example 2 are shown in Table 2 below.
  • a particle size distribution measuring device manufactured by HORIBA, Ltd., LA-950
  • Ekinen was used as the dispersion medium to disperse the liquid crystal polymer to be measured.
  • the liquid crystal polymer to be measured dispersed in the dispersion medium was subjected to sonication for 10 seconds, and then set in a particle size distribution measuring device to measure the particle size.
  • FIG. 15 is a graph showing changes in D50 of the liquid crystal polymer powder with respect to the number of times of crushing in the fibrosis step for Examples 1 to 3 and Comparative Example 2.
  • the liquid crystal polymer having 0 times of crushing means the liquid crystal polymer before crushing in the fibrosis step, that is, the finely pulverized liquid crystal polymer immediately after the coarse particles are removed.
  • Example 1 the value of D50 of the finely pulverized liquid crystal polymer immediately after being pulverized and the coarse particles were removed was 23 ⁇ m. Further, in Examples 1 to 3, D50 was significantly smaller than that in Comparative Example 2 in the first crushing. For example, in Example 1, the D50 of the liquid crystal polymer was 9.3 ⁇ m in the first crushing. In Examples 1 to 3, since the finely pulverized liquid crystal polymer is obtained by using a liquid nitrogen bead mill, the finely pulverized liquid crystal polymer is in a state of being sufficiently embrittled. Therefore, it is considered that the fine fiber formation in the fiberization step progresses rapidly, the entire fine powder liquid crystal polymer becomes fine fiber in one crushing, and the D50 becomes significantly smaller.
  • the value of D50 of the liquid crystal polymer in Comparative Example 2 was larger than the value of D50 obtained by one crushing in Example 1 even after 15 times of crushing. Since the liquid crystal polymer in Comparative Example 2 is not sufficiently embrittled in the fine pulverization step, it is considered that the fine fibrosis is difficult to proceed in the fibrosis step carried out after the fine pulverization step.

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JP2022190608A (ja) * 2021-06-14 2022-12-26 Ｅｎｅｏｓ株式会社 フィブリル状液晶ポリマー粒子の製造方法
JPWO2023007847A1 (https=) * 2021-07-26 2023-02-02
WO2023074737A1 (ja) * 2021-10-29 2023-05-04 株式会社村田製作所 多孔体および多孔体の製造方法
JPWO2023095593A1 (https=) * 2021-11-26 2023-06-01
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