Classifications

• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/123—Treatment by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
• • 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
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
  • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
  • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
• • 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
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/16—Cooling
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • 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
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
  • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
  • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
  • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2015/00—Gear wheels or similar articles with grooves or projections, e.g. control knobs
  • B29L2015/003—Gears
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
  • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
• • 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
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

• the present invention relates to an aromatic polyetherketone molded article that can be used for various parts, and a method for producing the same.
• the resin molded body can be further subjected to heat treatment such as annealing treatment.
• an object of the present invention is to provide a technology that can further improve the performance of aromatic polyetherketone molded articles.
• an aromatic polyetherketone molded article includes a main body and a surface layer covering the main body. Both the main body portion and the surface layer portion include a peak A that appears in the wave number range of 1295 to 1340 cm ⁇ 1 and a peak B that appears in the wave number range of 1265 to 1295 cm ⁇ 1 as measured by an infrared spectrophotometer. An infrared absorption spectrum is obtained. The ratio A'/B' of the intensity A' of the peak A to the intensity B' of the peak B is higher in the surface layer portion than in the main body portion.
• this aromatic polyetherketone molded article the degree of crystallinity is higher in the surface layer portion constituting the surface than in the main body portion inside the surface layer portion. As a result, this aromatic polyetherketone molded article has high mechanical strength in the surface layer portion, so that progress of wear and occurrence of chipping can be suppressed.
• this aromatic polyetherketone molded article the impact absorption property is maintained in the main body portion whose degree of crystallinity is not increased, so that the impact applied to the surface layer portion is absorbed by the main body portion. As a result, in this aromatic polyetherketone molded article, it becomes difficult to apply large stress locally to the surface layer portion, so that the occurrence of damage can be further suppressed.
• the aromatic polyetherketone molded article may be formed of at least one of polyetheretherketone and polyetherketone.
• the aromatic polyetherketone molded article may be formed of aromatic polyetherketone containing additives.
• the aromatic polyetherketone molded article may be configured as a sliding member.
• the aromatic polyetherketone molded article may be configured as a gear member.
• the method for producing an aromatic polyetherketone molded article according to one embodiment of the present invention is characterized in that a peak A appearing in a wave number range of 1295 to 1340 cm -1 and a wave number range of 1265 to 1295 cm -1 are obtained by measurement using an infrared spectrophotometer.
• the method includes the steps of: producing a molded article from which an infrared absorption spectrum including peak B appearing in is obtained; and irradiating the surface of the molded article with an electron beam. In the step of irradiating the electron beam, a ratio A'/B' of the intensity A' of the peak A to the intensity B' of the peak B in the surface layer portion of the molded body may be increased.
• the molded body In the step of irradiating the electron beam, the molded body may be heated. In these configurations, the degree of crystallinity can be selectively increased only in the surface layer portion constituting the surface of the aromatic polyetherketone molded product by irradiation with an electron beam.
• the present invention can provide a technology that can further improve the performance of aromatic polyetherketone molded articles.
• FIG. 1 is a flowchart showing a method for manufacturing a resin molded body according to an embodiment of the present invention. It is a figure which shows an example of the infrared absorption spectrum of the said resin molding. It is a graph showing a change in the ratio A'/B' depending on the irradiation dose of an electron beam. It is a top view which shows the example which comprised the said resin molded body as a gear member.
• Aromatic polyetherketone is a resin composed of a benzene ring, ether, and ketone, and typically includes polyetheretherketone (PEEK), which has excellent heat resistance and mechanical strength.
• PEEK polyetheretherketone
• the aromatic polyetherketone that can form the resin molded article of the present invention includes, for example, polyetherketone (PEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK). , polyetherketoneetherketoneketone (PEKEKK), and the like. Further, the aromatic polyetherketone forming the resin molded article of the present invention may be a blend of a plurality of types.
• the resin molded article of the present invention may be formed of an aromatic polyetherketone containing additives.
• the performance of the resin molded article can be further improved by using additives.
• additives that can be used in the present invention include fibrous fillers, non-fibrous fillers, and solid lubricants.
• fibrous additives include carbon fibers, nanocarbons (carbon nanotubes and carbon nanowires), glass fibers, and the like.
• non-fibrous fillers include graphite, mica, talc, and alumina.
• the solid lubricant include polytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), and the like.
• the performance of the resin molded article is improved by controlling the crystallinity of the aromatic polyetherketone that constitutes the resin molded article.
• the degree of crystallinity of an aromatic polyetherketone is determined from an infrared absorption spectrum obtained by measurement using an infrared spectrophotometer.
• the infrared absorption spectrum is obtained as a graph with the wavenumber as the horizontal axis and the absorbance as the vertical axis by measuring the absorbance with an infrared spectrophotometer while continuously changing the wavenumber.
• the absorbance of the resin molded article according to the present embodiment is measured in a wave number range including at least 1265 to 1340 cm -1 .
• the infrared absorption spectrum of aromatic polyetherketone includes a peak A appearing in the wave number range of 1295 to 1340 cm -1 and a peak B appearing in the wave number range of 1265 to 1295 cm -1 .
• the higher the crystallinity the higher the peak A relative to the peak B.
• the crystallinity of aromatic polyetherketone can be evaluated by the ratio A'/B' of intensity A' obtained as the height of peak A to intensity B' obtained as the height of peak B.
• the ratio A'/B' is, the higher the crystallinity is, and the smaller the ratio A'/B' is, the lower the crystallinity is.
• FIG. 1 is a flowchart showing a method for manufacturing a resin molded body according to the present embodiment.
• a raw material resin is prepared.
• a commercially available product configured as aromatic polyetherketone pellets or powder can be used.
• step S02 the raw resin prepared in step S01 is molded.
• known molding methods such as injection molding and extrusion molding can be used.
• step S02 the takt time can be shortened by rapidly cooling the mold after molding and before taking out the molded body of the raw resin.
• processing for modifying the shape such as cutting or grinding, may be applied to the molded body of the raw resin taken out from the mold.
• step S03 the entire surface of the molded body of the raw resin obtained in step S02 is irradiated with an electron beam.
• the electron beam incident on the surface promotes crystallization of the amorphous portion of the aromatic polyetherketone constituting the vicinity of the surface, increasing the degree of crystallinity in the vicinity of the surface.
• step S03 the resin molded body has a surface layer portion whose crystallinity has been increased by electron beam irradiation, and a main body portion that is located inside the surface layer portion and is not affected by the electron beam irradiation. is obtained.
• the crystallinity level immediately after step S02 is maintained in the main body portion covered with the surface layer portion.
• FIG. 2 shows an example of the infrared absorption spectrum of the surface layer portion and the main body portion of the resin molded article according to the present embodiment.
• the infrared absorption spectrum of the surface layer portion can be obtained, for example, by measuring the absorbance of the surface of the resin molded article.
• the infrared absorption spectrum of the main body can be obtained, for example, by measuring the absorbance of a cross section of the resin molded body that exposes the main body.
• the absorption spectrum of the surface layer portion is shown by a broken line
• the absorption spectrum of the main body portion is shown by a solid line.
• the intensity B' of peak B is the same in the surface layer part and the main body part, whereas the intensity A' of peak A is higher in the surface layer part than in the main body part. That is, in the resin molded article according to this embodiment, the ratio A'/B' of strengths A' and B is larger in the surface layer portion than in the main body portion.
• the same absorption spectrum should be obtained from the surface layer portion and the body portion.
• the peak A is higher in the surface layer than in the main body, which indicates that the degree of crystallinity is increased only in the surface layer.
• the crystallization of the surface layer adjacent to the mold does not progress sufficiently, resulting in amorphous parts. A lot of it often remains.
• the crystallization of the surface layer portion can be sufficiently progressed in step S03, and furthermore, the degree of crystallinity of the surface layer portion can be made higher than that of the main body portion.
• the resin molded article according to the present embodiment by increasing the degree of crystallinity of the surface layer portion, it is possible to increase the mechanical strength near the surface where large stress is easily applied from the outside. Thereby, in the resin molded article according to the present embodiment, it is possible to suppress the progression of wear and the occurrence of chipping near the surface constituted by the surface layer portion.
• the impact absorption properties of the main body portion which is not affected by electron beam irradiation, are maintained, so the impact applied to the surface layer portion is well absorbed.
• it becomes difficult to apply a large stress locally to the surface layer portion so that the occurrence of damage can be suppressed more effectively.
• the mechanical strength of only the surface layer portion can be increased without increasing the mechanical strength of the main body portion.
• the effect of suppressing the occurrence of damage due to the synergistic effect between the surface layer portion and the main body portion can be obtained.
• the portion whose crystallinity is changed by electron beam irradiation is limited to only the surface layer portion, and the crystallinity degree of the main body portion, which occupies most of the portion, is not changed. Therefore, in this resin molded article, the amount of shrinkage due to progress of crystallization after molding remains small, and dimensional changes from the shape immediately after molding can be suppressed to a small level.
• the thickness of the surface layer portion of the resin molded article according to the present embodiment can be determined as appropriate depending on the application and the like.
• the thickness of the surface layer is preferably 50 ⁇ m or more.
• the thickness of the surface layer of the resin molded body can be controlled in various ways by changing the electron beam irradiation conditions. However, since large-scale equipment is required to increase the thickness of the surface layer, it is preferable to keep the thickness of the surface layer at 700 ⁇ m or less, also from the viewpoint of keeping manufacturing costs low without using large-scale equipment.
• FIG. 3 is a graph plotting the ratio A'/B' of the surface layer portion when the electron beam irradiation dose is changed in step S03. Note that in all plots in FIG. 3, other electron beam irradiation conditions and the configuration of the molded body of the raw resin were made common. Moreover, the plot of zero irradiation dose in FIG. 4 shows the condition where no electron beam is irradiated.
• the electron beam irradiation dose As shown in FIG. 3, it can be seen that by setting the electron beam irradiation dose to 50 kGy or more, the effect of promoting crystallization as described above can be easily obtained. On the other hand, if the electron beam irradiation dose is too large, decomposition of the molecular chain of the aromatic polyetherketone will proceed. For this reason, it is preferable to keep the electron beam irradiation dose to 200 kGy or less.
• step S03 it is preferable to irradiate the molded body of the raw resin with an electron beam while heating it.
• the effect of improving the mechanical strength of the surface layer portion can be more easily obtained, and, for example, the fracture characteristics can be further improved.
• the temperature of the raw resin molded body during electron beam irradiation is, for example, 200° C. or higher.
• the resin molded article according to this embodiment is particularly suitable for application to parts where stress tends to concentrate on the surface.
• Examples of such parts include sliding members such as gear members, seal rings, thrust washers, and bearings.
• a resin molded body configured as a sliding member can not only suppress the occurrence of damage but also reduce friction loss.
• FIG. 4 shows a gear member as an application example of the resin molded body according to the present embodiment as a sliding member.
• stress tends to concentrate at the roots of a plurality of teeth T arranged in succession along the outer periphery, but by constructing the resin molded body according to this embodiment, the occurrence of chipping of the teeth T can be effectively prevented. can be suppressed to
• Examples and comparative examples (Outline explanation) Examples and comparative examples of the above embodiment will be described.
• Examples 1 to 8 and Comparative Examples 1 and 2 samples of resin molded bodies were produced, and each sample was evaluated.
• the molded body of the raw resin was irradiated with an electron beam
• Comparative Examples 1 and 2 the molded body of the raw resin was not irradiated with an electron beam.
• Example 1 PEEK was used as the raw material resin, and specifically "Vestakeep (registered trademark) 4000G” manufactured by Daicel Evonik was used. Further, in Example 4, PEK was used as the raw material resin, and specifically "VICTREX (registered trademark) HT” manufactured by Victrex was used. Further, in Example 5, the raw resin contained 20% by weight of carbon fiber and 10% by weight of PTFE as additives.
• Examples 1 to 5 In all Examples 1 to 5, electron beam irradiation was performed at room temperature. Further, in Examples 1 to 3, electron beams were irradiated with mutually different irradiation doses. Specifically, in Example 1, the irradiation dose was 50 kGy, in Example 2, the irradiation dose was 100 kGy, and in Example 3, the irradiation dose was 200 kGy. Further, in Example 4, the irradiation dose was 100 kGy, and in Example 5, the irradiation dose was 200 kGy.
• the samples according to Examples 1 to 5 all had the same configuration other than the above-described configuration. Further, as the sample according to Comparative Example 1, the molded body of the raw resin of the samples according to Examples 1 to 3 before being irradiated with the electron beam was used. The absorbance of the surface layer and main body of the samples according to Examples 1 to 5 and Comparative Example 1 was measured using an infrared spectrophotometer. The absorbance was measured by the ATR method using a Ge lens using a Fourier transform infrared spectrophotometer "FT/IR-4600" manufactured by JASCO.
• FT/IR-4600 Fourier transform infrared spectrophotometer
• the ratio A'/B' was calculated from each infrared absorption spectrum obtained by absorbance measurement.
• Table 1 shows the ratio A'/B' of the surface layer portion and the main body portion for Examples 1 to 5 and Comparative Example 1.
• Comparative Example 1 the ratio A'/B' was equal in the surface layer part and the main body part, whereas in Examples 1 to 5, the ratio A'/B' was higher in the surface layer part than in the main body part.
• Table 1 shows the results for each round trip number (10 round trips, 20 round trips, 30 round trips, 40 round trips, and 50 round trips) for Examples 1 to 5 and Comparative Example 1. As shown in Table 1, the samples according to Examples 1 to 5 all showed good results up to 50 cycles, and had higher durability than the sample according to Comparative Example 1, which failed after 40 cycles or more. Abrasion properties were obtained.
• Table 1 shows the rate of change (%) in breaking strength for Examples 1 to 3 relative to Comparative Example 1. As shown in Table 1, the samples of Examples 1 to 3 all had higher breaking strength than the sample of Comparative Example 1, indicating that the high breaking strength was obtained due to the action of the surface layer.
• each sample was formed into a strip of 10 mm x 80 mm x 0.1 mm (with a 1 mm notch).
• the tensile speed was 10 mm/min and other conditions were the same.
• Table 1 shows the rate of change (%) in tearing stroke for Examples 1 to 3 relative to Comparative Example 1. As shown in Table 1, all of the samples of Examples 1 to 3 had a larger tear stroke than the sample according to the comparative example, and it can be seen that the large tear stroke was obtained due to the action of the surface layer.
• Table 1 shows the rate of change (%) in the coefficient of dynamic friction for Examples 1 to 3 relative to Comparative Example 1.
• the samples of Examples 1 to 3 all have lower coefficients of dynamic friction than the samples of the comparative example, and high sliding characteristics as sliding members are obtained due to the action of the surface layer. I understand that.
• Table 1 shows the results of gear fatigue tests for Examples 1 to 3 and Comparative Example 1. As shown in Table 1, tooth chipping did not occur in any of the samples according to Examples 1 to 3, whereas tooth chipping occurred in the sample according to Comparative Example 1. This shows that in Examples 1 to 3, high fatigue characteristics as a gear member can be obtained.
• Example 6 the sample temperature during electron beam irradiation was changed from Example 2. Specifically, in Example 6, the sample temperature was 200°C, in Example 7, the sample temperature was 250°C, and in Example 8, the sample temperature was 300°C. Furthermore, in all of Examples 6 to 8, the electron beam irradiation dose was 100 kGy, as in Example 2.
• Example 6 the electron beam irradiation conditions are different from Example 2 in which the sample temperature is room temperature in that the sample is heated.
• a tensile test was conducted on each sample according to Examples 6 to 8 to evaluate the fracture characteristics. The conditions for the tensile test were the same as in Examples 1 to 3 and Comparative Example 1 above.
• Table 2 shows the percentage change (%) in breaking strength for Examples 2 and 6 to 8 relative to Comparative Example 1. As shown in Table 2, it can be seen that the samples of Examples 6 to 8, in which the samples were irradiated with an electron beam while being heated, had higher breaking strength than the sample of Example 2.
• a sample according to Comparative Example 2 was produced by subjecting the sample according to Comparative Example 1 to heat treatment (annealing treatment) at 300°C.
• the sample according to Comparative Example 2 is similar to the sample according to Example 8 in that the raw resin molded body is heated to 300°C, but it is different from the sample according to Example 8 in that it is not irradiated with an electron beam. Different from the sample.
• Example 8 The same tensile test as in Example 8 was conducted on the sample according to Comparative Example 2.
• Table 3 shows the breaking strength of Example 8 as a change rate (%) with respect to Comparative Example 2. As shown in Table 3, it can be seen that the sample according to Example 8, in which the sample was irradiated with an electron beam while heating, had a higher breaking strength than the sample according to Comparative Example 2, in which the sample was simply heated. .
• the method for increasing the crystallinity of the surface layer portion of the aromatic polyetherketone molded product is not limited to electron beam irradiation.
• Other methods for increasing the crystallinity of the surface layer include, for example, laser irradiation, UV irradiation, excimer irradiation, plasma irradiation, corona irradiation, flame treatment, chemical treatment, and the like.

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
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• Treatments Of Macromolecular Shaped Articles (AREA)
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• Injection Moulding Of Plastics Or The Like (AREA)
• Investigating Or Analysing Materials By Optical Means (AREA)
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• 2022
  • 2022-04-27 JP JP2022073067A patent/JP7721480B2/ja active Active
• 2023
  • 2023-03-27 US US18/852,855 patent/US20250215151A1/en active Pending
  • 2023-03-27 CN CN202380035672.3A patent/CN119072521A/zh active Pending
  • 2023-03-27 EP EP23795982.0A patent/EP4516847A1/en not_active Withdrawn
  • 2023-03-27 WO PCT/JP2023/012216 patent/WO2023210235A1/ja not_active Ceased

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