WO2021002316A1 - Composition de résine et article moulé - Google Patents

Composition de résine et article moulé Download PDF

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Publication number
WO2021002316A1
WO2021002316A1 PCT/JP2020/025471 JP2020025471W WO2021002316A1 WO 2021002316 A1 WO2021002316 A1 WO 2021002316A1 JP 2020025471 W JP2020025471 W JP 2020025471W WO 2021002316 A1 WO2021002316 A1 WO 2021002316A1
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Prior art keywords
resin composition
core
shell
elastomer
resin
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PCT/JP2020/025471
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English (en)
Japanese (ja)
Inventor
裕太 山元
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三菱エンジニアリングプラスチックス株式会社
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Priority to JP2021530010A priority Critical patent/JPWO2021002316A1/ja
Publication of WO2021002316A1 publication Critical patent/WO2021002316A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

Definitions

  • the present invention relates to a resin composition and a molded product.
  • the present invention relates to a resin composition containing a polyacetal resin as a main component.
  • Polyacetal resins are used in a wide range of applications as plastics having excellent mechanical properties, electrical properties, and chemical properties such as chemical resistance. Further, in order to impart various functions to the polyacetal resin, it is being studied to add various additives. For example, a composition composed of a polyacetal resin and a thermoplastic polyurethane has been proposed and put into practical use. However, since the composition composed of the polyacetal resin and the thermoplastic polyurethane has poor compatibility, it tends to cause delamination, and has a problem that the adhesion of the weld portion formed by injection molding is poor. It is known (Patent Document 1).
  • An object of the present invention is to provide a resin composition and a molded product having excellent adhesion of a weld portion and excellent weather resistance under such a situation.
  • a resin composition containing a polyacetal resin and a core-shell type elastomer wherein the resin composition is molded into a 1.6 mm-thick test piece having a weld portion in the center, and at 10 mm / min according to ASTM D638.
  • the resin composition contains 60 to 95% by mass of the polyacetal resin and 40 to 5% by mass of the core-shell elastomer (however, the total of the polyacetal resin and the core-shell elastomer does not exceed 100% by mass). ), The resin composition according to ⁇ 1>. ⁇ 3> The resin composition contains 70 to 95% by mass of the polyacetal resin and 30 to 5% by mass of the core-shell elastomer (however, the total of the polyacetal resin and the core-shell elastomer does not exceed 100% by mass). ), The resin composition according to ⁇ 1>.
  • the resin composition according to one. ⁇ 5> The resin composition is molded into a flat plate test piece of 100 mm ⁇ 40 mm ⁇ 2 mm, and is measured with a sunshine weather meter at 83 ° C. (black panel temperature), no rain, and an optical filter: 60 in a test environment of # 255.
  • ⁇ E * (( ⁇ L *) 2 + ( ⁇ a *) 2 + ( ⁇ b *) 2 ) 1/2 ⁇ 6>
  • L / D which is the ratio of the screw length L (mm) of the extruder to the screw diameter D (mm), includes 20 ⁇ (L / D) ⁇ 100.
  • the resin composition of the present invention is a resin composition containing a polyacetal resin and a core-shell type elastomer, and the resin composition is molded into a 1.6 mm thick test piece having a weld portion in the center, and ASTM D638.
  • the weld elongation when pulled at 10 mm / min is 20% or more
  • the core-shell type elastomer contains a butadiene-containing rubber
  • the shell portion contains an acrylic resin.
  • polyacetal resins are expected to have various uses, and one of them is expected to have weather resistance. Then, in the present invention, a weather-resistant resin composition was obtained by using a specific core-shell type elastomer.
  • a core-shell type elastomer is used instead of the thermoplastic polyurethane, and further, the core-shell type elastomer having small particles is adjusted so as to be dispersed and present in the vicinity of the weld portion, thereby increasing the weld elongation. This has succeeded in improving the adhesion of the weld portion.
  • the details of the present invention will be described below.
  • the resin composition of the present invention contains a polyacetal resin.
  • the polyacetal resin is not particularly limited, and even if it is a homopolymer containing only a divalent oxymethylene group as a constituent unit, it has a divalent oxymethylene group and a divalent oxyalkylene having 2 to 6 carbon atoms. It may be a copolymer containing a group as a constituent unit.
  • Examples of the oxyalkylene group having 2 to 6 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • the ratio of the oxyalkylene group having 2 to 6 carbon atoms to the total number of moles of the oxymethylene group and the oxyalkylene group having 2 to 6 carbon atoms is not particularly limited, and is 0.5 to 10 mol. It may be%.
  • trioxane is usually used as a main raw material.
  • cyclic formal or cyclic ether can be used.
  • Specific examples of cyclic formal include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepan, 1,3-dioxocan, 1,3,5-trioxepan, 1,3,6-trioxocan and the like.
  • Specific examples of the cyclic ether include ethylene oxide, propylene oxide and butylene oxide.
  • 1,3-dioxolane may be used as a main raw material
  • 1,3-dioxane may be used as a main raw material
  • 1,3-dioxepan may be used as the main raw material.
  • the amount of hemiformal terminal groups, the amount of formyl terminal groups, and the amount of terminal groups unstable to heat, acid, and base are small.
  • the hemiformal terminal group is represented by -OCH 2 OH
  • the formyl terminal group is represented by -CHO.
  • polyacetal resin in addition to the above, the polyacetal resins described in paragraphs 0018 to 0043 of JP2015-07724A can be used, and these contents are incorporated in the present specification.
  • the resin composition of the present invention preferably contains a polyacetal resin in an amount of 60% by mass or more, more preferably 65% by mass or more, further preferably 70% by mass or more, and further preferably 75% by mass or more. It is even more preferable to contain 78% by mass or more.
  • the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. Within such a range, the effects of the present invention tend to be exhibited more effectively.
  • the resin composition of the present invention may contain only one type of polyacetal resin, or may contain two or more types of polyacetal resin. When two or more types are included, the total amount is preferably in the above range.
  • the resin composition of the present invention contains a butadiene-containing rubber and a core-shell type elastomer containing an acrylic resin in the shell portion.
  • a resin composition having excellent weather resistance can be obtained by using a predetermined core-shell type elastomer.
  • the core-shell type elastomer is a polymer having a multi-layer structure having a core portion and a shell layer covering a part or all of the core portion, and Kaneka Corporation's Kaneace series and Mitsubishi Chemical Corporation's Metabrene series are known.
  • the Kaneka M910 series manufactured by Kaneka Corporation can be preferably used.
  • the core-shell type elastomer by using the core-shell type elastomer, it is possible to prevent the particles from being crushed even in the vicinity of the weld portion. Further, by selecting the type of core-shell elastomer so that the average secondary particle diameter of the core-shell elastomer existing in the vicinity of the weld portion is within a predetermined range, small particles of the core-shell elastomer are dispersed in the vicinity of the weld portion. be able to. As will be described in more detail later, the secondary average particle size of the core-shell elastomer can be adjusted to be within a predetermined range by adjusting various conditions during melt-kneading.
  • the type of core-shell elastomer used in the present invention is not particularly limited, but a core-shell elastomer containing butadiene-containing rubber and an acrylic resin in the shell portion is preferable. When such a core-shell type elastomer is used, the effect of the present invention is exhibited more effectively.
  • the core-shell elastomer used in the present invention is the ratio of the longitudinal elastic modulus of the shell portion of the core-shell elastomer to the longitudinal elastic modulus of the polyacetal resin (shell) measured using an SPM (scanning probe microscope, cantilever spring constant: 9 N / m).
  • the longitudinal elastic modulus of the portion / the longitudinal elastic modulus of the polyacetal resin) is preferably 0.08 or more, more preferably 0.10 or more, further preferably 0.15 or more, and 0.2 or more. Is more preferable.
  • the upper limit value of the longitudinal elastic modulus of the shell portion / the longitudinal elastic modulus of the polyacetal resin is not particularly determined, but is practically 1.0 or less.
  • the longitudinal elastic modulus is measured according to the description of Examples described later.
  • the resin composition of the present invention preferably contains a core-shell type elastomer in an amount of 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, and 22% by mass or less. Is even more preferable. Within such a range, the effects of the present invention tend to be exhibited more effectively.
  • the resin composition of the present invention may contain only one type of core-shell type elastomer, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
  • the resin composition of the present invention contains 60 to 95% by mass (preferably 70 to 95% by mass) of the polyacetal resin and 40 to 5% by mass (preferably 30 to 5% by mass) of the core-shell elastomer (however, polyacetal).
  • the total of the resin and the core-shell type elastomer does not exceed 100% by mass).
  • the total amount of the polyacetal resin and the core-shell type elastomer preferably occupies 95% by mass or more, and more preferably 98% by mass or more of the resin composition.
  • the resin composition of the present invention may contain any conventionally known additives and fillers as long as the object of the present invention is not impaired.
  • the additives and fillers used in the present invention include thermoplastic resins other than polyacetal resins, ultraviolet absorbers, antioxidants, stabilizers, formaldehyde traps, antistatic agents, carbon fibers, glass fibers, and glass flakes.
  • examples include potassium titanate whiskers.
  • the resin composition of the present invention also does not contain thermoplastic polyurethane, or the content of the thermoplastic polyurethane is 3% by mass or less (preferably 1% by mass or less, more preferably 0.% by mass) of the content of the core-shell type elastomer. 1% by mass or less) is preferable. With such a configuration, the weld adhesion can be further improved.
  • the resin composition of the present invention is molded into a multipurpose test piece having a thickness of 4 mm, and the flexural modulus measured according to ISO178 is preferably 1700 MPa or less, more preferably 1650 MPa or less, and more preferably 1600 MPa or less. More preferred.
  • the lower limit value is not particularly specified, but is practically, for example, 1000 MPa or more, further 1100 MPa or more, 1300 MPa or more, 1400 MPa or more, and 1500 MPa or more.
  • the present invention has high value in that it can be made excellent in weather resistance while improving the softness.
  • the resin composition of the present invention has a weld elongation of 20% or more when molded into a 1.6 mm thick test piece having a weld portion in the center and pulled at 10 mm / min according to ASTM D638, which is 25%.
  • the above is preferable, 30% or more is more preferable, and 35% or more is further preferable.
  • the upper limit of the weld elongation is not particularly defined, but for example, 99% or less, further 90% or less, and 80% or less are practical.
  • the resin composition of the present invention has an average secondary particle diameter of 50 nm or more of the core-shell elastomer present in the weld portion when molded into a 3.2 mm thick test piece having a weld portion in the center.
  • the average secondary particle diameter is preferably 500 nm or less, more preferably 300 nm or less, further preferably 200 nm or less, further preferably 150 nm or less, and further preferably 120 nm or less. Even more preferably, it may be 110 nm or less, and even 100 nm or less.
  • the resin composition is molded into a flat plate test piece of 100 mm ⁇ 40 mm ⁇ 2 mm, and is measured with a sunshine weather meter at 83 ° C. (black panel temperature), no rain, and an optical filter: # 255 for 60 hours.
  • the color difference ( ⁇ E *) of the test pieces before and after the test is preferably 12 or less, more preferably 11 or less, further preferably 10 or less, and even more preferably 9 or less.
  • the lower limit is practically 1 or more.
  • ⁇ E * (( ⁇ L *) 2 + ( ⁇ a *) 2 + ( ⁇ b *) 2 ) 1/2
  • the polyacetal resin composition of the present invention contains the above-mentioned essential components and, if necessary, any of the above-mentioned optional components.
  • the production method thereof is arbitrary, and any conventionally known method for producing a resin composition may be used to mix and knead these raw materials.
  • Examples of the kneading machine include a kneader, a Banbury mixer, and an extruder.
  • the various conditions and devices for mixing and kneading are also not particularly limited, and may be appropriately selected and determined from any conventionally known conditions.
  • the kneading is preferably performed at a temperature equal to or higher than the melting temperature of the polyacetal resin, specifically, a temperature higher than the melting temperature of the polyacetal resin.
  • the following methods can be preferably used in order to suppress the secondary aggregation of the core-shell type elastomer and adjust the average secondary particle size to an appropriate value.
  • the polyacetal resin and the core-shell type elastomer are mixed with a tumbler, extruded by an extruder, formed into a strand, and then cut. There is a method of making pellets.
  • the extruder it is preferable to use a twin-screw extruder because secondary agglutination is likely to occur in a single-screw extruder.
  • L / D which is the ratio of the screw length L (mm) to the diameter D (mm) of the screw, satisfies the relationship of 20 ⁇ (L / D) ⁇ 100, and 25 ⁇ (L / L /). D) It is more preferable to satisfy ⁇ 70.
  • the shape of the die nozzle is not particularly limited, but in terms of pellet shape, a circular nozzle having a diameter of 1 to 10 mm is preferable, and a circular nozzle having a diameter of 2 to 7 mm is more preferable.
  • the term "circle” as used herein is not limited to a circle in a geometrical sense, but includes a circle that is interpreted as a substantially circle in the technical field of the present embodiment.
  • the melting temperature of the resin composition at the time of melt-kneading is appropriately determined in relation to the melting temperature of the resin, but is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and 190 ° C. or higher. It is more preferable to have. Further, the melting temperature is preferably 250 ° C. or lower, more preferably 230 ° C. or lower. By setting the melting temperature to 170 ° C. or higher, melting is sufficiently performed, and the production amount tends to be remarkably improved. Further, by setting the temperature to 250 ° C. or lower, discoloration of the resin composition due to thermal deterioration can be more effectively suppressed.
  • the screw rotation speed during melt-kneading is preferably 50 to 500 rpm, more preferably 70 to 350 rpm.
  • the screw rotation speed is preferably 50 to 500 rpm, more preferably 70 to 350 rpm.
  • the screw rotation speed is preferably 50 to 500 rpm or more, the core-shell type elastomer can be easily finely dispersed, and the occurrence of secondary aggregation can be suppressed more effectively.
  • the discharge amount is preferably 5 to 1,000 kg / hr, and more preferably 7 to 800 kg / hr.
  • the core-shell type elastomer can be easily finely dispersed, and the occurrence of secondary aggregation can be effectively suppressed. Further, by setting the weight to 1,000 kg / hr or less, heat generation during melt-kneading can be effectively suppressed, and discoloration of the resin composition due to thermal deterioration can be more effectively suppressed.
  • the molded article of the present invention is formed from the polyacetal resin composition of the present invention. Further, the pellet obtained by pelletizing the polyacetal resin composition of the present invention is usually injection-molded to obtain a molded product.
  • the pellet in the present invention is preferably cylindrical, preferably has a diameter of 1 to 10 mm, and more preferably 2 to 7 mm.
  • the term "cylindrical" as used herein means that, in addition to the cylindrical one in the geometrical sense, the one interpreted as a cylindrical one in the technical field of the present invention is included. For example, a shape obtained by cutting a strand discharged from a nozzle having a circular discharge port is included in a columnar shape.
  • a preferable example of the molded product of the present invention is an injection molded product.
  • the injection-molded product is a molded product molded by injection molding, and usually, a fragile portion (weld portion) is formed in a portion where the molten resin joins in the mold.
  • the thickness of the molded product of the present invention preferably has, for example, a portion of 0.005 to 20 mm, and an appropriate thickness can be selected according to the application.
  • the shape of the molded product is not particularly limited and may be appropriately selected depending on the intended use and purpose of the molded product. For example, plate-shaped, plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, etc.
  • the molded product of the present invention may be a part or a finished product.
  • the polyacetal resin composition of the present invention and a molded product formed from the polyacetal resin composition are widely used in applications requiring weather resistance. Specifically, it is used for vehicle parts, building material parts, electrical / electronic parts, office equipment parts, daily miscellaneous goods parts, and the like. In particular, it is used for parts that are irradiated with ultraviolet rays.
  • Elastomer manufactured by Mitsubishi Chemical
  • Elastomer 4 Core-shell type elastomer containing silicone rubber for the core and acrylonitrile styrene resin for the shell, Metabrene, manufactured by Mitsubishi Chemical Corporation, SRK-200
  • Elastomer 5 Thermoplastic polyurethane, manufactured by BASF, product number: Elastolan S80ASH10
  • Examples 1 to 8, Comparative Examples 1 to 5, Reference Example 1 Each component shown in Tables 1 to 3 was uniformly mixed using a super mixer manufactured by Kawada Seisakusho Co., Ltd. at the ratio (parts by mass) shown in Tables 1 to 3. The obtained mixture was subjected to cylinder temperature (“PCM-30” manufactured by Ikegai Corp.) with a vented twin-screw extruder (“PCM-30” manufactured by Ikegai Corp.) having a screw diameter (D) of 30 mm, a screw length (L) of 760 mm, and a die nozzle diameter of 3.5 mm.
  • PCM-30 cylinder temperature
  • PCM-30 vented twin-screw extruder
  • Pellets of a polyacetal resin composition were produced by melt-shear mixing at a melting temperature of 200 ° C., a screw rotation speed of 120 rpm, and a discharge rate of 10 kg / hour.
  • UR20H manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used.
  • ⁇ Flexural modulus> The pellets obtained above were heat-treated for 4 hours in a hot air circulation dryer at a temperature of 80 ° C. Next, the dried pellets were injection-molded in accordance with the ISO9998-2 standard by setting the cylinder temperature to 195 ° C. and the mold temperature to 90 ° C. using an injection molding machine. In this way, a multipurpose test piece (ISO test piece) having a thickness of 4 mm was obtained. Next, the 4 mm-thick multipurpose test piece (ISO test piece) is subjected to a bending test at a bending test speed of 2 mm / min according to the method described in ISO178 using a fully automatic bending tester which is a bending tester. , The flexural modulus was measured. As an injection molding machine, EC-100S manufactured by Toshiba Machine Co., Ltd. was used. A fully automatic bending tester manufactured by Shimadzu Corporation was used. The results are shown in Tables 1 to 3 below. The unit is shown in MPa.
  • ⁇ Weld growth> The pellets obtained above were heat-treated for 4 hours in a hot air circulation dryer at a temperature of 80 ° C. Next, the dried pellets were set to a cylinder temperature of 195 ° C. and a mold temperature of 90 ° C. using an injection molding machine, and an ASTM tensile test piece (thickness 1.6 mm) having a weld portion in the center. ) was prepared, and a tensile test was performed according to ASTM D638 to measure the weld elongation. As an injection molding machine, EC-100S manufactured by Toshiba Machine Co., Ltd. was used. The results are shown in Tables 1 to 3 below. The unit is shown in%.
  • ⁇ Weather resistance> The pellets obtained above were heat-treated for 4 hours in a hot air circulation dryer at a temperature of 80 ° C. Next, using an injection molding machine, the cylinder temperature was set to 215 ° C. and the mold temperature was set to 80 ° C. to prepare a flat plate test piece of 100 mm ⁇ 40 mm ⁇ 2 mm. Using the obtained flat plate test piece, test before and after 60 hours in a test environment of 83 ° C (black panel temperature), no rain, optical filter: # 255 with a sunshine weather meter. The color difference ( ⁇ E *) of one piece was measured by the following method.
  • ⁇ E * (( ⁇ L *) 2 + ( ⁇ a *) 2 + ( ⁇ b *) 2 ) 1/2 It can be said that the smaller ⁇ E * is, the smaller the discoloration property is and the better the weather resistance is.
  • PS-40 manufactured by Nissei Resin Industry Co., Ltd.
  • sunshine weather meter a sunshine weather meter S80 manufactured by Suga Test Instruments Co., Ltd. was used.
  • SE2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. was used. The results are shown in Tables 1 to 3 below.
  • ⁇ Average secondary particle size of elastomer> The pellets obtained above were heat-treated for 4 hours in a hot air circulation dryer at a temperature of 80 ° C. Next, the dried pellets were set to a cylinder temperature of 195 ° C. and a mold temperature of 90 ° C. using an injection molding machine, and an ASTM tensile test piece (thickness 3.2 mm) having a weld portion in the center. ) was prepared. From this ASTM tensile test piece, a test piece for scanning electron microscope (SEM) observation was cut out with a diamond knife so as to be parallel to the flow direction at the time of molding and include a weld portion.
  • SEM scanning electron microscope
  • an SEM image was acquired using a scanning electron microscope (SEM). From the obtained SEM image, the average value of the maximum lengths of the island-shaped portions derived from the elastomer was taken as the average secondary particle diameter of the elastomer.
  • SEM scanning electron microscope
  • As an injection molding machine EC-100S manufactured by Toshiba Machine Co., Ltd. was used.
  • the vapor deposition of osmium tetroxide was carried out using a "osmium coater" manufactured by Meiwaforsis Co., Ltd. under the conditions of 8 mA and 60 seconds.
  • SEM scanning electron microscope
  • ⁇ Measurement of longitudinal elastic modulus> A test piece for observation with a scanning probe microscope (SPM) was cut out in the same procedure as the measurement of the average secondary particle size, and a longitudinal elastic modulus image was obtained by a force curve mapping method of the scanning probe microscope (SPM). From the obtained longitudinal elastic modulus image, the longitudinal elastic modulus at a total of 10 points was measured for the polyacetal resin portion. Next, from the longitudinal elastic modulus image, the longitudinal elastic modulus was measured at a total of 10 locations for the shell portion of the core-shell type elastomer. For the non-core shell type elastomer, the longitudinal elastic modulus near the interface with the polyacetal resin was measured.
  • the longitudinal elastic modulus ratio (the longitudinal elastic modulus of the shell portion / the longitudinal elastic modulus of the polyacetal resin) was calculated from the longitudinal elastic modulus of the shell portion of the core-shell type elastomer and the longitudinal elastic modulus of the polyacetal resin.
  • the scanning probe microscope uses "SPM-9700HT” manufactured by Shimadzu Corporation, scanner: 30 ⁇ m ⁇ 30 ⁇ m, cantilever: “AC200 (spring constant 9 N / m)” manufactured by Olympus, sweep speed: 1 Hz, sweep range: 1500 nm, I gain: An elastic modulus image was obtained under 100 conditions.

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Abstract

L'invention concerne une composition de résine excellente en termes d'adhésion d'une partie soudée et de résistance aux intempéries, ainsi qu'un article moulé. La composition de résine selon l'invention contient une résine de polyacétal et un élastomère de type coeur-écorce et est telle que lorsqu'elle est utilisée pour former un spécimen dont l'épaisseur est de 1,6 mm et qui possède en son centre une partie soudée, l'allongement de la soudure lors d'une traction de 10mm/min. selon un test ASTM D638 est supérieure ou égale à 20%. L'élastomère de type coeur-écorce contient un caoutchouc contenant un butadiène et contient une résine acrylique dans la partie écorce .
PCT/JP2020/025471 2019-07-03 2020-06-29 Composition de résine et article moulé WO2021002316A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023238790A1 (fr) * 2022-06-09 2023-12-14 グローバルポリアセタール株式会社 Composition de résine et article moulé
WO2023238788A1 (fr) * 2022-06-09 2023-12-14 グローバルポリアセタール株式会社 Composition de résine et article moulé

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JP7550321B2 (ja) 2022-06-09 2024-09-12 グローバルポリアセタール株式会社 樹脂組成物、および、成形品

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