WO2004024821A1 - Composition de moulage contenant du nylon 6 et un agent renforçant fibreux - Google Patents

Composition de moulage contenant du nylon 6 et un agent renforçant fibreux Download PDF

Info

Publication number
WO2004024821A1
WO2004024821A1 PCT/NL2003/000631 NL0300631W WO2004024821A1 WO 2004024821 A1 WO2004024821 A1 WO 2004024821A1 NL 0300631 W NL0300631 W NL 0300631W WO 2004024821 A1 WO2004024821 A1 WO 2004024821A1
Authority
WO
WIPO (PCT)
Prior art keywords
tlcp
nylon
composition
composition according
fibrous reinforcing
Prior art date
Application number
PCT/NL2003/000631
Other languages
English (en)
Inventor
Jiasong He
Xuejing Zheng
Original Assignee
Dsm Ip Assets B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to AU2003269714A priority Critical patent/AU2003269714A1/en
Publication of WO2004024821A1 publication Critical patent/WO2004024821A1/fr

Links

Classifications

    • 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
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the invention relates to a polyamide moulding composition comprising Nylon-6 and a fibrous reinforcing agent.
  • Nylon-6 is a widely used engineering plastic, having good mechanical and thermal properties. Fibrous reinforcing agents are generally added to increase the mechanical strength and modulus.
  • a disadvantage of the polyamide moulding composition comprising Nylon-6 and a fibrous reinforcing agent is that a moulded part prepared from said composition tends to warp.
  • the extent of warpage can be too large and the part does not comply anymore with the required dimensional accuracy.
  • the aim of the invention is to provide a Nylon-6 moulding composition, which does not have these disadvantages or in a lesser extent.
  • composition according to the invention comprising 30-75 wt.% nylon 6, 9-50 wt% fibrous reinforcing agent and 1-20 wt.% of a thermotropic liquid crystalline polymer (TLCP), the weight percentages being relative to the total weight of the composition.
  • TLCP thermotropic liquid crystalline polymer
  • the advantage of the composition according to the invention is that moulded parts made of the composition show less warpage and more precise dimensions than moulded parts made of a corresponding composition without the TLCP
  • the reduced warpage also allows more freedom of design for the moulded part as well as of moulded parts having thinner wall sections. Therefore, the composition according to the invention is particularly suitable for preparing large and thin-walled moulded products or moulded products with more precise dimension requirements.
  • the Nylon-6 that can be used in the composition according to the invention can be any Nylon-6 polymer suitable for use in fiber reinforced moulding compositions for preparing moulded articles.
  • Nylon 7 6 is herein understood to be a polyamide consisting essentially of monomeric units derived from ⁇ -caprolactam.
  • the Nylon-6 in the composition according to the invention comprises at least 90 wt.% monomeric units, derived from ⁇ -caprolactam, preferably at least 95 wt.% ⁇ -caprolactam.
  • Nylon-6 consisting essentially of monomeric units derived from ⁇ -caprolactam may optionally also comprise other monomer units, such as monomeric units derived from monomers including other lactam monomers (such as lauryllactam), or the ⁇ , ⁇ -aminocarboxylic acid equivalent thereof (such as r ⁇ -amino lauric acid), diamines and/or dicarboxylic acids.
  • the other monomer units may also comprise monomeric units derived from branching agents.
  • Branching agents when used in the preparation of Nylon-6, are typically used in very small amounts. Suitable branching agents are, for example, trifunctional amines and trifunctional carboxylic acids.
  • the other monomeric units may be also be derived from aliphatic and /or aromatic components.
  • any known component suitable for the preparation of polyamides may be used.
  • suitable aliphatic diamines that can be used as basis for a monomeric unit in the Nylon-6 according to the invention are 1 ,4-butanediamine and 1 ,6-hexanediamine.
  • An example of a suitable aliphatic dicarboxylic acid that can be used is adipic acid.
  • An example of a suitable aromatic diamine that can be used is 1 ,4-diaminomethylbenzene.
  • Example of a suitable aromatic dicarboxylic acid that can be used is isophthalic acid and therephatalic acid.
  • any reinforcing agent known in the art suitable for use in polyamide moulding compositions may be used.
  • Such fibrous reinforcing agent typically has a short fiber length, allowing the moulding composition to be processed in a melt processing step.
  • the length of the fiber may be in the range of millimeters, for example, 1 to 20 mm, but it may also be in the ⁇ m range, for example 50-500 ⁇ m and even in the nm range, for example 100- 5000 nm.
  • Suitable fibrous reinforcing agents are, for example, glass fibers (GF), carbon fibers (CF), Kevlar fibers or whiskers.
  • Suitable whiskers are for example, inorganic whiskers, such as K 2 Ti 6 O ⁇ 3 whiskers.
  • the TLCP suitable for use in the composition of the present invention may be any TLCP that is immiscible or partially miscible with nylon 6.
  • Particular suitable TLCPs are TLCPs having a melting temperature of 190-360°C, more preferably 230-300 °C.
  • the TLCP that is comprised by the composition according to the invention is a main-chain aromatic copolyester.
  • main-chain liquid crystalline polymer is normally used in the field of liquid crystalline polymers and is understood to be a liquid crystalline polymer comprising a main chain and liquid crystalline polymer segments, wherein the liquid crystalline polymer segments are comprised by the main chain (see for instance H. Finkelman in Materials Science Series / Polymer Liquid Crystals, A. Ciferri, W.R. Krigbaum and R.R. Meyer, editors, Acadamic Press, New York, 1982, page 36; and G.W. Gray and P.A. Windsor, editors, Liquid Crystals & Plastic Crystals, Vol. I, Wiley, New York, 1974).
  • the main-chain aromatic copolyester preferably is a copolyester chosen from the group consisting of copolyesters of 2,6-hydroxynaphthoic acid (HNA) and p-hydroxybenzoic acid (PHB) (e.g., commercially known as Vectra A900 and VectraA950 manufactured by Ticona Co., USA), copolyester-amides of 6-hydroxy-2-naphthoic acid (HNA), terephthalic acid (TA), and aminophenol (APO), (e.g., commercially known as Vectra B900, and Vectra B950 manufactured by Ticona Co, USA), copolyesters of p-hydroxybenzoic acid (PHB) and poly(ethylene terephthalate) (PET) (e.g., commercially known as LC 3000, LC 5000 manufactured by Unitika Co., Japan; X7G manufactured by Eastman Co., USA), and copolymers of terephthalic acid (TA),
  • HNA 2,6-hydroxynaphthoic acid
  • PHB p-hydroxybenzoic acid
  • the composition according to the invention may optionally also comprise at least one additive.
  • the at least one additive that may be comprised in the composition according to the invention may be any additive generally used in polyamide moulding compositions and which can lend desirable qualities to the composition.
  • Such additives include, for example, flame retardants, nucleating agents, antioxidants, stabilizers, colorants, dyes, pigments, plasticizers, non-fibrous fillers, non-fibrous reinforcing agents, processing aids and polymers other than Nylon-6, such as impact modifiers and compatibilizers.
  • the composition according to the invention may comprise the at least one additive in an amount which can vary over a large range.
  • the composition according to the invention consists of a) 30-75 wt.% nylon-6, b) 9-50 wt% fibrous reinforcing agent c) 1 -20 wt.% thermotropic liquid crystalline polymer (TLCP), d) 0.1 -60 wt% of at least one additive chosen form the group of flame retardants, nucleating agents, antioxidants, stabilizers, colorants, dyes, pigments, plasticizers, non-fibrous fillers, non-fibrous reinforcing agents, and processing aids the weight percentages being relative to the total weight of the composition.
  • TLCP thermotropic liquid crystalline polymer
  • composition comprises between 20 to 40 % by weight, relative to the weight of the composition, of the at least one additive.
  • the moulding composition according to the invention containing a fibrous reinforcing agent and a TLCP can be produced by conventional melt blending techniques involving melt-blending of the respective components in the required amounts.
  • any apparatus suitable for that process may be used.
  • suitable for that process may be used.
  • the TLCP and the Nylon-6 may be fed to the melt-blending apparatus, for example, in the form of pellets or a melt.
  • the TLCP and the Nylon-6 are added in the form of a pellet blend.
  • TLCP is used as one component in a polymeric formulation.
  • one or more other polymers e.g. a compatibilizer, are blended with the TLCP prior to blending with the Nylon-6.
  • the reinforcing agent is preferably added to the melt of the TLCP and the Nylon-6.
  • the invention also relates to a process for preparing a moulded product comprising melt-processing and moulding of the composition according to the invention.
  • melt-processing and moulding of the composition according to the invention conventional melt-processing and moulding techniques, involving the use of any apparatus suitable for that process, may be used.
  • melt-processing and moulding equipment such as single-screw extruders and twin-screw extruders.
  • the invention further relates to a moulded product obtainable by the moulding process according to the invention.
  • the advantage thereof is that it shows less warpage compared to a corresponding moulded product made by a process wherein the composition that is moulded is a corresponding polyamide moulding composition comprising Nylon-6 and a fibrous reinforcing component which does not comprise a TLCP.
  • the moulded product preferably is a thin walled product such as thin-walled products for automotive applications and a connector for E&E applications.
  • the TLCP used in the examples is Vectra A950, a copolyester with a melt temperature of 280°C.
  • the Nylon-6 used was a standard grade Nylon 6 with a relative viscosity value of 2.2, and is denoted as PA6.
  • the glass fibers used was a standard grade for use in polyamide moulding compositions, and is denoted as GF. All the materials, Nylon-6, glass fibers and TLCP, were carefully dried at 90°C under vacuum for at least 24 hours prior to use.
  • Example 1 A composition of PA6/GF/TLCP, weight ratio 65/30/5, was prepared by feeding the PA6 and TLCP components via a hopper to a Werner & Pfleiderer ZSK30 twin-screw extruder, melt-blending the PA6 and TLCP in the extruder, thereby forming a polymer melt, dosing the glass fibers to the polymer melt and mixing the polymer melt and the glass fibers in the extruder, thereby forming a melt of a molding composition and extruding the melt of the molding composition from a die.
  • the temperatures of the barrel sections of the extruder, in the order from the hopper to the die, were set at 280, 310, 310, 280, 280, 280, 280 and 280°C.
  • the rotor speed was fixed at 200 rpm, the throughput was 10 kg/hour.
  • the extrudate was cooled with water and pelletized.
  • the pelletized material was injection moulded with a Kraus Maffei
  • KM 120 extruder in a mould with dimensions 60 mm (length) x 60 mm (width) x 1 mm (thickness).
  • the temperature of the extruder was set at 250-280°C to have a melt temperature at the die of 280°C.
  • the temperature of the mould was set at 80°C.
  • the flat square moulded part was ejected after 30 seconds and left to cool to room temperature.
  • a composition of PA6/GF, weight ratio 70/30 was prepared in the same manner as the composition of Example I. Form the resulting pelletized extrudate a flat square moulded part was prepared in the same way as Example I. Warpage test.

Landscapes

  • 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)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention se rapporte à une composition de moulage à base de polyamide, qui contient de 30 % à 75 % poids de nylon 6, de 9 % à 50 % poids d'un agent renforçant fibreux, et de 1 % à 20 % poids d'un polymère cristallin liquide thermotropique (TLCP). Ladite composition présente un gauchissement réduit, et peut servir à fabriquer des produits de grande taille et à fines parois, ou des produits dotés de dimensions d'une meilleure précision.
PCT/NL2003/000631 2002-09-13 2003-09-11 Composition de moulage contenant du nylon 6 et un agent renforçant fibreux WO2004024821A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003269714A AU2003269714A1 (en) 2002-09-13 2003-09-11 Moulding composition comprising nylon-6 and a fibrous reinforcing agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN02143127.2 2002-09-13
CN 02143127 CN1187410C (zh) 2002-09-13 2002-09-13 一种含短纤维和热致液晶聚合物的复合材料

Publications (1)

Publication Number Publication Date
WO2004024821A1 true WO2004024821A1 (fr) 2004-03-25

Family

ID=31983687

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2003/000631 WO2004024821A1 (fr) 2002-09-13 2003-09-11 Composition de moulage contenant du nylon 6 et un agent renforçant fibreux

Country Status (3)

Country Link
CN (1) CN1187410C (fr)
AU (1) AU2003269714A1 (fr)
WO (1) WO2004024821A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103694679A (zh) * 2013-12-18 2014-04-02 上海日之升新技术发展有限公司 一种TLCP增强的导电TiO2/PA复合材料
JP2015183159A (ja) * 2014-03-26 2015-10-22 上野製薬株式会社 液晶ポリエステルブレンド

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100465231C (zh) * 2006-08-24 2009-03-04 华南理工大学 一种含热致液晶聚合物的耐热尼龙材料及其制备方法
CN101195708B (zh) * 2007-12-19 2010-08-11 华南理工大学 一种增强耐热尼龙复合材料及其制备方法
CN101230195B (zh) * 2008-01-18 2011-09-14 银禧工程塑料（东莞）有限公司 一种尼龙复合材料及其制备方法
CN101602888B (zh) * 2009-06-26 2011-05-18 北京工业大学 可循环应用的热致聚酰胺液晶与尼龙复合材料的制备方法
CN102140236B (zh) * 2011-05-10 2012-12-26 刘立文 一种硫酸钙晶须改性聚酯复合材料及其制备工艺
CN102276980B (zh) * 2011-08-04 2013-05-22 金发科技股份有限公司 一种高流动性半芳香族聚酰胺组合物及其制备方法
CN102516762B (zh) * 2011-12-02 2013-10-02 宁波锦海模具塑膠有限公司 一种含生物基高分子的尼龙复合材料及其制备方法
CN103642204A (zh) * 2013-12-11 2014-03-19 绵阳市鹏洋高分子材料有限公司 高性能、高流动性尼龙(液晶)复合材料及其制备工艺
CN103965619B (zh) * 2014-05-15 2017-01-04 扬州赛尔达尼龙制造有限公司 一种高强度超耐热mc尼龙复合材料制备方法及其应用
CN105860036B (zh) * 2016-02-01 2018-09-11 金发科技股份有限公司 一种液晶聚酯以及由其组成的模塑组合物和其应用
CN105860035B (zh) * 2016-02-01 2019-01-22 金发科技股份有限公司 一种液晶聚酯以及由其组成的模塑组合物和其应用
US12037499B2 (en) * 2019-12-11 2024-07-16 The Boeing Company Processable polymer, method, and apparatus for additive manufacture
CN114031910B (zh) * 2021-11-18 2023-02-28 润华(江苏)新材料有限公司 一种tlcp-对位芳纶粉体共混树脂及其制备方法
CN117683344B (zh) * 2023-12-15 2024-09-20 无锡市华羽精密模塑有限公司 一种高分子复合材料及汽车线束卡扣

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02206644A (ja) * 1989-02-06 1990-08-16 Toray Ind Inc 熱可塑性樹脂組成物の製造方法
EP0416430A1 (fr) * 1989-09-06 1991-03-13 BASF Aktiengesellschaft Composition à mouler thermoplastique à résistance élevée à la déformation à chaud
US5102935A (en) * 1988-09-13 1992-04-07 Bayer Aktiengesellschaft Free-flowing polyamide molding compounds and blends
US5143956A (en) * 1990-03-01 1992-09-01 Bayer Aktiengesellschaft Free-flowing polyamide molding compounds
JPH07135042A (ja) * 1993-11-08 1995-05-23 Unitika Ltd 表面実装用コネクタ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5102935A (en) * 1988-09-13 1992-04-07 Bayer Aktiengesellschaft Free-flowing polyamide molding compounds and blends
JPH02206644A (ja) * 1989-02-06 1990-08-16 Toray Ind Inc 熱可塑性樹脂組成物の製造方法
EP0416430A1 (fr) * 1989-09-06 1991-03-13 BASF Aktiengesellschaft Composition à mouler thermoplastique à résistance élevée à la déformation à chaud
US5143956A (en) * 1990-03-01 1992-09-01 Bayer Aktiengesellschaft Free-flowing polyamide molding compounds
JPH07135042A (ja) * 1993-11-08 1995-05-23 Unitika Ltd 表面実装用コネクタ

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199529, Derwent World Patents Index; AN 1995-221560, XP002267043, "Surface mounting connector" *
PATENT ABSTRACTS OF JAPAN vol. 014, no. 497 (C - 0774) 30 October 1990 (1990-10-30) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103694679A (zh) * 2013-12-18 2014-04-02 上海日之升新技术发展有限公司 一种TLCP增强的导电TiO2/PA复合材料
JP2015183159A (ja) * 2014-03-26 2015-10-22 上野製薬株式会社 液晶ポリエステルブレンド

Also Published As

Publication number Publication date
CN1482176A (zh) 2004-03-17
AU2003269714A1 (en) 2004-04-30
CN1187410C (zh) 2005-02-02

Similar Documents

Publication Publication Date Title
JP2862303B2 (ja) ポリマーブレンドの成形方法
WO2004024821A1 (fr) Composition de moulage contenant du nylon 6 et un agent renforçant fibreux
EP0423311B1 (fr) Thermoplastique hautes performances renforce par une fibre polyester entierement aromatique et procede pour sa preparation
KR101391054B1 (ko) 열― 및 광―안정화 폴리아미드 조성물
KR101472650B1 (ko) 고점도 폴리아미드 조성물
EP0543953B1 (fr) Composite autorenforce de polymeres de cristaux liquides thermotropiques
JP2011504941A (ja) フローインデックスの高いポリアミド
CA1262390A (fr) Melanges de polyester/polyesteramide
EP1005502B1 (fr) Elaboration de composites à haute résistance de polymères renforcés par des fibres
US5321099A (en) Blends of semi-crystalline polyamides and polyesteramides
JPH055059A (ja) ポリアミド及びポリエステルの熱可塑性配合物に基づくプラスチツク組成物
JP2003020389A (ja) 熱可塑性樹脂組成物
JP4996668B2 (ja) ポリ乳酸樹脂組成物、ポリ乳酸樹脂組成物の製造方法、成形品、携帯電話機用卓上ホルダー、携帯電話機の内部シャーシ部品、電子機器用筐体及び電子機器用内部部品
JP3181697B2 (ja) 結晶性ポリアミド及びその組成物
US6277909B1 (en) Fiber reinforced resins with improved physical properties and process for producing same
JPS63221157A (ja) 樹脂組成物
US6403728B1 (en) Formed articles from polyester resins
US5362809A (en) Polymer blends of polyglutarimides
JP4186477B2 (ja) 樹脂組成物ならびにそれからなる成形品
JP4786151B2 (ja) 樹脂組成物
US5346967A (en) Blends of thermoplastic polyester resins and amorphous polyamides
KR100409068B1 (ko) 기계적 강도가 향상된 폴리에스테르계 열가소성 수지 조성물
US11753542B2 (en) Thermoplastic resin composition
JPH1149939A (ja) 熱可塑性ポリエステル樹脂組成物
CN118359899A (zh) 低熔指高焊接性热塑性聚醚酯弹性体组合物及其制备方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP