WO2021038723A1 - 複合材料 - Google Patents

複合材料 Download PDF

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WO2021038723A1
WO2021038723A1 PCT/JP2019/033547 JP2019033547W WO2021038723A1 WO 2021038723 A1 WO2021038723 A1 WO 2021038723A1 JP 2019033547 W JP2019033547 W JP 2019033547W WO 2021038723 A1 WO2021038723 A1 WO 2021038723A1
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composite material
cellulose nanofibers
cellulose
amide
cnf
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PCT/JP2019/033547
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English (en)
French (fr)
Japanese (ja)
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剛士 大本
徹也 山田
宮本　和幸
蓮貞 林
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リョービ株式会社
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Priority to PCT/JP2019/033547 priority Critical patent/WO2021038723A1/ja
Priority to JP2021541843A priority patent/JP7237165B2/ja
Publication of WO2021038723A1 publication Critical patent/WO2021038723A1/ja

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material

Definitions

  • the present invention relates to a composite material containing a polyacetal resin and cellulose nanofibers.
  • polyacetal resin has excellent mechanical strength and is inexpensive, so it has been used as a material for various products.
  • polyacetal resin is used as a material for gears, zippers, etc. because it has excellent slidability.
  • FRP fiber reinforced plastics
  • examples of the fiber material contained in FRP include glass fiber, carbon fiber and cellulose nanofiber.
  • cellulose nanofibers are excellent in light weight, and are preferable fiber materials from the viewpoints of ease of recycling and low environmental load.
  • the dispersibility of the cellulose nanofibers in the resin is important.
  • cellulose has many hydroxyl groups, cellulose nanofibers have high hydrophilicity, so that cellulose nanofibers are usually difficult to mix with a highly hydrophobic resin.
  • a composite material in which a resin contains modified cellulose nanofibers in which the hydroxyl group of cellulose is modified to an organic group has been proposed.
  • Patent Document 1 describes a composite material containing a polyacetal resin and modified cellulose nanofibers in which a part of the hydroxyl group of cellulose is acetylated.
  • the acetylated modified cellulose nanofibers have improved hydrophobicity because some of the hydroxyl groups of the cellulose are acetylated.
  • the acetylated modified cellulose nanofibers have improved affinity with the polyacetal resin and may exhibit better dispersibility in the polyacetal resin as compared with the unmodified cellulose nanofibers.
  • the composite material described in Patent Document 1 has a problem that the effect of adding the cellulose nanofibers is not sufficiently exhibited.
  • the composite material has a problem that the functions required when it is molded into various products are not sufficient.
  • the composite material has a drawback that it is not sufficiently dimensionally stable and shrinks during molding, which causes difficulty in molding.
  • cellulose nanofibers have a reduced crystallinity due to chemical modification such as acetylation. Further, since the amorphous portion is thermally unstable as compared with the crystalline portion, the cellulose nanofibers having a reduced degree of crystallinity are easily thermally decomposed.
  • the present inventors have found that the degree of crystallinity of the cotton-derived cellulose nanofibers is relatively high among the cellulose nanofibers, and further, the cotton-derived cellulose nanofibers are used before and after the chemical modification. We have found that the degree of crystallinity does not easily decrease, and have completed the present invention.
  • the composite material according to the present invention is Contains polyacetal resin and cellulose nanofibers, In the cellulose nanofiber, a part of the hydroxyl group of cellulose is acylated.
  • the cellulose nanofibers are a composite material derived from cotton.
  • the acylation is acetylation.
  • the composite material according to the present invention further contains an amide-based dispersant.
  • the amide-based dispersant is polyoxyethylene alkylamide.
  • FIG. 1 is an SEM image of the CNF of Production Example 1 in the example.
  • FIG. 2 is an SEM image of the CNF of Production Example 2 in the example.
  • FIG. 3 is an SEM image of the CNF of Production Example 3 in the example.
  • FIG. 4 is an IR spectrum of CNFs of Production Examples 1 to 3 in Examples.
  • FIG. 5 is an XRD chart of CNFs of Production Examples 1 to 5 in Examples.
  • FIG. 6 is a TG chart of CNFs of Production Examples 1 to 5 in Examples.
  • FIG. 7 shows an example of a DMA chart, and is a diagram for showing a method of obtaining a softening temperature from the DMA chart.
  • the composite material according to the present embodiment contains a polyacetal resin, cellulose nanofibers, and an amide-based dispersant, and the cellulose nanofibers have a part of the hydroxyl group of cellulose acylated.
  • the cellulose nanofibers are made from cellulose fibers obtained from cotton.
  • the composite material is used as a molding material for various parts, and can be molded into automobile parts, precision parts, etc. by injection molding, for example.
  • the composite material is molded when the temperature at the time of molding is usually set to 180 to 220 ° C, preferably 180 to 200 ° C. Therefore, it is preferable that the composite material has excellent moldability under such molding conditions.
  • the coefficient of linear expansion of the composite material at 30 to 120 ° C. is preferably 90 ppm / ° C. or lower, more preferably 70 ppm / ° C. or lower, still more preferably 50 ppm / ° C. or lower.
  • the coefficient of linear expansion of the composite material is usually 10 ppm / ° C. or higher.
  • the coefficient of linear expansion is measured by the measuring method described in the examples.
  • the storage elastic modulus (E') of the composite material at 100 ° C. is preferably 1000 MPa or more, more preferably 1100 MPa or more, still more preferably 1200 MPa or more, and even more preferably 1500 MPa or more. Thereby, the composite material may have excellent heat resistance and mechanical properties.
  • the storage elastic modulus (E') of the composite material at 100 ° C. is usually 2500 MPa or less. The storage elastic modulus is measured by the measuring method described in the examples.
  • the polyacetal resin is a polymer having an acetal structure-(-O-CRH-) n- (R represents a hydrogen atom or an organic group) in a repeating structure.
  • R represents a hydrogen atom or an organic group
  • the oxymethylene group (-OCH 2- ) in which R is a hydrogen atom is the main constituent unit.
  • the polyacetal resin may be a polyacetal homopolymer or a polyacetal copolymer. Further, the content of the polyacetal homopolymer or the polyacetal copolymer is usually 90% by mass or more, preferably 95% by mass or more, and the polyacetal resin may contain other polymer components in part. Good.
  • the raw material is seed hair fiber collected from the seeds of seed hair plants.
  • the seed hair plant include cotton, acundo, and kapok, and among these, cotton is preferable.
  • the cotton seeds are covered with fibers called cotton balls, which are formed of a linter covering the seeds and a lint covering the outside of the linters. Since lint has a longer fiber length than linter, lint is generally used as a raw material for cotton yarn and cotton fabric, and linter is used as linter pulp and rayon.
  • the cellulose nanofibers may be produced from lint or may be produced from linter. In the present embodiment, the cellulose nanofibers are made from linter pulp produced from linter.
  • the cotton-derived cellulose nanofibers have a lower lignin content than other plants, such as coniferous cellulose nanofibers.
  • the thermal stability of the cellulose nanofibers may be lowered when the content of the lignin is large. Therefore, the composite material containing the cellulose nanofibers derived from cotton can have excellent thermal stability.
  • the content of the lignin in the cellulose nanofibers is preferably 500 ppm or less, more preferably 100 ppm or less. The content of the lignin is measured by the Klason method.
  • the cellulose nanofibers are defibrated at the nano level.
  • the nano-level means that the average fiber diameter of the cellulose nanofibers is usually 15 to 800 nm, preferably 20 to 500 nm.
  • the cellulose nanofibers may have the above average fiber diameter in the composite material.
  • cellulose fibers having an average fiber diameter of about several tens of ⁇ m may be defibrated at the nano level by kneading with the polyacetal resin. Further, the average fiber diameter is measured by the measuring method described in the examples.
  • the average fiber length of the cellulose nanofibers is usually 0.5 to 100 ⁇ m, preferably 1 to 80 ⁇ m.
  • the average fiber length is measured by the measuring method described in the examples.
  • a part of the hydroxyl group of cellulose is acylated.
  • part of the hydroxyl groups of the cellulose of the cellulose nanofiber is substituted with acyl group title by Formula R 1 COO.
  • R 1 is preferably an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. preferable.
  • R 1 is preferably an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. preferable.
  • the acyl group an acetyl group, a butyryl group or a lauryl group is preferable.
  • the cellulose nanofiber having an acetyl group is preferable from the viewpoint of exhibiting excellent thermal stability and reducing the production cost.
  • the ratio of the acylated hydroxyl group to the hydroxyl group of cellulose in the cellulose nanofiber is shown as the average degree of substitution.
  • the average degree of substitution is usually 0.1 to 0.5, preferably 0.2 to 0.45 in the case of wood pulp.
  • cotton-derived linter pulp it is 0.1 to 1.5, preferably 0.2 to 1.2, and more preferably 0.3 to 1.0.
  • the preferable value of the average degree of substitution differs depending on the type of the acyl group. For example, in the case of an acetyl group, it is preferably 0.1 to 1.5, more preferably 0.2 to 1.2, and in the case of a butyryl group, it is preferably 0.05 to 1.3, and more.
  • the lauryl group has 12 carbon atoms in R 1 , and the alkyl side chain is relatively long, and the alkyl side chain can cover the surface of cellulose. Therefore, the cellulose nanofiber having a lauryl group can have an excellent affinity with the polyacetal resin even when the average degree of substitution is relatively low. Further, when the average degree of substitution is low, a decrease in the crystallinity of the cellulose nanofibers can be suppressed, which is preferable.
  • the average degree of substitution is measured by the measuring method described in the examples.
  • the cellulose nanofibers have cellulose type I crystals.
  • the content of the cellulose type I crystal in the cellulose nanofiber is shown as the degree of crystallinity.
  • the cotton-derived cellulose nanofibers have a higher degree of crystallinity than other plant-derived cellulose nanofibers. Further, usually, when the cellulose nanofibers are acylated, the acylated portion becomes amorphous, so that the crystallinity is lowered. On the other hand, the cotton-derived cellulose nanofibers are less likely to decrease in crystallinity due to acylation.
  • the reason for this is that the cellulose nanofibers derived from cotton are difficult for the acylating agent to permeate into the inside, and the surface portion that greatly affects the affinity with the polyacetal resin is efficiently acylated. Further, the fact that the acylating agent does not easily penetrate into the cellulose nanofibers means that the cellulose inside is less likely to be acylated, that is, the degree of crystallinity inside is less likely to decrease. Cellulose nanofibers having a high crystallinity have high thermal stability and are not easily thermally decomposed during kneading with the polyacetal resin. Therefore, the composite material containing such cellulose nanofibers can exhibit excellent functions.
  • the crystallinity is preferably 45% or more, more preferably 50% or more, further preferably 70% or more, even more preferably 75% or more, and most preferably 80% or more. ..
  • the temperature at the time of kneading is also set to a relatively high temperature (usually 180 to 220 ° C, preferably 180 to 200 ° C). Further, usually, the temperature of the kneaded product may be several tens of degrees higher than the set temperature due to heat generation during kneading. Therefore, it is preferable that the cellulose nanofibers have heat resistance under such temperature conditions. From such a viewpoint, the thermal decomposition temperature (5% weight loss temperature) of the cellulose nanofibers is preferably 290 ° C. or higher, more preferably 300 ° C. or higher, and more preferably 310 ° C. or higher.
  • the cotton-derived cellulose nanofibers have higher heat resistance than other plant-derived cellulose nanofibers, that is, they can have the above-mentioned thermal decomposition temperature. As a result, the cellulose nanofibers are less likely to be thermally decomposed when kneaded with the polyacetal resin, and the composite material can exhibit excellent functions.
  • the thermal decomposition temperature of the cellulose nanofibers is usually 360 ° C. or lower. Further, the thermal decomposition temperature is measured by the measuring method described in the examples.
  • the content of the cellulose nanofibers is usually 4 to 50% by mass, preferably 10 to 30% by mass, and more preferably 10 to 20% by mass with respect to the total amount of the composite material.
  • the amide-based dispersant is a dispersant having an amide group in the molecule, and is designated by the chemical formula R 2 CONR 3 R 4 .
  • the amide-based dispersant is preferably a liquid under the temperature conditions during kneading, and preferably does not easily volatilize under the temperature conditions during kneading.
  • the melting point of the amide-based dispersant is usually 200 ° C. or higher, preferably 250 ° C. or higher.
  • the boiling point of the amide-based dispersant is usually 200 ° C. or higher, preferably 250 ° C. or higher.
  • amide-based dispersant examples include one or more selected from the group consisting of fatty acid amides, fatty acid alkanolamides, polyoxyethylene alkylamides and polyoxypropylene alkylamides.
  • the R 2 moiety of such amide-based dispersant is preferably a structure capable of exhibiting an affinity with the polyacetal resin. From this point of view, R 2 is preferably an alkyl group or an alkenyl group having 3 to 25 carbon atoms, more preferably 5 to 20 carbon atoms.
  • fatty acid amide examples include stearic acid monoamide, oleic acid monoamide, erucic acid monoamide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide.
  • fatty acid alkanolamide examples include coconut fatty acid monoethanolamide, coconut fatty acid diethanolamide, lauric acid isopropanolamide, beef fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.
  • polyoxyethylene alkyl amide examples include polyoxyethylene coconut oil fatty acid monoethanolamide and polyoxyethylene lauric acid monoethanolamide.
  • polyoxypropylene alkylamide examples include polyoxypropylene coconut oil fatty acid monoisopropanolamide.
  • the hydrogen atom can form a hydrogen bond with the carbonyl oxygen atom of the acyl group in the cellulose nanofiber. Therefore, such an amide-based dispersant can exhibit an affinity for the cellulose nanofibers.
  • R 3 in the chemical formula is a hydrogen atom and R 4 is ⁇ (C 2 H 4 O) n H (polyoxyethylene alkyl group).
  • examples of such an amide-based dispersant include NOF Corporation's Nymid (registered trademark).
  • the polyoxyethylene group portion exhibits a high affinity with the polyacetal resin, and the hydrogen atom forms a hydrogen bond with the carbonyl oxygen atom of the acyl group in the cellulose nanofiber.
  • the content of the amide-based dispersant is usually 1 to 10% by mass, preferably 2 to 5% by mass, based on the entire composite material.
  • the raw material for the cellulose nanofibers is the linter pulp.
  • the crystallinity of the linter pulp is preferably 50% or more, more preferably 70% or more, further preferably 75% or more, and even more preferably 80% or more.
  • As the linter pulp commercially available ones can be used.
  • acylating and defibrating the cellulose fiber As a method for acylating and defibrating the cellulose fiber, a conventionally known method can be adopted. As a preferable method, a defibrating device such as a super mascoroider is used, and the cellulose fiber is subjected to an acylating agent such as a carboxylic acid vinyl ester or a carboxylic acid anhydride and an acid catalyst or a base catalyst and an organic solvent such as DMSO. Examples thereof include a method of obtaining an acylated cellulose fiber by treating with a treatment liquid containing the mixture. According to this method, a decrease in the crystallinity of the cellulose fibers can be suppressed as compared with a mechanical defibration method using a refiner, a high-pressure homogenizer, or the like.
  • an acylating agent such as a carboxylic acid vinyl ester or a carboxylic acid anhydride and an acid catalyst or a base catalyst and an organic
  • acylating agent examples include carboxylic acid anhydrides such as acetic acid anhydride, butyric anhydride and lauric anhydride; carboxylic acids such as acetic acid, butyric acid and lauric acid; vinyl carboxylates such as vinyl acetate, vinyl butyrate and vinyl laurate: Examples thereof include carboxylic acid halides such as acetic acid halide, butyric acid halide, and lauric acid halide.
  • organic solvent in addition to DMSO, aprotic polar solvents such as formamide, dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
  • a defibrating agent that promotes defibration of cellulose fibers may be added to the treatment liquid.
  • the treatment liquid is removed from the acylated cellulose fibers by filtration, centrifugation, or the like, and the treated cellulose fibers are washed with 2-propanol and / or dimethylacetamide as a washing solvent. By concentrating, a part of the washing solvent is removed to obtain a paste-like cellulose nanofiber.
  • the content of the cellulose nanofibers contained in the paste-like cellulose nanofibers is usually 5 to 30% with respect to the total amount.
  • the paste-like cellulose nanofibers and the amide-based dispersant are mixed using a generally used stirrer to obtain the dispersant-treated cellulose nanofibers.
  • the dispersant-treated cellulose nanofibers and the polyacetal resin are dispersed in a kneading solvent and kneaded using a kneader to obtain a kneaded product.
  • the kneading temperature is 180 to 195 ° C.
  • the rotation speed and kneading time of the kneading machine at the time of kneading can be appropriately changed in consideration of the amount of the composite material to be acquired, the amount of cellulose nanofibers contained in the composite material, and the like.
  • an alcohol solvent such as ethanol or 2-propanol
  • an amide solvent such as dimethylacetamide or 2-methyl-2-pyrrolidone
  • two or more kinds of these solvents may be mixed and used.
  • the organic solvent the amide-based solvent is preferable, and among these, dimethylacetamide is preferable.
  • the kneaded product is dried using a vacuum dryer or the like to obtain the composite material.
  • the drying temperature is usually 80 to 125 ° C.
  • the composite material according to the present invention is Contains polyacetal resin and cellulose nanofibers, In the cellulose nanofiber, a part of the hydroxyl group of cellulose is acylated.
  • the cellulose nanofibers are derived from cotton.
  • the cellulose nanofibers are derived from cotton, they show a high degree of crystallinity as compared with other plant-derived cellulose nanofibers, and the degree of crystallinity is unlikely to decrease due to acylation. Therefore, according to such a configuration, the cellulose nanofibers are less likely to be thermally decomposed at the time of kneading with the polyacetal resin, so that the composite material can exhibit excellent functions. For example, the composite may have excellent dimensional stability, thereby having excellent moldability.
  • the acylation may be acetylation.
  • the composite material can have more excellent functions and can be manufactured at a relatively low cost.
  • the composite material may further contain an amide-based dispersant.
  • the amide-based dispersant may be a polyoxyethylene alkyl amide.
  • the composite material according to the present invention is not limited to the configuration of the above embodiment. Further, the composite material according to the present invention is not limited by the above-mentioned effects. The composite material according to the present invention can be variously modified without departing from the gist of the present invention.
  • the CNF of Production Example 1 in Table 1 was produced as follows. 10 g of vinyl acetate, 1.5 g of sodium carbonate and 90 g of DMSO were placed in a three-necked flask and mixed to prepare a treatment solution. 3 g of linter pulp was added to the obtained treatment liquid, and the mixture was reacted at 50 ° C. for 3 hours and then washed with water. Then, the acetylated CNF of Production Example 1 was obtained by defibrating with a super mascoroider.
  • FIGS. 1 to 3 show SEM images of CNFs of Production Examples 1 to 3.
  • (Measurement condition) ⁇ Pt coating condition: 10mA, 60 seconds ⁇ Acceleration voltage: 5kV ⁇ SEI: Secondary electron image ⁇ LEI: Downward detector image (secondary electron image + backscattered electron image)
  • the average degree of substitution of cellulose nanofibers was measured by the following titration method.
  • the acyl group was hydrolyzed by dispersing 0.5 g of CNF in 100 mL of a mixture of sodium hydroxide (molar number A) / ethanol / water and stirring at 23 ° C. for 4 hours.
  • the ratio of sodium hydroxide, ethanol and water is adjusted according to the type of acyl group. For example, in the case of acetylated CNF, a mixed solution of 5 g of sodium hydroxide / 50 g of ethanol / 50 g of water was used.
  • Table 1 shows the measurement results of CNF in Production Examples 1 to 5.
  • the linter that is, the cotton-derived CNF
  • the coniferous CNF showed relatively low crystallinity and pyrolysis temperature. From these results, it was considered that the cotton-derived CNF has a relatively high thermal stability and is therefore unlikely to be thermally decomposed during kneading with the polyacetal resin when the composite material is produced. Therefore, it is considered that such a composite material containing CNF can exhibit excellent functions.
  • the composite material was prepared as a sheet-like composite sheet according to the formulation shown in Table 2.
  • the blending amount of CNF in Table 2 represents the blending amount with respect to 100 parts by mass of the polyacetal resin.
  • ethanol (EtOH), 2-propanol (IPA), dimethylacetamide (DMAc) or N-methyl-2-pyrrolidone (NMP) was used as the kneading solvent (in Example 8).
  • EtOH ethanol
  • IPA 2-propanol
  • DMAc dimethylacetamide
  • NMP N-methyl-2-pyrrolidone
  • Example 8 DMAc / EtOH mixed solvent
  • CNF in which the composite material contains an amide-based dispersant
  • CNF is added to a solvent in which the amide-based dispersant is dissolved, and the mixture is used as a stirrer or mechanically stirred at 20 to 180 ° C. Dispersed and dispersant-treated CNFs were prepared.
  • a lab plast mill was used for kneading CNF (or dispersant-treated CNF) and POM, and the mixture was kneaded at 180 to 195 ° C. and a rotation speed of 45 to 100 rpm for 20 to 70 minutes.
  • the obtained kneaded product was dried at 120 ° C. for 5 hours to obtain an unmolded composite material.
  • the unmolded composite material was heated at 190 ° C. for 4 minutes using a hot press machine, pressurized at a pressure of 180 kg / cm 2 for 1 minute, and then allowed to cool at room temperature to prepare a composite sheet.
  • Various data were acquired from the acquired composite sheet by the following measurement methods, and the dimensional stability, dynamic viscoelasticity and tensile properties were evaluated.
  • the dynamic viscoelasticity (DMA) of the composite sheet was measured using the dynamic viscoelasticity measuring device.
  • the cotton-derived CNF-containing composite material showed a relatively high storage elastic modulus at 100 ° C., and was found to have excellent heat resistance.
  • the composite material containing the amide-based dispersant has a higher storage elastic modulus and has better heat resistance than the composite material not containing the amide-based dispersant, and therefore can be used even in a higher temperature range. ..

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PCT/JP2019/033547 2019-08-27 2019-08-27 複合材料 WO2021038723A1 (ja)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2022215756A1 (ja) * 2021-04-09 2022-10-13 旭化成株式会社 ポリアセタール樹脂組成物及びその製造方法

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JP2017014406A (ja) * 2015-07-01 2017-01-19 味の素株式会社 樹脂組成物
JP6091589B2 (ja) * 2015-03-19 2017-03-08 国立大学法人京都大学 化学修飾セルロースナノファイバー及び熱可塑性樹脂を含有する繊維強化樹脂組成物
JP2018197304A (ja) * 2017-05-24 2018-12-13 川研ファインケミカル株式会社 レベリング剤及びこれを含有する組成物
JP2019006875A (ja) * 2017-06-22 2019-01-17 旭化成株式会社 化学修飾されたセルロース微細繊維を含有する高耐熱性樹脂複合体
JP2019014865A (ja) * 2016-12-28 2019-01-31 旭化成株式会社 セルロース含有樹脂組成物

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Publication number Priority date Publication date Assignee Title
JP6091589B2 (ja) * 2015-03-19 2017-03-08 国立大学法人京都大学 化学修飾セルロースナノファイバー及び熱可塑性樹脂を含有する繊維強化樹脂組成物
JP2017014406A (ja) * 2015-07-01 2017-01-19 味の素株式会社 樹脂組成物
JP2019014865A (ja) * 2016-12-28 2019-01-31 旭化成株式会社 セルロース含有樹脂組成物
JP2018197304A (ja) * 2017-05-24 2018-12-13 川研ファインケミカル株式会社 レベリング剤及びこれを含有する組成物
JP2019006875A (ja) * 2017-06-22 2019-01-17 旭化成株式会社 化学修飾されたセルロース微細繊維を含有する高耐熱性樹脂複合体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022215756A1 (ja) * 2021-04-09 2022-10-13 旭化成株式会社 ポリアセタール樹脂組成物及びその製造方法

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