WO1995007170A1 - Moulage perdu - Google Patents

Moulage perdu Download PDF

Info

Publication number
WO1995007170A1
WO1995007170A1 PCT/US1994/009588 US9409588W WO9507170A1 WO 1995007170 A1 WO1995007170 A1 WO 1995007170A1 US 9409588 W US9409588 W US 9409588W WO 9507170 A1 WO9507170 A1 WO 9507170A1
Authority
WO
WIPO (PCT)
Prior art keywords
core material
water soluble
injection molding
filler
molding according
Prior art date
Application number
PCT/US1994/009588
Other languages
English (en)
Inventor
Norihito Shibahara
Jiro Hattori
Shinji Torigoe
Original Assignee
Minnesota Mining And Manufacturing Company
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 Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Publication of WO1995007170A1 publication Critical patent/WO1995007170A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/40—Removing or ejecting moulded articles
    • B29C45/44—Removing or ejecting moulded articles for undercut articles
    • B29C45/4457—Removing or ejecting moulded articles for undercut articles using fusible, soluble or destructible cores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • B29C33/52—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles soluble or fusible

Definitions

  • a core material excellent in heat resistance and fluidity which is to be used for injection molding, especially for the production of a fine injection molded product, e.g. a fastener member.
  • an engaged face fastener member by injection molding by utilization of a water soluble core material capable of being broken away. That is, if the stem portion alone is produced by use of such a water soluble core material, and the base portion and head portion are produced by combination of permanent molds, the aforesaid production process for an engaged face fastener is applicable also to the aforesaid engaged face fastener having a fine pitch and complicated base shape or head shape.
  • the following materials as general water soluble material.
  • these materials are poor in heat resistance, fluidity, and water solubility, and have generally been insufficient in such properties as a core material for injection molding, especially as a core material for the production of fine injection molded products, e.g. the aforesaid engaged face fastener member.
  • the purpose of the present invention is to provide a core material excellent in heat resistance, fluidity, and water solubility, which is to be used for injection molding, especially for the production of fine injection molded products, e.g. an engaged face fastener member.
  • the present invention relates to a water soluble core material to be used in a mold for injection molding, said core material containing a water soluble high molecular weight compound having a hydroxyl group.
  • a hydroxyl group-containing high molecular weight compound is excellent in water solubility, and the core material consisting essentially of such a compound is easily dissolved in water or hot water.
  • the core material consisting essentially of this high molecular weight compound is excellent in thermal stability, and even at a melting temperature of an injection molded resin at the time of molding of an injection molded product, e.g. at a temperature exceeding 200 °C, the period of time during which a high temperature is maintained is so short that.it is possible to retain a pertinent shape.
  • the core material having hydroxyl groups of the present invention is favorable as a core material used for the above purpose.
  • hydroxyl group containing water soluble high molecular weight compound examples include polyvinyl alcohol (PVA), hydroxypropyl cellulose, alkyl cellulose, polyvinyl butyral, polyvinyl formal, and the like.
  • PVA polyvinyl alcohol
  • hydroxypropyl cellulose alkyl cellulose
  • polyvinyl butyral polyvinyl formal
  • proportional amount of hydroxyl group content e.g. saponification degree is favorably within the range between 70 and 95 mol-%.
  • the hydroxyl group concentration is less than 70 mol-%, it is difficult to obtain excellent water solubility, and on the contrary, when the hydroxyl group concentration exceeds 95 mol-%, the hydroxyl groups are mutually reacted at a temperature of about 240 °C, and dehydration and crosslinking reaction are caused, which often result in noticeable lowering of water solubility.
  • the functional group(s) contained in the water soluble high molecular weight compound in the present invention although hydroxyl groups are preferable, the high molecular weight compound may contain other functional groups, e.g. carboxyl group or amino group together with hydroxyl groups.
  • the Tg value of the core material of the present invention is within the range preferably between 40 and 100°C.
  • the Tg value is less than 40 °C, the core material becomes poor in heat resistance, and it becomes difficult for the core material to be used in a mold for injection molding, on the other hand, when the Tg value exceeds 100°C, it becomes difficult for the core itself to be injection molded, and the water solubility of the core material becomes lowered, resulting in difficulty of the use thereof for an injection molded product of a fine shape.
  • the above Tg value can be determined by a differential scanning calorimeter (DSC).
  • melt index (Ml) of the core material of the present invention is preferably within the range between 0.1 and 50 (determined according to ASTM D-1238, at 210°C, under loading of 2160g).
  • Ml is less than 0.1 , the core material becomes poor in fluidity, and it becomes difficult to use it especially as a core material for an injection molded product of a fine shape.
  • Ml exceeds 50, the average molecular weight of the core material becomes comparatively lowered and poor in heat resistance.
  • the core material of the present invention may optionally contain an oxazoline compound, in addition to the aforesaid water soluble high molecular weight compound.
  • the oxazoline compound is defined as a molecular material containing an oxazoline skeleton in a molecule, and as the oxazoline compound, there may be used e.g.
  • 2-vinyl-2-oxazoline 5-methyl-2-vinyl-2- oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-5,6-dihydro- 4 H-1 ,3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4 H-1 ,3-oxazine or a polymeric product thereof, e.g. poly(2-ethyl-2-oxazoline) and the like.
  • the reason why it is favorable to herein add an oxazoline compound is that the fluidity and water solubility of the core resin can be improved, retaining the heat resistance of the core resin.
  • the amount of the added oxazoline compound is favorably within the range between 5 and 3-0 parts by weight based on 100 parts by weight of the aforesaid hydroxyl group- containing water soluble high molecular weight compound.
  • this amount exceeds 30 parts by weight, there is a risk of lowering the heat resistance of the core material.
  • the core material of the present invention may contain a polyh ⁇ dric alcohol compound.
  • a pol ⁇ hydric alcohol compound is favorable, for the reason that the fluidity of the core resin is noticeably improved by addition of a small amount of the pol ⁇ h ⁇ dric alcohol compound, and that since the polyhydric alcohol compound has a plurality of hydroxyl groups in a molecule, there are hydrogen bonds in a molecule, and therefore, the boiling point of the alcohol compound is comparatively high and the alcohol compound does not often cause the troubles such as foaming and bleeding.
  • a pol ⁇ hydric alcohol compound is preferable also in the point that it improves the dispersibility of fillers of inorganic matter or metallic oxide, when the core material of the present invention contains these fillers.
  • the polyhydric alcohol compound herein referred to is defined as a compound having 2 or more hydroxyl groups in a molecule, and as the polyhydric alcohol compound, there can be used e.g. glycerine, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, propylene glycol, 2,3-butanediol, 1 ,3-butanediol, diethylene glycol, triethylene glycol, lecithin, and the like.
  • glycerine e.g. glycerine, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, propylene glycol, 2,3-butanediol, 1 ,3-butanediol, diethylene glycol, triethylene glycol, lecithin, and the like.
  • the amount of the added pol ⁇ hydric alcohol compound is favorably within the range between 0.1 and 10 parts b ⁇ weight based on 100 parts b ⁇ weight of the h ⁇ drox ⁇ l group-containing high molecular weight compound.
  • the amount of the added pol ⁇ h ⁇ dric alcohol compound is less than 0.1 part b ⁇ weight, there is obtained onl ⁇ poor improving effect due to the addition of the pol ⁇ h ⁇ dric alcohol compound, and on the other hand, when the amount exceeds 10 parts b ⁇ weight, there is a fear that the Tg value of the aforesaid water soluble high molecular weight compound, and in its turn, the Tg value of the core material should extremely be lowered.
  • the core material of the present invention ma ⁇ contain a filler, and owing thereto, the heat resistance of the core material is improved, and the mechanical strength thereof is improved, an extending effect (reduction of production cost) results, the fluidity of the core material is improved, when the material is injection molded, the solubility of the core material in water is increased, the surface of the injection mol ded product becomes flat and smooth, and the storage stability of the core material is improved.
  • filler there may be used talc, glass beads, hollow glass beads, silica particles, alumina oxide, calcium carbonate, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, alumino siliocate, mica, barium sulfate, calcium phosphate, kaolin, zeolite, iron, titanium, nickel, copper, magnesium, tin, lead, zinc, metallic salts, crosslinked silicon resin, and the like.
  • the amount of the aforesaid filler to be added is favorably within the range between 1 and 200 parts by weight based on 100 parts b ⁇ weight of the h ⁇ drox ⁇ l group-containing water soluble high molecular weight compound. When this amount is less than 1 part b ⁇ weight, the improving effect caused b ⁇ the addition of the filler is poor. When this amount exceeds 200 parts b ⁇ weight, the moldabilit ⁇ of the core becomes poor, and there is a fear that an injection molding machine should be abraded.
  • the aforesaid filler has an average particle diameter, measured b ⁇ an image processing device, preferabl ⁇ ranging from 0.1 to 600 ⁇ m, particularl ⁇ preferabl ⁇ ranging from 1 to 200 ⁇ m.
  • preferabl ⁇ ranging from 0.1 to 600 ⁇ m, particularl ⁇ preferabl ⁇ ranging from 1 to 200 ⁇ m.
  • the particle diameter is less than 0.1 ⁇ m, there can be obtained onl ⁇ a poor improving effect due to the addition of the filler, and it is difficult to disperse the filler into the aforesaid high molecular weight compound.
  • the particle diameter of the filler exceeds 600 ⁇ m, the injection molded product becomes poor in surface smoothness.
  • the filler is to be applied to an injection molded product of a fine shape, it is possible to optionally adjust the particle diameter b ⁇ pulverization of the filler, in the case where the filler is to be dispersed int o a high molecular weight compound b ⁇ use of a screw or the like, so long as the original particle diameter of the filler is 600 ⁇ m or less, and therefore, the filler having a particle diameter of 600 ⁇ m or less can be used in the present invention.
  • the filler when the particle diameter of the filler is within the range between 1 and 200 ⁇ m, the filler has the advantages that there is little fear that the filler should abrade the injection molding machine used, that it can be easil ⁇ separated from the high molecular weight compound, and that the waste liquid can easil ⁇ be disposed, so that the filler can easil ⁇ be applied to an injection molding of a fine shape.
  • the densit ⁇ of the aforesaid filler is favorabl ⁇ 1 .05 or more or 0.95 or less.
  • the reason therefor is that when the densit ⁇ is 1 .05 or more, the particles thereof are likely to be settled when dissolving the water soluble core, and it is possible to dissolve the water soluble core more easil ⁇ b ⁇ use of a centrifugal separator.
  • more preferable densit ⁇ of the filler is 1.3 or more, because separation and recover ⁇ of the particles of the filler from the water soluble core become easier.
  • the reason wh ⁇ the densit ⁇ of the filler is preferabl ⁇ 0.95 or less is that since the particles of the filler float on the water surface in the case of dissolving the water soluble core, separation and reutilization of the particles are ver ⁇ eas ⁇ .
  • the shape of the aforesaid filler particles is desirabl ⁇ a spherical one having a uniform particle size distribution.
  • the filling rate of the filler into the resin can be made ver ⁇ noticeably higher as compared with the case where an indeterminate filler is used, and that even if the filler is added in a large amount, it gives little influence to the fluidity of the core resin when injection molding the core resin, so long as the filler is composed of particles of a uniform spherical shape.
  • the filler can be reutilized, and the production cost thereof can be lowered.
  • the filler is easily arranged on the core surface, the surface smoothness and reproducibility of the produced injection molded product become higher.
  • the core material of the present invention ma ⁇ contain a pigment or a d ⁇ e.
  • a step of dissolving the core material in water since the concentration of the core material in water exhibits a strong influence to the dissolving rate of the core material, handling of the aqueous solution becomes important. Accordingl ⁇ , it becomes possible to ver ⁇ simpl ⁇ conduct such handling b ⁇ viewing or the like b ⁇ utilization of a pigment or d ⁇ e which is dissolved out together with the core.
  • b ⁇ use of a pigment or d ⁇ e with a color different from that of the injection molded product it becomes possible to ver ⁇ easil ⁇ judge the insufficienc ⁇ of the solubilit ⁇ of the core material b ⁇ viewing or the like.
  • the kind of the aforesaid pigment or d ⁇ e is not particularl ⁇ limited.
  • organic pigments or organic d ⁇ es e.g. azo d ⁇ es, nitroso d ⁇ es, anthraquinone t ⁇ pe d ⁇ es, indigo t ⁇ pe d ⁇ es, sulfur d ⁇ es, basic d ⁇ es, acid d ⁇ es, thiazole t ⁇ pe d ⁇ es, naphthol d ⁇ es and the like.
  • the amount of the aforesaid pigment or d ⁇ e to be added can be determined, judged from the chromaticit ⁇ , color value, chroma and the like.
  • the amount of the pigment or d ⁇ e to be added is favorabl ⁇ within the range between 0.01 and 5 parts b ⁇ weight based on 100 parts b ⁇ weight of the h ⁇ drox ⁇ l group-containing water soluble high molecular weight compound.
  • this amount is less than 0.01 part b ⁇ weight, there is generall ⁇ obtained onl ⁇ a poor coloring effect.
  • this amount exceeds 5 parts b ⁇ weight handling of the aqueous solution produced in the step of dissolving the core material in water becomes difficult, on the contrar ⁇ .
  • the core of the present invention ma ⁇ contain carbon black. Owing to the contained carbon black, there can be improved the heat resistance and reinforcing effect of the core material. Owing to the comparativel ⁇ small particle diameter of carbon black, the surface smoothness of the injection molded product is improved. In addition, since carbon black is excellent in hiding power, the core material can be turned black b ⁇ addition of a small amount of carbon black. On the other hand, if the color of the injection molded product is made blackish one, even in the case where the core material is somewhat adhered to the injection molded product in such an extent as ma ⁇ not impair the function of the injection molded product, there is little fear that the external appearance of the injection molded product should be marred b ⁇ the core material. It becomes possible to effect handling of the aqueous solution b ⁇ viewing or the like, with the carbon black flown out together with the core. In addition, since carbon black is inexpensive, it produces also an extending effect.
  • the kind of carbon black is not particularly limited.
  • carbon black there ma ⁇ be used channel black, thermal black, furnace black, and the like.
  • the amount of carbon black to be added can be set, judging from the degree of blackness or the like. In concrete, this amount is favorabl ⁇ within the range between 0.05 and 20 parts b ⁇ weight based on 100 parts b ⁇ weight of the h ⁇ drox ⁇ l group containing water soluble high molecular weight compound. When this amount is less than 0.05 part b ⁇ weight, the added carbon black generall ⁇ produces onl ⁇ a poor improving effect. On the other hand, when this amount exceeds 20 parts b ⁇ weight, handling of the aqueous solution produced in the step of dissolving the core material in water becomes difficult, on the contrar ⁇ .
  • Examples 1 to 8 and Comparative Example 1 Pol ⁇ vin ⁇ l alcohols produced b ⁇ Japan S ⁇ nthetic Chemistr ⁇ Co., Ltd. or acr ⁇ lic water soluble resins produced b ⁇ Berrant Inc., which are set forth in Table 1 , were, respectivel ⁇ , dried for 24 hours or longer b ⁇ use of a hot-air dr ⁇ er, the temperature of which had been controlled at 50 °C, whereafter cores were molded, at a temperature of 210°C or 225°C, b ⁇ use of a core t ⁇ pe 6 produced b ⁇ Sumitomo 3M Co., Ltd., b ⁇ a molding machine of PS-40 t ⁇ pe manufactured b ⁇ Nissei Resin Industries Co., Ltd.
  • the prepared core materials were dipped in water or hot-water of 23°C or 70°C for 24 hours, whereafter the solubilit ⁇ of each core material was judged b ⁇ viewing according to the following criterion.
  • KP06, KL05, KMll, GL03, GL05, GM14, GH23, and NL05 are trade names of polyvinyl alcohols produced by Japan Synthetic Chemistry
  • GBC 1330TE is a trade name of an acrylic water soluble - resin produced by Berrant Inc.
  • GRI glycerine, produced by Wako Pure Chemical Industries, Ltd.
  • PEOX trade mark of polyethylene oxazoline produced by Dow Chemical Inc.
  • C.B. carbon black produced by Asahi Carbon Co. Ltd. , "Asahi Carbon Black” (trade mark).
  • Average particle diameter determined by an electron microscope or an image-processing device; the same as hereafter: 80 WM.
  • ML3050 trade name of "Macrolite” (trade mark), spherical particles of alumina silicate produced by 3 M Co., U. S. A., Average particle diameter: 300 to 600 ⁇ m, Density: 1.05
  • SO-C65 trade name of "Admafine” (trade mark), silica powder of spherical particles produced by Admatechs Inc., Average particle diameter: 1.5 to 2 ⁇ , Density: 2.21 Examples 14 to 17
  • GB731 Trade name of the glass beads produced by Toshiba Ballotiene Inc.
  • SO-C2 trade name of "Admafine” (trade mark), silica powder of spherical particles produced by Admatechs Co., Ltd.
  • C15/250 trade name of "Scotch Light Glass Bulbs” (trade mark), glass balloons produced by 3M Co., U.S.A.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Mold Materials And Core Materials (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne un matériau de noyau soluble dans l'eau servant à réaliser un moulage par injection.
PCT/US1994/009588 1993-09-06 1994-08-26 Moulage perdu WO1995007170A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5/220948 1993-09-06
JP22094893A JPH0780598A (ja) 1993-09-06 1993-09-06 射出成形用水溶性中子材料

Publications (1)

Publication Number Publication Date
WO1995007170A1 true WO1995007170A1 (fr) 1995-03-16

Family

ID=16759066

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/009588 WO1995007170A1 (fr) 1993-09-06 1994-08-26 Moulage perdu

Country Status (2)

Country Link
JP (1) JPH0780598A (fr)
WO (1) WO1995007170A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1004109C2 (nl) * 1996-09-25 1998-03-26 Avebe Coop Verkoop Prod Verwijderbare kern ten gebruike in gietproducten.
EP0917943A1 (fr) * 1997-06-03 1999-05-26 Taisei Plas Co., Ltd. Procede de fabrication de produits moules en matiere plastique
WO2002098498A1 (fr) * 2001-06-04 2002-12-12 Japan Lifeline Co., Ltd. Catheter a ballonnet et mode de fabrication
US7018496B1 (en) 1999-04-26 2006-03-28 3M Innovative Properties Company Curable mechanical fasteners
CN114043650A (zh) * 2021-12-02 2022-02-15 上海新旺科技有限公司 一种水溶性芯模

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001293742A (ja) * 2000-04-11 2001-10-23 Daisee Kogyo Kk 射出成形品の製造方法
US20040167270A1 (en) * 2003-02-25 2004-08-26 Dane Chang Fugitive pattern for casting
JP6057598B2 (ja) * 2012-08-09 2017-01-11 株式会社キャステム 中空部を有する金属粉末焼結体の製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1100359A (fr) * 1954-03-01 1955-09-20 Procédé de fabrication d'objets creux en matières plastiques et en particulier en plastique renforcé
US4877569A (en) * 1988-06-06 1989-10-31 Motorola, Inc. Method of making a one-piece injection molded battery contact assembly
JPH03227609A (ja) * 1990-02-02 1991-10-08 Mitsubishi Kasei Corp 樹脂製中空多岐管の製造法
FR2672536A1 (fr) * 1991-02-13 1992-08-14 Mauro James Procede pour la fabrication d'un produit creux en matiere plastique, en utilisant une resine soluble dans l'eau.
US5184874A (en) * 1990-04-10 1993-02-09 Olson Paul D Injection molded plastic bicycle wheel
WO1993022120A1 (fr) * 1992-05-07 1993-11-11 Minnesota Mining And Manufacturing Company Elements d'attache interpenetrants et leur procede de fabrication
JPH0639844A (ja) * 1992-07-24 1994-02-15 Riken Viny Kogyo Kk 中子用組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1100359A (fr) * 1954-03-01 1955-09-20 Procédé de fabrication d'objets creux en matières plastiques et en particulier en plastique renforcé
US4877569A (en) * 1988-06-06 1989-10-31 Motorola, Inc. Method of making a one-piece injection molded battery contact assembly
JPH03227609A (ja) * 1990-02-02 1991-10-08 Mitsubishi Kasei Corp 樹脂製中空多岐管の製造法
US5184874A (en) * 1990-04-10 1993-02-09 Olson Paul D Injection molded plastic bicycle wheel
FR2672536A1 (fr) * 1991-02-13 1992-08-14 Mauro James Procede pour la fabrication d'un produit creux en matiere plastique, en utilisant une resine soluble dans l'eau.
WO1993022120A1 (fr) * 1992-05-07 1993-11-11 Minnesota Mining And Manufacturing Company Elements d'attache interpenetrants et leur procede de fabrication
JPH0639844A (ja) * 1992-07-24 1994-02-15 Riken Viny Kogyo Kk 中子用組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 15, no. 513 (M - 1196) 26 December 1991 (1991-12-26) *
PATENT ABSTRACTS OF JAPAN vol. 18, no. 258 (M - 1606) 17 May 1994 (1994-05-17) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1004109C2 (nl) * 1996-09-25 1998-03-26 Avebe Coop Verkoop Prod Verwijderbare kern ten gebruike in gietproducten.
WO1998013183A1 (fr) * 1996-09-25 1998-04-02 Coöperatieve Verkoop- En Productievereniging Van Aardappelmeel En Derivaten Avebe B.A. Noyau amovible utile dans un procede de moulage par injection et procede de fabrication d'un produit creux moule par injection
EP0917943A1 (fr) * 1997-06-03 1999-05-26 Taisei Plas Co., Ltd. Procede de fabrication de produits moules en matiere plastique
EP0917943A4 (fr) * 1997-06-03 2000-02-23 Taisei Plas Co Ltd Procede de fabrication de produits moules en matiere plastique
US7018496B1 (en) 1999-04-26 2006-03-28 3M Innovative Properties Company Curable mechanical fasteners
WO2002098498A1 (fr) * 2001-06-04 2002-12-12 Japan Lifeline Co., Ltd. Catheter a ballonnet et mode de fabrication
EP1393769A1 (fr) * 2001-06-04 2004-03-03 Japan Lifeline Co., Ltd Catheter a ballonnet et mode de fabrication
EP1393769A4 (fr) * 2001-06-04 2006-06-21 Japan Lifeline Co Ltd Catheter a ballonnet et mode de fabrication
CN114043650A (zh) * 2021-12-02 2022-02-15 上海新旺科技有限公司 一种水溶性芯模

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