WO2023163417A1 - Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci - Google Patents

Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci Download PDF

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Publication number
WO2023163417A1
WO2023163417A1 PCT/KR2023/001729 KR2023001729W WO2023163417A1 WO 2023163417 A1 WO2023163417 A1 WO 2023163417A1 KR 2023001729 W KR2023001729 W KR 2023001729W WO 2023163417 A1 WO2023163417 A1 WO 2023163417A1
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WO
WIPO (PCT)
Prior art keywords
polyamide
thermoplastic resin
resin composition
weight
flame retardant
Prior art date
Application number
PCT/KR2023/001729
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English (en)
Korean (ko)
Inventor
강성우
배윤석
반균하
Original Assignee
롯데케미칼 주식회사
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Publication of WO2023163417A1 publication Critical patent/WO2023163417A1/fr

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/00—Use of organic ingredients
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article made therefrom.
  • Thermoplastic resin compositions used in automobile parts or electrical appliances have industry standards for flame retardancy, and excellent electrical insulation and flame retardancy are required.
  • the supply of electric vehicles is being supported by governments of each country, and accordingly, the demand for electric vehicle batteries is increasing.
  • flame retardancy in a thin film of a thermoplastic resin composition is considered important as safety becomes an issue in automotive battery applications.
  • mechanical properties such as tensile strength and flexural modulus must be excellent while satisfying the above properties.
  • Polyamide resins provide excellent heat resistance and formability, so they are useful as thermoplastic resins used in automobile parts or electrical appliances. However, polyamide resins lack flame resistance, so a flame retardant must be added to provide flame retardancy required for specific applications. Bromine-based compounds and antimony-based compounds may be used as the flame retardant, but bromine-based compounds may cause environmental problems when the composition is burned, so when bromine-based compounds and antimony-based compounds are included, their use may be limited. .
  • a non-brominated flame retardant such as a phosphorus flame retardant is used, but the addition of the flame retardant causes a decrease in heat resistance and impact resistance. In this case, a phenomenon in which the flame retardancy is lowered again occurs.
  • additives for improving electrical insulation improve electrical properties, but are accompanied by deterioration of physical properties.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, mechanical properties and the like.
  • Another object of the present invention is to provide a molded article manufactured from the thermoplastic resin composition.
  • thermoplastic resin composition may include (A) about 40 to about 70% by weight of a polyamide resin; (B) about 5 to about 25% by weight of a phosphorus-based flame retardant; (C) about 20 to about 50 weight percent glass fibers; And (D) based on about 100 parts by weight of the base material including about 1 to about 5% by weight of a melamine-based flame retardant, (E) about 0.5 to about 3 parts by weight of zinc borate; and (F) about 0.3 to about 2 parts by weight of magnesium oxide.
  • the polyamide resin (A) is polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6I, polyamide 6T, polyamide 4T, polyamide 410, polyamide 510, polyamide 1010, polyamide 1012, polyamide 10T, polyamide 1212, polyamide 12T, polyamide MXD6, or combinations thereof.
  • the (A) polyamide resin may be polyamide 66.
  • the (B) phosphorus flame retardant is aluminum diethyl phosphinate, triphenyl phosphate, ammonium polyphosphate, resorcinol-di (bis-2,6-dimethylphenyl) phosphate (resorcinol-di (bis-2,6-dimethylphenyl) phosphate), bisphenol A diphenyl phosphate, cyclophosphazene (cyclophosphazene), diethyl phosphite diethyl phosphinate ammonium salt, or a combination thereof.
  • the (B) phosphorus-based flame retardant may be aluminum diethyl phosphinate.
  • the (C) melamine-based flame retardant is melamine polyphosphate, melamine/ammonium polyphosphate, melamine phosphate, melamine pyrophosphate ( melamine pyrophosphate), or a combination thereof.
  • the (C) melamine-based flame retardant may be melamine polyphosphate.
  • the weight ratio of (B) the phosphorus-based flame retardant and (D) the melamine-based flame retardant may be about 2:1 to about 15:1.
  • thermoplastic resin composition is selected from antibacterial agents, flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, and dyes It may further include at least one additive.
  • the molded article is prepared from the thermoplastic resin composition of 1 to 9 above.
  • the molded article may have an Izod impact strength of about 7 kgf cm/cm or more measured according to ASTM D256 for a notched 1/4 inch thick specimen.
  • 2 g of the molded article in the form of a pellet was placed in a glass Petri dish having a diameter of 80 mm, covered with a glass plate on top, and then heated on a hot plate at 290 ° C.
  • the gas generation amount measured through the weight increase of the glass plate after heating for 2 hours in a hot plate may be less than about 7,000 ppm.
  • the molded article may have a flame retardance of V0 or higher as measured according to UL94 standard for a 0.75 mm thick specimen.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, mechanical properties, etc., and a molded article manufactured therefrom.
  • thermoplastic resin composition includes (A) a polyamide resin; (B) a phosphorus-based flame retardant; (C) glass fibers; (D) a melamine-based flame retardant; (E) zinc borate; and (F) magnesium oxide.
  • copolymerization means block copolymerization, random copolymerization, and graft copolymerization
  • copolymer means block copolymer, random copolymer, and graft copolymer
  • the weight average molecular weight is measured by dissolving a powder sample in an appropriate solvent and using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (standard sample is Shodex's polystyrene). used).
  • GPC Gel Permeation Chromatography
  • the polyamide resin enables the thermoplastic resin composition to realize excellent mechanical properties.
  • polyamide resins known in the art may be used as the polyamide resin, for example, an aromatic polyamide resin, an aliphatic polyamide resin, or a mixture thereof, and is not particularly limited.
  • the aromatic polyamide resin is a polyamide resin including an aromatic group in a main chain, and may be a wholly aromatic polyamide resin, a semi-aromatic polyamide resin, or a mixture thereof.
  • the wholly aromatic polyamide resin refers to a polymer of aromatic diamine and aromatic dicarboxylic acid, and the semi-aromatic polyamide resin includes at least one aromatic unit and at least one non-aromatic unit between amide bonds. do.
  • the semi-aromatic polyamide resin may be a polymer of an aromatic diamine and an aliphatic dicarboxylic acid, or a polymer of an aliphatic diamine and an aromatic dicarboxylic acid.
  • the aliphatic polyamide resin refers to a polymer of aliphatic diamine and aliphatic dicarboxylic acid.
  • aromatic diamine examples include p-xylene diamine and m-xylene diamine, but are not limited thereto. In addition, these may be used alone or in combination of two or more.
  • aromatic dicarboxylic acid examples include, but are not limited to, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and (1,3-phenylenedioxy)diacetic acid. . In addition, these may be used alone or in combination of two or more.
  • aliphatic diamine examples include, but are not limited to, ethylenediamine, trimethylenediamine, hexamethylenediamine, dodecamethylenediamine, and piperazine. In addition, these may be used alone or in combination of two or more.
  • aliphatic dicarboxylic acid examples include adipic acid, sebacic acid, succinic acid, glutaric acid, azelaic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, and the like, but are not limited thereto no. In addition, these may be used alone or in combination of two or more.
  • the polyamide resin is polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6I, polyamide 6T, polyamide 4T, polyamide amide 410, polyamide 510, polyamide 1010, polyamide 1012, polyamide 10T, polyamide 1212, polyamide 12T, polyamide MXD6, or combinations thereof.
  • the polyamide resin may be polyamide 66.
  • the polyamide resin may be included in about 40 to about 70% by weight, for example, about 50 to about 70% by weight, for example, about 50 to about 60% by weight, based on 100% by weight of the base material. there is.
  • thermoplastic resin composition and molded articles manufactured therefrom may exhibit excellent mechanical properties due to the polyamide resin.
  • the phosphorus-based flame retardant reinforces the basic flame retardancy of the thermoplastic resin composition to realize a high level of flame retardancy.
  • a conventional phosphorus-based flame retardant used to reinforce flame retardancy of a thermoplastic resin composition may be used.
  • phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, metal salts thereof, and the like can be used.
  • the phosphorus-based flame retardants may be used alone or in combination of two or more.
  • the phosphorus-based flame retardant is aluminum diethyl phosphinate, triphenyl phosphate, ammonium polyphosphate, resorcinol-di (bis-2,6-dimethylphenyl) phosphate (resorcinol-di(bis-2,6-dimethylphenyl) phosphate), bisphenol A diphenyl phosphate, cyclophosphazene, diethyl phosphinate ammonium salt, or Combinations of these may be included.
  • the phosphorus-based flame retardant may be aluminum diethyl phosphinate.
  • the phosphorus-based flame retardant is about 5 to about 25% by weight, for example about 5 to about 20% by weight, for example about 10 to about 20% by weight, for example about 10 to about 15% by weight, based on 100% by weight of the base material. may be included in weight percent.
  • the thermoplastic resin composition and molded articles manufactured therefrom may maintain excellent moldability and flame retardancy and excellent mechanical properties.
  • glass fiber may serve to improve flame retardancy as well as improve mechanical properties such as tensile strength of the thermoplastic resin composition.
  • Glass fibers usable in one embodiment may be glass fibers used in conventional thermoplastic resin compositions.
  • the diameter of the glass fiber may be about 1 to about 20 ⁇ m, for example about 1 to about 15 ⁇ m, for example about 1 to about 10 ⁇ m, for example about 1 to about 5 ⁇ m, but Not limited.
  • the average length of the glass fibers before processing may be about 10 mm or less, for example about 1 to about 8 mm, for example about 1 to about 5 mm, for example about 1 to about 3 mm, but Not limited.
  • thermoplastic resin composition including the glass fibers When the average diameter and average length of the glass fibers are within the above ranges, mechanical properties of the thermoplastic resin composition including the glass fibers may be excellent.
  • the glass fiber may be circular, elliptical, rectangular, or dumbbell-shaped in cross section, and two or more types having different cross-sectional shapes, diameters, lengths, etc. may be mixed and used.
  • the surface of the glass fiber may be surface-treated with a predetermined material, and the fluidity and impact resistance of the thermoplastic resin composition may vary depending on the type of surface treatment agent.
  • the thermoplastic resin composition includes (D) a melamine-based flame retardant, and the (D) melamine-based flame retardant is used together with (B) a phosphorus-based flame retardant to reinforce the flame retardancy of the thermoplastic resin composition to achieve a high level of flame retardancy.
  • the (D) melamine-based flame retardant may be included in about 1 to about 5% by weight, for example, about 1 to about 4% by weight, for example, about 1 to about 3% by weight, based on 100% by weight of the base material. .
  • the melamine-based flame retardant usable in one embodiment may include a conventional melamine-based flame retardant used to reinforce flame retardancy of a thermoplastic resin composition.
  • the melamine-based flame retardant includes melamine polyphosphate, melamine/ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, or a combination thereof can do.
  • the melamine-based flame retardant may be melamine polyphosphate.
  • the weight ratio of the (B) phosphorus-based flame retardant and (D) melamine-based flame retardant is about 2:1 to about 10:1, about 2:1 to about 5:1, or about 3:1 to about 5:1 can Within the above weight ratio range, flame retardancy of the thermoplastic resin composition and molded articles manufactured therefrom may be further improved.
  • zinc borate (ZnB) may impart excellent flame retardancy to the thermoplastic resin composition.
  • the zinc borate may be included in about 0.5 to about 3 parts by weight, for example, about 0.5 to about 2 parts by weight, for example, about 0.5 to about 1 part by weight, based on about 100 parts by weight of the base material. In the range of parts by weight, flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition and molded articles prepared therefrom may be excellent.
  • magnesium oxide can significantly reduce the amount of gas generated due to the use of a phosphorus-based flame retardant. Accordingly, the thermoplastic resin composition according to one embodiment and a molded article manufactured therefrom may have excellent appearance characteristics.
  • magnesium oxide may be included in about 0.3 to about 2 parts by weight, for example, about 0.3 to about 1.5 parts by weight, for example, about 0.3 to about 1 part by weight, based on about 100 parts by weight of the base material. In the range of parts by weight, the impact resistance, mechanical properties and appearance of the thermoplastic resin composition and molded products manufactured therefrom can be excellently maintained.
  • thermoplastic resin composition in addition to the components (A) to (F), can exhibit excellent mechanical properties, flame retardancy, and appearance characteristics, while balancing each physical property, or the final use of the thermoplastic resin composition. According to the necessary one or more additives may be further included.
  • antibacterial agents such as sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite
  • thermoplastic resin composition may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, for example, about 20 parts by weight or less based on about 100 parts by weight of the base material, but is not limited thereto.
  • thermoplastic resin composition according to one embodiment may be mixed with other resins or other rubber components and used together.
  • thermoplastic resin composition a molded article manufactured using the thermoplastic resin composition according to the embodiment.
  • the molded article may be manufactured by various methods known in the art, such as injection molding and extrusion molding, using the thermoplastic resin composition.
  • the molded article may have an Izod impact strength of about 7 kgf ⁇ cm/cm or more measured according to ASTM D256 standard for a notched 1/4 inch thick specimen.
  • the molded article may have a tensile strength of about 1,500 kgf/cm 2 or more when measured under a tensile speed condition of 5 mm/min according to ASTM D638 standard for a 3.2 mm thick specimen.
  • the molded article was prepared by putting about 2 g of the molded article in the form of a pellet into a glass Petri dish having a diameter of about 80 mm, covering the top with a glass plate, and then heating it on a hot plate at 290 ° C. for 2 hours.
  • the gas generation amount measured through the weight increase of the glass plate after processing may be less than about 7,000 ppm.
  • the molded article according to one embodiment may have a flame retardance of V0 or higher measured according to the UL94 standard for a 0.75 mm thick specimen.
  • thermoplastic resin compositions of Examples 1 to 3 and Comparative Examples 1 to 7 were prepared according to the component content ratios shown in Table 1 below, respectively.
  • thermoplastic resin composition in the form of pellets was manufactured. Then, after drying the thermoplastic resin composition pellets at about 80 ° C. for about 4 hours, a cylinder temperature of about 280 ° C. and a mold temperature of about 80 ° C. were set using a 6 oz injection molding machine, and a specimen for measuring physical properties was prepared. The measured physical properties are shown in Tables 2 and 3 below.
  • each of (A), (B), (C) and (D) is a weight% value expressed as a percentage of the weight of each component when the sum of their total weight is 100% by weight
  • contents of components (E) and (F) are relative parts by weight when the sum of the total weights of (A), (B), (C), and (D) is 100 parts by weight.
  • Heat deflection temperature was measured under a load condition of 1.86 MPa according to ASTM D648.
  • thermoplastic resin compositions of Examples are excellent in physical properties such as impact strength, tensile strength, flexural modulus, etc., as well as flame retardancy and appearance characteristics, compared to the thermoplastic resin compositions of Comparative Examples. can
  • Comparative Example 2 which does not contain magnesium oxide, has a significantly higher amount of gas generation than Examples. From this, it can be seen that by including magnesium oxide in the thermoplastic resin composition, it is possible to manufacture a molded article having excellent appearance characteristics by significantly reducing the amount of gas generated during manufacture of the molded article.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition de résine thermoplastique de la présente invention comprend, sur la base d'environ 100 parties en poids d'un matériau initial comprenant (A) environ 40 à 70 % en poids d'une résine polyamide, (B) environ 5 à 25 % en poids d'un agent ignifuge à base de phosphore, (C) environ 20 à 50 % en poids d'une fibre de verre, et (D) environ 1 à 5 % en poids d'un agent ignifuge à base de mélamine, (E) environ 0,5 à 3 parties en poids de borate de zinc et (F) environ 0,3 à 2 parties en poids d'oxyde de magnésium. La composition de résine thermoplastique présente d'excellentes caractéristiques d'ignifugation, de résistance aux chocs, d'aspect extérieur, de propriétés mécaniques et autres.
PCT/KR2023/001729 2022-02-25 2023-02-07 Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci WO2023163417A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2022-0025438 2022-02-25
KR1020220025438A KR20230127758A (ko) 2022-02-25 2022-02-25 열가소성 수지 조성물 및 이로부터 제조되는 성형품

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990021573A (ko) * 1997-08-30 1999-03-25 성재갑 비할로겐 난연 스티렌계 수지 조성물
KR20030036878A (ko) * 2000-10-05 2003-05-09 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 무 할로겐 난연제 조성물 및 난연성 폴리아미드 조성물
KR20150091266A (ko) * 2014-01-31 2015-08-10 이엠에스-패턴트 에이지 난연성 및 우수한 장기 내열노화성을 가진 폴리아미드 성형 화합물
CN105062050A (zh) * 2015-07-17 2015-11-18 中国科学院理化技术研究所 一种耐酸碱无卤阻燃玻璃纤维增强尼龙66复合材料及其制备方法
JP2021522357A (ja) * 2018-04-18 2021-08-30 インヴィスタ テキスタイルズ（ユー．ケー．）リミテッド 難燃剤ポリアミド組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990021573A (ko) * 1997-08-30 1999-03-25 성재갑 비할로겐 난연 스티렌계 수지 조성물
KR20030036878A (ko) * 2000-10-05 2003-05-09 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 무 할로겐 난연제 조성물 및 난연성 폴리아미드 조성물
KR20150091266A (ko) * 2014-01-31 2015-08-10 이엠에스-패턴트 에이지 난연성 및 우수한 장기 내열노화성을 가진 폴리아미드 성형 화합물
CN105062050A (zh) * 2015-07-17 2015-11-18 中国科学院理化技术研究所 一种耐酸碱无卤阻燃玻璃纤维增强尼龙66复合材料及其制备方法
JP2021522357A (ja) * 2018-04-18 2021-08-30 インヴィスタ テキスタイルズ（ユー．ケー．）リミテッド 難燃剤ポリアミド組成物

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