EP0754109A1 - Materiau pour noyau moulage et procede de moulage par injection - Google Patents
Materiau pour noyau moulage et procede de moulage par injectionInfo
- Publication number
- EP0754109A1 EP0754109A1 EP95915552A EP95915552A EP0754109A1 EP 0754109 A1 EP0754109 A1 EP 0754109A1 EP 95915552 A EP95915552 A EP 95915552A EP 95915552 A EP95915552 A EP 95915552A EP 0754109 A1 EP0754109 A1 EP 0754109A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- core material
- pva
- core
- peo
- range
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 239000011162 core material Substances 0.000 title claims abstract description 104
- 238000001746 injection moulding Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 10
- 230000008569 process Effects 0.000 title claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 63
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 63
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- -1 oxazoline compound Chemical class 0.000 claims description 15
- 238000007127 saponification reaction Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 description 56
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 239000000945 filler Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000007836 Chlorogalum pomeridianum Nutrition 0.000 description 1
- 240000006670 Chlorogalum pomeridianum Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 239000012861 aquazol Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2829/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof, as mould material
- B29K2829/04—PVOH, i.e. polyvinyl alcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2871/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as mould material
- B29K2871/02—Polyalkylene oxides, e.g. PEO, i.e. polyethylene oxide, or derivatives thereof
Definitions
- the present invention relates to a core material composed of a water soluble material.
- the core material of the present invention is useful especially for the preparation of a core for the injection molding of plastic products or parts with a fine structure, e.g., a face fastener (Hook-and-Loop fastener) used in the automotive industrial field, and so forth.
- a face fastener Hook-and-Loop fastener
- the material for the preparation of core for injection molding of high molecular weight material products or parts with a fine structure it is needed to satisfy the conditions that it is easy to mold a core having a fine structure in itself, and that after said high molecular weight material products or parts have been molded, the used core can be easily dissolved in water and eliminated.
- U.S. Pat. No. 5,242,646 discloses a process for the production of a face fastener composed of a head portion, stem portion and base, and in this process, PVA is used as a core material.
- PVA is simultaneously melted and decomposed (thermal crosslinking), difficulty has been attended with the formation itself of a core.
- a water soluble core material for the injection molding of a high molecular weight material there is described an acrylic high molecular weight material having a carboxyl group in Japanese Unexamined Patent Publication No. 60-155212 and EP 0314156.
- U.S. Pat. No. 4,990,146 and U.S. Pat. No. 4,870,148 there is described amino group-containing high molecular weight materials soluble in an acid solvent or alkaline solvent.
- Japanese Unexamined Patent Publication No. 1-198609 there is described, as a water soluble core material, a material obtained by addition of a filler to a carboxyl group- containing acrylic high molecular weight material.
- these water soluble materials have been defective in the insufficiency of heat resistance and fluidity, in forming a core, or has had the drawback that they are poor in water solubility in the case where a used core is to be eliminated by use of water.
- the present invention relates to a core material for injection molding, and the purpose of the present invention is to provide a core material, which has sufficient heat resistance and fluidity in forming a core, thereby facilitating precise formation of a core having a minute structure, and which is easily dissolved in water in the case of used core being dissolved in water and eliminated.
- the present inventors studied in various ways for solving the aforesaid problem, and consequently found that a composition comprising a polyvinyl alcohol (PVA) and polyethylene oxide (PEO) satisfies the aforesaid requirements, so as to achieve the present invention.
- PVA polyvinyl alcohol
- PEO polyethylene oxide
- the present invention provides a core material for injection molding, comprising a copolymer of a polyvinyl alcohol (PVA) and polyethylene oxide (PEO), and the use thereof.
- PVA polyvinyl alcohol
- PEO polyethylene oxide
- PVA polyvinyl alcohol
- PEO polyethylene oxide
- a polyvinyl alcohol (PVA) has a melting point ranging from 170°C to 230°C according to the difference of saponification degrees.
- any PVA begins to be thermally decomposed at a temperature exceeding 200°C, and at a temperature of 240°C or more, dehydration and crosslinking reaction of PVA proceed, and therefore, PVA has the defect that the water solubility thereof becomes noticeably lowered.
- PVA polyethylene oxide
- PEO polyethylene oxide
- PEO is also known as a water soluble resin.
- PEO is very poor in injection fluidity, as compared with a PVA having a molecular weight in the same degree as that of the PEO, and therefore unsuitable for the production of an injection molded product of a fine shape.
- the copolymer of a polyvinyl alcohol (PVA) and polyethylene oxide (PEO) is capable of relatively lowering the hydroxyl group concentration causing a chemical reaction. While a high water solubility is maintained, because the copolymer has a hydroxyl group and ether linkage in the structure thereof, and therefore, the copolymer is more stable than a PVA. In addition, the introduction of an ether linkage gives a low melting point to the copolymer, and therefore, can solve the problem related to the thermal workability of PVA.
- the PVA portion constituting the above copolymer includes the range from a partially saponified PVA having an acetic group to the fully saponified PVA, according to the extent of the saponification degree.
- the molar ratio between the PVA and PEO in the aforesaid copolymer is preferably within the range of 99 to 50 (PVA): 1 to 50 (PEO). Within this range of ratio, there can be obtained sufficient thermal stability and sufficient fluidity at the time of forming a core, as well as sufficient water solubility of the used core, but, when the proportional amount exceeds 50%, the viscosity of the core becomes so high that it becomes difficult to form a core having a fine shape. On the other hand, when the proportional amount is less than 1%, the thermal stability of the core material is so low that thermal crosslinking occurs owing to the heating during the formation of the core, and the water solubility of the used core is likely to be lowered.
- the molar ratio between the PVA and PEO in the polymer is more preferably within the range of 95 to 55 (PVA): 5 to 45 (PEO). Within this range, the aforesaid characteristics are emphasized to a greater extent.
- the molar ratio between the PVA and PEO in the polymer is still more preferably within the range of 90 to 70 (PVA): 30 to 10 (PEO). Within this range, the aforesaid characteristics are emphasized to a still greater extent.
- the saponification degree of the PVA in preferably 65 mol-% or more, e.g., within the range between 65 and 99 mol-%.
- the saponification degree of 99 mol-% means the maximum value of the actually available saponification degree.
- the saponification degree of the PVA is more preferably 70 mol-% or more, e.g., within the range between 70 and 99 mol-%. When the saponification degree is 70 mol-% or more, especially the water solubility of the PVA becomes high.
- the saponification degree of the PVA is still more preferably 80 mol-% or more, e.g., within the range between 80 and 99 mol-%. When the saponification degree is 80 mol-% or more, the melting point of the PVA increases, while the water solubility thereof is maintained, and the heat resistance of the PVA is improved in the case of parts or the like being injection molded.
- the preferred embodiment of the water soluble core material of the present invention is one having a T g value ranging from 40°C to 100°C. Because, when the T g value is less than 40°C, the core material is poor in heat resistance, and unsuitable as a core material to be used in a mold for injection molding. On the other hand, when the T g value exceeds 100°C, the injection molding of the core itself becomes difficult, and what is more, water solubility of the core material becomes lowered. Therefore, it becomes difficult to use the core material, especially for an injection molded product having a fine shape.
- the preferred embodiment of the water soluble core material of the present invention includes a water soluble high molecular weight material in which the MI value of the aforesaid water soluble core material is within the range between 0.1 and 50 (according to ASTM D-1238, at 210°C, under a load of 2160g).
- the reason why the MI value is limited within the range between 0.1 and 50 in the present invention is that when the MI value is less than 0.1, the fluidity of the core material becomes poor in a mold for injection molding, resulting in the difficulty of the use of the core material, especially for an injection molded product having a fine shape, and on the other hand, when the MI value exceeds 50, the average molecular weight of the core material becomes relatively lower, resulting in lowering of the heat resistance of the core material.
- PVA PEO copolymer As concrete commercially available PVA PEO copolymer, there may be mentioned water soluble PVA PEO copolymers, "Ax 300", “Ax 2000”, and the like produced by Nihon Gosei Kagaku Kogyo K.K. (Japan Synthetic Chemistry Ind. Co., Ltd.).
- water soluble PVA PEO copolymers "Ax 300", “Ax 2000”, and the like produced by Nihon Gosei Kagaku Kogyo K.K. (Japan Synthetic Chemistry Ind. Co., Ltd.).
- oxazoline compound polyethylene oxide (PEO), and/or PVA.
- An oxazoline compound is defined as a high molecular weight material having an oxazoline skeleton in the molecule, and as an oxazoline compound, there may be used, e.g., poly(2-ethyl-2- oxazoline) and the like.
- an oxazoline compound, PEO or PVA is herein added is that it thereby becomes possible to improve the fluidity and water solubility of the core material without impairing the heat resistance thereof.
- PVA there is preferred a one having a hydroxyl group concentration ranging from 70 to 95 mol-%.
- the reason therefor is that, when the hydroxyl group concentration is less than 70 mol-%, the water solubility of PVA lowers, on one hand, and on the other hand, when the hydroxyl group concentration exceeds 95 mol-%, not only the water solubility of PVA becomes lowered, but also the heat resistance thereof becomes noticeably worsened.
- the proportional amount of the oxazoline compound, POE or POE to be added is preferably within the range between 5 and 60 parts by weight based on 100 parts by weight of the present water soluble copolymer.
- a polyhydric alcohol compound such as inorganic matters or metal oxides and coloring pigments.
- Addition of a small amount of a polyhydric alcohol compound can improve the fluidity of the core resin.
- a polyhydric alcohol compound since a polyhydric alcohol compound has a hydroxyl group in the molecule, the boiling point thereof is relatively high, and also in the use thereof in a mold of the present invention, there are not caused the problems such as foaming and bleeding.
- the polyhydric alcohol compound is more effective also because it improves the dispersibility of fillers such as inorganic matters or metal oxides and coloring pigments.
- a polyhydric alcohol is defined as a compound having at least 2 hydroxyl groups in the molecule, and as a polyvalent alcohol, there can be used, e.g., glycerine, ethylene glycol, trimethylene glycol, tetramethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2,3-butanediol, 1,3-butanediol, pentamethylene glycol, and the like.
- Fillers are effective for the improvement of the heat resistance, mechanical strength, weighting effect (reduction of cost), fluidity, and solubility of the core material of the resent invention, and as the fillers, there can be used e.g., talc, glass beads, hollow glass beads, magnesium carbonate, mica, alumino silicate, calcium phosphate, zeolite, metal salts, as well as oxides of the metals such as titanium, tin, magnesium, and zinc.
- the amount of the fillers to be added is preferably within the range between 1 and 150 parts by weight based on 100 parts by weight of the aforesaid water soluble core material, in general, although it is not particularly limited. Within a range other than the aforesaid range, the fillers are poor in the aforesaid improving effects. In addition, it is favorable to improve the compatibility of the fillers such as glass beads with the core material by subjecting them to coupling treatment.
- Pigments or dyes are very effective for recognizing the dissolved state of the core material of the present invention, and in its turn, the adhesion of the core material to an injection molded product such as face fastener, by visual observation or the like. For example, by use of a core color different from the color of the injection molded product, adhesion of the core material to the product can easily be recognized.
- the kinds of the pigments or dyes to be used are not particularly limited, there can be used, as the pigments or dyes, carbon black, organic pigments, titanium white, and organic dyes such as azo dyes, acid dyes, basic dyes, thiazole dyes, and naphthol dyes.
- the amount of the pigments or dyes to be added is preferably within the range between 0.01 and 5 parts by weight, based on 100 parts by weight of the water soluble core material.
- this amount is less than 0.01 part by weight, the aforesaid recognizing effect becomes poor, and on the other hand, when it exceeds 5 parts by weight, on the contrary, the pigments or dyes are adhered to the injection molded product, and time and labor are required to eliminate them, on the contrary.
- a process for production of a core characterized by melting the present core material at a temperature of at least 50°C, and injection-molding said molten core material into a mold.
- the reason why the core material is headed to at least 150°C is because by this method a lower melting viscosity can be obtained, and a fine injection molded article such as a face fastener part having a base portion and a regularly positioned plurality of projections having a leg generating from the base portion and a mushroom-shaped head linked to the end of the leg can be produced with high accuracy in a short time.
- a heater infrared light, etc. can be used.
- a melting temperature 160-260°C, 190-240°C is preferable. In the former range, a lower melt viscosity is obtained and a core material is not crosslinked by over heating. In the latter range, a more lower melt temperature is obtained, and a core material is neither crosslinked and nor discolored.
- a molten core material is molded into a desired shape in a mold. Fine shaped articles can be easily produced in a short time. Note that to accelerate solidification of a core and to remove the core early and in a short time, a mold is preferably cooled to a predetermined temperature with, for example, cooled air.
- water soluble core for injection molding which is excellent in thermoresistance, fluidity and water solubility.
- a molten material for injection molding can be injection-molded.
- a complicated and fine shaped article such as surface fastener part can be molded in a single step.
- the injection is desirably carried out at a temperature lower than the melting temperature of the core.
- Ax3OO Water soluble PVA/PEO copolymer resin, "ECOMATY” produced by Japan Synthetic Chemistry Ind. Co., Ltd.
- Ax2OOO Water soluble PVA/PEO copolymer resin, "ECOMATY” produced by Japan Synthetic Chemistry Ind. Co., Ltd. AL03-2: Polyvinyl alcohol produced by Japan Synthetic Chemistry Ind. Co., Ltd.
- GL05 Polyvinyl alcohol produced by Japan Synthetic Chemistry Ind. Co., Ltd.
- KP08 Polyvinyl alcohol produced by Japan Synthetic Chemistry Ind. Co., Ltd.
- KL05 Poly-vinyl alcohol produced by Japan Synthetic Chemistry Ind. Co., Ltd.
- GBI330TE Water soluble acrylic resin produced by Berrant Co., Ltd.
- PEOX200 Poly(ethyl oxazoline) produced by Dow Chemical Co., Ltd.
- PEO-1 Poly(ethylene oxide) produced by Sumitomo Seika Co., Ltd.
- GB731B Glass beads produced by Toshiba Barotini Co., Ltd.
- Talc "Talc MS-A11 produced by Japan Talc Co., Ltd.
- Examples 1 and 2 and Comparative Examples 1 to 3 A water soluble resin, "ECOMATY”, produced by Nihon Gosei Kagaku Kogyo K.K. (Japan Synthetic Chemistry Ind. Co., Ltd.) and a PVA were dried for 24 hours by use of a hot air dryer, whereafter a core was produced at a temperature of 210°C, by use of a core mold No. 6 produced by Sumitomo 3M Co., Ltd. by an injection molding machine of "PS-40" type produced by Nissei Jushi Kogyo K.K. [Nissei Resin Ind. Co., Ltd.].
- the saponification degree was calculated from the integrated intensity ratio determined by use of a nuclear magnetic resonance device "EX 270", produced by Nihon Denshi K.K. [Japan Electronic Co., Ltd.]
- the temperature of the core material was elevated from -60 to 300°C at a rate of 10°C/min by use of "DSC-2C" manufactured by Perkin Elmer Ind. Co., Ltd., and the Tm and T g values were determined from the change of specific heats.
- the temperature of the core material was elevated at a rate of 10°C/min by use of an apparatus for thermogravimetry "951" manufactured by Dupon Co., Ltd., and the decomposition temperature in the air atmosphere was determined.
- MI Melt Index
- the melt index (MI) values of the core materials were determined, respectively, by use of a Melt Indexer S-1001 manufactured by Toyo Seiki Ind. Co., Ltd., according to ASTM D-1238 (at 210°C, under a loading of 2160g).
- face fasteners were prepared under the under-described temperature conditions, respectively. Subsequently, a stem line was cut out from each face fastener in the longitudinal direction, and the heat resistances of the core materials were evaluated by microscopically judging the shape and uniformity of the stem group viewed from the direction of the cross section of the stem line, according to the following criterion.
- MI melt indices
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Matériau pour noyau destiné au moulage par injection, formé d'un copolymère obtenu à partir d'un alcool polyvinylique (PVA) et d'un oxyde de polyéthylène, et noyau composé dudit matériau.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP66918/94 | 1994-04-05 | ||
JP6066918A JPH07276372A (ja) | 1994-04-05 | 1994-04-05 | 中子材料及びその使用 |
PCT/US1995/004194 WO1995026864A1 (fr) | 1994-04-05 | 1995-04-03 | Materiau pour noyau moulage et procede de moulage par injection |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0754109A1 true EP0754109A1 (fr) | 1997-01-22 |
Family
ID=13329845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95915552A Withdrawn EP0754109A1 (fr) | 1994-04-05 | 1995-04-03 | Materiau pour noyau moulage et procede de moulage par injection |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0754109A1 (fr) |
JP (1) | JPH07276372A (fr) |
KR (1) | KR970702136A (fr) |
CN (1) | CN1144502A (fr) |
CA (1) | CA2187180A1 (fr) |
WO (1) | WO1995026864A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6070107A (en) * | 1997-04-02 | 2000-05-30 | Stratasys, Inc. | Water soluble rapid prototyping support and mold material |
US6067480A (en) * | 1997-04-02 | 2000-05-23 | Stratasys, Inc. | Method and apparatus for in-situ formation of three-dimensional solid objects by extrusion of polymeric materials |
US6228923B1 (en) | 1997-04-02 | 2001-05-08 | Stratasys, Inc. | Water soluble rapid prototyping support and mold material |
JP4071846B2 (ja) * | 1997-06-03 | 2008-04-02 | 大成プラス株式会社 | プラスチック製成形体の製造方法 |
JP2001293742A (ja) * | 2000-04-11 | 2001-10-23 | Daisee Kogyo Kk | 射出成形品の製造方法 |
ATE449796T1 (de) | 2001-05-14 | 2009-12-15 | Kuraray Co | Modifiziertes ethylen-vinylalkohol-copolymer und herstellungsverfahren dafür |
CN106496908A (zh) * | 2016-10-07 | 2017-03-15 | 常州创索新材料科技有限公司 | 一种水溶性芯模材料的制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3639507A (en) * | 1966-09-07 | 1972-02-01 | Trw Inc | Plastic pattern material for investment casting |
DE69118622T2 (de) * | 1990-09-04 | 1996-09-19 | Nippon Synthetic Chem Ind | Biologisch abbaubare, schmelzgeformte Gegenstände, Laminate daraus und ihre Verwendung |
US5242646A (en) * | 1992-05-07 | 1993-09-07 | Minnesota Mining And Manufacturing Company | Method of making an interengaging fastener member |
JP3029347B2 (ja) * | 1992-07-24 | 2000-04-04 | 理研ビニル工業株式会社 | 中子用組成物 |
-
1994
- 1994-04-05 JP JP6066918A patent/JPH07276372A/ja active Pending
-
1995
- 1995-04-03 CN CN95192310A patent/CN1144502A/zh active Pending
- 1995-04-03 KR KR1019960705523A patent/KR970702136A/ko not_active Application Discontinuation
- 1995-04-03 EP EP95915552A patent/EP0754109A1/fr not_active Withdrawn
- 1995-04-03 CA CA002187180A patent/CA2187180A1/fr not_active Abandoned
- 1995-04-03 WO PCT/US1995/004194 patent/WO1995026864A1/fr not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9526864A1 * |
Also Published As
Publication number | Publication date |
---|---|
MX9604403A (es) | 1997-07-31 |
JPH07276372A (ja) | 1995-10-24 |
WO1995026864A1 (fr) | 1995-10-12 |
KR970702136A (ko) | 1997-05-13 |
CA2187180A1 (fr) | 1995-10-12 |
CN1144502A (zh) | 1997-03-05 |
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