CN1197696C - Method for making sole of shoe - Google Patents
Method for making sole of shoe Download PDFInfo
- Publication number
- CN1197696C CN1197696C CNB021028427A CN02102842A CN1197696C CN 1197696 C CN1197696 C CN 1197696C CN B021028427 A CNB021028427 A CN B021028427A CN 02102842 A CN02102842 A CN 02102842A CN 1197696 C CN1197696 C CN 1197696C
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- CN
- China
- Prior art keywords
- air bag
- sole
- polyurethane
- polyurethane foam
- powder
- 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.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
-
- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The present invention relates to a method for making sole of shoe which not only produces the shoe sole without causing a peeling between an air bag and a formed polyurethane foam but also easily removes burr formed on the periphery of a window part of the air bag after the molding. The production method of the shoe sole made of a polyurethane foam filled with the air bag includes adhering powders to the window part of the air bag, followed by mounting the air bag in a mold and then, forming the polyurethane foam in the mold. The production method of the shoe sole made of a polyurethane foam filled with the air bag includes adhering a urethane reaction accelerator to the window part of the air bag, followed by mounting the air bag in a mold and then, forming the polyurethane foam in the mold.
Description
Technical field
The present invention relates to the manufacture method of sole.More specifically relate to after the sole manufacturing is intact the manufacture method of the sole that the burr that can easily the pore position at air bag be formed are removed.
Background technology
In recent years, not only light but also solid polyurethane foam plastics is widely used in sole.Wherein, in order to reduce the impact that is applied on the pin, developed the inner sole that the air bag that can improve the sole shock-absorbing capacity is housed.In order to improve the cohesive with polyurethane foam plastics, usually heat-curable urethane is used for this air bag.
But, the opposite effects that the good adhesive property of this air bag and polyurethane foam plastics brings is, because look that from the outside the burr and the air bag of the polyurethane foam plastics that produces on the edge at pore position of the air bag that is loaded into are bonded together securely, for will spending, the aesthetic property that improves appearance removes so-called burr for a long time, when the burr of dissolving removal with an organic solvent, itself also is subjected to the erosion of organic solvent air bag and sole, has caused the decline of sole quality.
The content of invention
The manufacture method that the purpose of this invention is to provide sole, this method can make between the polyurethane foam plastics of air bag and shaping and not peel off, and can easily remove again simultaneously after being shaped in the burr of the edge formation at the pore position of air bag.
Promptly, one of the present invention is the manufacture method that is equipped with at the bottom of the polyurethane foam plastics shoemaking of air bag, described air bag contains in sole, its part is exposed outside in the side of sole, this method is to make powder adherence behind the pore position of air bag, this air bag is installed in the finishing die, then in finishing die, form the manufacture method of polyurethane foam plastics sole.
The present invention's two is the manufacture methods that are equipped with at the bottom of the polyurethane foam plastics shoemaking of air bag, described air bag contains in sole, its part is exposed outside in the side of sole, this method is after making the polyurethane-reinforcement reaction promoter stick to the pore position of air bag, this air bag is installed in the finishing die, then in finishing die, form the manufacture method of polyurethane foam plastics sole.
The working of an invention mode
The air bag of being made by heat-curable urethane can be suitable as air bag.The advantage of the air bag that heat-curable urethane is made is that the sole that it and polyurethane foam plastics are made has good cohesive.But its shortcoming is, as previously mentioned, the burr and the air bag that produce around the pore position of air bag during shaping are bonded together securely, are difficult to remove burr.But this shortcoming can all be overcome by the present invention 1 and the present invention 2.
The shape of air bag and size are different because of the kind and the size of footwear, cannot treat different things as the same.Therefore, desirable way is the suitable air bag of different choice according to shoes kind etc.
Though air bag contains in the sole usually, look from the outside in the side of sole and can observe air bag that its part is exposed.In this specification this part of exposing is called the pore position.
Among the present invention 1 and the present invention 2, powder and polyurethane-reinforcement reaction promoter are sticked to the pore position.Like this, powder and polyurethane-reinforcement reaction promoter are sticked under the situation at pore position, the polyurethane foam plastics burr that are formed at the edge at pore position in the sole manufacture process are peeled off from the pore position easily, therefore can shorten the required time of so-called unhairing limit.With organic solvent unhairing limit the time,, can not worry almost that sole and air bag are subjected to the erosion of organic solvent owing to infer the time that can shorten this operation again.Therefore, the present invention 1 and the present invention's 2 manufacture method all can be described as the method that significantly improves the shoe sole production rate.
At first, the present invention 1 is described.
The object lesson of powder can be enumerated inorganic powders such as talcum powder, kaolin, silica, sodium sulphate, olefine kind resin powder, nylon powder, organosilicon powder, fluorine resin powder, polyester powders such as wheat flour, corn flour, starch, polyethylene and polypropylene, organic carboxylate powder etc.Wherein, the surface of organosilicon powder and fluorine resin powder can be lower, so be more satisfactory.In the organic carboxylate, from adhering powder consideration equably, water miscible alkali metal carboxylate is comparatively desirable.
According to the easy degree that adheres to air bag pore position and the uniformity of powder coating, the average grain diameter of powder is to be advisable below 50 μ m, be preferably below 30 μ m, be more preferably below 20 μ m, lower limit is more than 0.01 μ m, be preferably more than 0.05 μ m, be more preferably more than 0.1 μ m.From above scope, the average grain diameter of powder is generally 0.01～50 μ m, is preferably 0.05～30 μ m, more preferably 0.1～20 μ m.This powder contains various shapes, and is for example fibrous.Except that spheric granules, average grain diameter is shown it with the mean value of the length of the length of the long axis direction of 1 particle and short-axis direction, and the average grain diameter of each particle is in above-mentioned number range.Again, the average grain diameter of powder looks like to measure by the SEM analysis diagram.
Powder can directly adhere to the pore position of air bag.Perhaps, powder is disperseed and even be dissolved in the solvent, after forming dispersion liquid or solution (hereinafter referred to as dispersion soln) and sticking to the pore position of air bag, dry dispersion soln and make powder adherence also passable at the pore position of air bag.Again, the dispersion soln described in this specification is meant and powder disperseed and even is dissolved in the solvent and the homogeneous mixture that forms.
The method that powder is directly adhered to the pore position of air bag can adopt powder adherence in the conventional method that is attached body.Coating, spraying, impregnating method are for example arranged.
Employing disperses powder and even is dissolved in the solvent and the dispersion soln that forms sticks to when making the method for this dispersion soln drying behind the pore position of air bag, as long as solvent can make powder disperse or make powder dissolution.Such solvent comprises water, the monohydric alcohol of carbon numbers 1～4 such as methyl alcohol, ethanol, isopropyl alcohol, butanols, acetone, ethyl acetate, methyl ethyl ketone, ether, dimethyl ether, LPG etc.Wherein, the monohydric alcohol of water and carbon number 1～4 is owing to the material that is difficult for air bag produces harmful effect, so be suitable for use.
Dispersion soln can be powder to be dispersed in the solvent and the solution that forms, also can be a part of powder is dispersed in the solvent and with other part powder dissolutions in solvent and the solution that forms can also be with whole powder dissolutions solution that face forms in solvent.Content to powder in the dispersion soln is not particularly limited, and is generally about 0.5～50 weight %, more preferably 2～20 weight %.The method that makes dispersion soln stick to the pore position of air bag can be used conventional method, for example, and coating, spraying, injection, impregnating.After dispersion soln sticks to the pore position of air bag, can make the dispersion soln drying, form the powder coating at the pore position by general stove or drier.
In order to form uniform powder coating at the pore position, improve the performance on unhairing limit, preferably contain surfactant in the dispersion soln.
Can exemplify out soap as surfactant, alkyl sulfate/salt, polyethylene oxide alkyl ethers sulfuric ester/salt, alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkyl sulfo succinate, alkyl diphenyl ether disulfonate, alkylphosphonic, anion surfactants such as naphthalene sulfonic acid-formaldehyde condensation product, polyethylene oxide alkyl ethers, polyoxygenated alkene alkyl ether, the polyethylene glycol oxide sorbitan aliphatic ester, polyethylene glycol oxide D-sorbite fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid esters, the polyethylene glycol oxide alkylamine, non-ionic surface active agents such as alkyl alkanolamide, alkylamine salt, cationic surfactants such as quaternary ammonium salt, alkyl betaine, amphoteric surfactantes such as amine oxide etc.
As surfactant, should use can effectively reduce the surface can silicone surfactant and fluorine-containing surfactant.
As the example of silicone surfactant, comprise the organosiloxane of the modified side chain shown in the formula (I),
In the formula, X is that polyethers residue, polyglycereol residue, pyrrolidones residue, betaine residue, sulfate residue, phosphate residue or quaternary ammonium salt residue, m represent 0～100 integer, and n represents 0～100 integer; Two terminal-modified organosiloxanes shown in the formula (II),
In the formula, X and m are the same; A terminal-modified organosiloxane shown in the formula (III),
In the formula, X and m are the same; Two organosiloxanes that end side is chain modified shown in the formula (IV),
In the formula, X, m and n are the same.In these silicone surfactants, best is the organosiloxane of the modified side chain shown in the formula (I).
Again, the X in the formula is the polyethers residue preferably, especially with the group shown in the formula (V),
-C
3H
6O(C
2H
4O)
a(C
3H
6)
bR
1 (V)
In the formula, a represents 5～9 integer, and b represents 0～10 integer, and R1 represents the alkyl of carbon number 1～10.
Good especially silicone surfactant is the organosiloxane of the modified side chain represented of following formula,
In the formula, p represents 1～3 integer, and a is the same.The organosiloxane of this modified side chain has as long as can reduce the good result of surface energy on a small quantity.
Again, fluorine-containing surfactant can be enumerated anionic fluorosurfactants such as perfluoroalkyl carbonate, perfluoralkyl phosphate, fluorine sulfosuccinic acid, cationic fluorochemical surfactants such as perfluoroalkyl leptodactyline, amphoteric fluorotensides such as perfluoroalkyl betaine, fluorine sulfobetaines, nonionic fluorine-containing surfactants such as perfluoroalkyl amine oxide, perfluoroalkyl ethanol ethylene oxide adduct etc.Wherein, be preferably amphoteric fluorotensides and non-ionic surface active agent, be more preferably perfluoroalkyl ethanol ethylene oxide adduct (for example, perfluoroalkyl ethanol ethoxy-ethanol salt).
Surface-active contents in the dispersion soln is different because of its kind etc., though cannot treat different things as the same, in general, also can give full play to performance and cost angle and consider even change from service condition, be preferably 0.05～5 weight %, more preferably 0.1～1 weight %.In addition, contain surfactant dispersion soln can with the aforesaid same means of dispersion soln that do not contain surfactant, powder and surfactant are adhered to the pore position of air bag.
The amount of powder that adheres to air bag pore position is different because of kind of powder etc., though cannot treat different things as the same, is generally 1～100g/m
2, 5～50g/m more preferably
2
Among the present invention 2, adhering to the polyurethane-reinforcement reaction promoter at the pore position.Be stained with at the pore position under the situation of polyurethane-reinforcement reaction promoter, peel off from the pore position, just can shorten the needed time of unhairing limit if can in the sole manufacture process, easily will be formed at the polyurethane foam plastics burr at edge, pore position.Moreover, during with organic solvent unhairing limit, owing to infer the time that can shorten its operation, can not worry almost therefore that sole and air bag are subjected to invading to touch.So we can say the present invention 2 manufacture method is the method that can significantly improve the shoe sole production rate.
Can exemplify out the low molecular weight compound that polyurethane-reinforcement catalyst, molecule contain plural reactive hydrogen as the polyurethane-reinforcement reaction promoter.Wherein, the polyurethane-reinforcement catalyst is as long as just can quicken the polyurethane-reinforcement reaction on a small quantity, so should be used in the present invention 2.
Use when in advance the polyurethane-reinforcement catalyst being adhered to the air bag at pore position, when burr touch the pore position, because the effect of polyurethane-reinforcement catalyst constitutes the rapid resinification of polyurethane foam plastics of burr, before being affixed to the pore position, just solidified, thereby thought that these burr can easily peel off from the pore position.
Can exemplify out triethylenediamine as the polyurethane-reinforcement catalyst, N, N, N ', N '-4-methyl hexamethylene diamine, N, N, N ', N '-4-methyl-diaminopropane, N, N, N ', N "; N "-five methyl diethylentriamine, N, N ', N '-trimethyl aminoethylpiperazine, N, the N-dimethyl cyclohexyl amine, N, the N-dimethyl benzylamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, tri-n-butylamine, two (dimethylamino alkyl) piperazine, N, N, N ', N '-tetramethylethylenediamine, N, N '-diethyl benzylamine, two (N, N-diethyl amino ethyl group) adipate, N, N, N ', N '-tetramethyl-1, the 3-butanediamine, N, N-dimethyl-beta-phenyl ethylamine, 1-isobutyl group-glyoxal ethyline, 1, the 2-methylimidazole, the 1-methylimidazole, glyoxal ethyline, N, N-dimethylamino hexanol etc.These catalyst can use separately separately, also can mix use more than 2 kinds.In these catalyst, what possess higher promotion resinification effect is 1,2-methylimidazole, triethylenediamine, N, N, N ', N '-4-methyl hexamethylene diamine.
Again, the polyurethane-reinforcement catalyst also can use in the lump with organo-metallic compounds such as dibutyl tin dilaurate, stannous oleate, cobalt naphthenate, lead naphthenates.
The low molecular weight compound that molecule is contained two above reactive hydrogens is during as polyurethane-reinforcement promoter, when polyurethane foam plastics forms, part polyurethane foam plastics becomes burr and has touched the pore position, at this moment, the low molecular weight compound that molecule contains two above reactive hydrogens has quickened the foaming of this polyurethane foam plastics, reduced the contact area at burr and pore position, thereby thought and easily burr to be peeled off from the pore position.
The low molecular weight compound that includes two above reactive hydrogens as molecule can exemplify out ethylene glycol, diethylene glycol (DEG), propane diols, 1,4-butanediol, 1,5-pentanediol, methyl pentanediol, 1, the polyalcohol of carbon numbers 2～6 such as 6-hexylene glycol, trimethylolpropane, glycerine, pentaerythrite, two glycerine, glucose, D-sorbite, the aliphatic polyamine of carbon numbers such as ethylenediamine, hexamethylene diamine 2～6; The aromatic polyamine of carbon numbers 6～10 such as diethyl toluene diamine, dimethyl methyl phenylenediamine, the alkanolamine of carbon numbers such as diethanol amine, triethanolamine, diisopropanolamine (DIPA) 2～6 etc.Wherein be preferably and be the compound of liquid under 20 ℃ of temperature.The molecular weight of these compounds is preferably 60～200 generally below 300, is preferably 60～120.
In order to make the polyurethane-reinforcement reaction promoter stick to the pore position as far as possible equably, improve the performance of removing burr, can use surfactant and polyurethane-reinforcement reaction promoter in the lump and stick to the pore position.For example, can mix the pore position that sticks to air bag to polyurethane-reinforcement reaction promoter and surfactant.
Used surfactant is identical with the surfactant of use among aforementioned the present invention 1.
The amount of surfactant is different because of its kind etc., though cannot treat different things as the same, but in general, even consider from the service condition angle that also can give full play to performance and cost that changes, polyurethane-reinforcement reaction promoter for 100 weight portions, be 0.05～5 weight portion, be preferably 0.1～1 weight portion.
The method that the polyurethane-reinforcement reaction promoter is adhered to the pore position of air bag is not particularly limited, can adopts conventional adhesion means, as coating, spraying, impregnating.
The amount of polyurethane-reinforcement reaction promoter that adheres to air bag pore position is different because of kind of polyurethane-reinforcement reaction promoter etc., though cannot treat different things as the same, is generally 1～60g/m
2, 5～30g/m more preferably
2
In the present invention 1 and the present invention 2, it is that polyurethane, polyester are polyurethane etc. that the raw material of the polyurethane foam plastics of formation sole can exemplify out polyethers.
Urethane raw is not particularly limited, can adopts known raw material.As urethane raw, it is desirable to polyhydric alcohol solutions and isocyanate prepolymer.Polyhydric alcohol solutions contains polyol components such as PPG and PEPA, chain extender, water, defoamer and required catalyst etc.Isocyanate prepolymer is become to be grouped into PICs such as diphenyl methylene diisocyanate or its modified products by the polyol component of PPG, PEPA etc.All available known compounds such as these PPGs, PEPA, chain extender, defoamer, catalyst, PIC composition, isocyanate prepolymer.
Polyurethane foam plastics can be by reactions such as polyol component and PIC composition, isocyanate prepolymer and water as required, chain extender, defoamer, catalyst and is made.
The bonding strength of long more polyurethane foam plastics that then forms of the surface viscosity extinction time of polyurethane foam plastics and air bag is high more.Therefore, from improving the angle of this bonding strength, the surface viscosity extinction time of polyurethane foam plastics is generally more than 40 seconds, and more than 45 seconds, better more than 50 seconds, good especially is more than 55 seconds, is preferably in more than 60 seconds more fortunately.Even the surface viscosity extinction time of polyurethane foam plastics as mentioned above, utilize the present invention 1 and the present invention's 2 the formed polyurethane foam plastics burr of manufacture method also can easily remove.
When the surface viscosity extinction time of the polyurethane foam plastics of indication is meant free foaming in this specification, touch foam sensation viscosity diminishes required time with finger tip in foaming beginning back.
From the outward appearance and the light-weighted viewpoint of foamed plastics, polyurethane foam plastics formed body close is with 0.2-0.4g/m
2Be advisable, more preferably 0.25～0.35g/m
2
Material to sole finishing die used among the present invention is not particularly limited, and comprises iron, stainless steel, copper, aluminium, aluminium alloy, epoxy resin, phenolic resins etc.Interior shape to the sole finishing die also is not particularly limited, as long as have the shape corresponding to the shape of final sole.
Be to improve demolding performace, will be coated with in advance, spray, flood releasing agent, make releasing agent stick to the finishing die inner face and get final product at the inner face of finishing die.Used releasing agent comprises dimethicone, mineral oil, paraffin etc., but the present invention is not limited to this.
The sole that air bag is housed can adopt conventional method manufacturing.Promptly, the air bag that the pore position is stained with powder places in the sole finishing die with needed interior shape, the raw material that forms polyurethane foam plastics is injected in this finishing die, in finishing die, forms polyurethane foam plastics behind the matched moulds, just can make the sole that air bag is housed.
The back demoulding that is shaped just can obtain being equipped with the sole of having of the air bag shape that formalizes.
Because air bag itself has elasticity,, burr have so just been produced so between finishing die around the pore position of gained sole and pore position, trickle gap is arranged.But, utilize method of the present invention, year easily peels off these burr from the pore position, so process the needed time again after shortening the unhairing limit.
Again, the manufacture method of sole of the present invention is not limited in the method for only making sole, also comprises the sole autofrettage in the shoemaking process of making sole and footwear main body (so-called vamp) simultaneously.
Embodiment
Example I-1～I-6 and Comparative Example I-1～I-2
Polyhydric alcohol solutions [flower king (strain) system, commodity エ デ by name at 100 weight portions
イOff
オOne system AS-6-51U] middle 2.0 weight portion PEPAs [flower king (strain) system, the commodity エ デ by name of adding
イOff
オOne system E-540], 0.3 weight portion surfactant [flower king (strain) system, commodity エ デ by name
イOff
オOne system AS-60H], 0.5 weight portion ethylene glycol [Japanese catalyst (strain) system], 1.2 weight parts waters, 1.2 weight portion catalyst [flower king (strain) system, commodity エ デ by name
イOff
オOne system AS-651-60C], 2 weight portion pigment [Japanese ピ ダ メ Application ト (strain) system, commodity NV-9-953 by name], mix [worker of Hitachi machine (strain) system, trade name: UM-15] with hand mixer.
In pouring into a bucket of type low pressure foaming machine, add above-mentioned polyhydric alcohol solutions, the liquid temperature is transferred to 40 ℃, and adding polyisocyanate compounds in another bucket (flower king (strain) system, commodity エ デ イ Off オ one system B-3525 by name], its liquid temperature is transferred to 35 ℃.
With above-mentioned foaming machine polyhydric alcohol solutions and polyisocyanate compounds are mixed stirring, be injected in the sole finishing die, generate polyurethane foam plastics.The surface viscosity extinction time of this moment is 60 seconds.The density of the polyurethane foam plastics that makes is 0.32g/cm
3
With the prescription of this polyurethane foam plastics, the unhairing limit performance and the anti-stripping performance of the air bag that adhered to the powder shown in the table 1 are investigated according to following test method.Its result is as shown in table 2.
Table 1
| The embodiment sequence number | Powder etc. |
| I-1 | The dry thing of the 30% Sodium Benzoate aqueous solution (average grain diameter: 1～20 μ m *6) *1 |
| I-2 | The dry thing of 30% potassium acetate solution *1(average grain diameter: 1～20 μ m *6) 99 weight % and polyether modified siloxanes *21 weight % |
| I-3 | The dry thing of the 10% Sodium Benzoate aqueous solution *1(average grain diameter: 1～20 μ m *6) 99 weight % and fluorine-containing surfactants *31 weight % |
| I-4 | Sodium Benzoate (average grain diameter: 5～20 μ m *6) |
| I-5 | Organosilicon powder *4(average grain diameter: 0.5 μ m *7) |
| I-6 | The 10% Sodium Benzoate aqueous solution, 99 weight % and fluorine-containing surfactants *3The dry thing of 1 weight % *1(average grain diameter: 1～20 μ m *6) |
| Comparative Example I-1 | Do not have |
| I-2 | Dimethicone *5 |
(notes) * 1: dry again gained after the aqueous solution is adhered to; * 2: the organosiloxane of modified side chain [SHIN-ETSU HANTOTAI's chemical industry (strain) system, commodity are called KF640]; * 3: perfluoroalkyl ethanol ethoxy-ethanol salt [Network ラ リ ア Application ト ジ
ャパ Application (strain) system, commodity Fluowet OTN by name]; * the シ リ of 4:GE Toshiba コ one (strain) system, commodity are called ト ス パ one Le 105; * 5: releasing agent; * 6: average grain diameter is in aforementioned number range; * 7: the value of putting down in writing in the catalogue.
A. unhairing limit performance
(every side has the air bag of two about 8mm * 20mm to use pore as pattern to be ready to the sole finishing die, have corresponding to be about 300mm, the about 110mm of Breadth Maximum, the about 90mm of minimum widith, the about 50mm of heel maximum height in be iron with metal mould for formation, the material of the interior shape of sole), releasing agent [flower king (strain) system, commodity プ ラ パ ワ 1 by name] is sprayed on the inner face of finishing die, after wiping with wasted ends, the temperature of finishing die is transferred to 60 ± 2 ℃.
Then, powder shown in the table 1 etc. is sticked to air bag behind the pore position of air bag packs in the finishing die with the amount shown in the table 2, then, polyurethane solutions (mixed solution of polyhydric alcohol solutions and polyisocyanate compounds) is injected in the finishing die along the direction straight line from the heel to the tiptoe, and matched moulds is made the polyurethane foam plastics sole that air bag is housed.Again, once soluble in water powder in example I-1～I-3 and I-6, make this aqueous solution attached on the air bag, evaporation drying water makes powder adherence to air bag.
Inject beginning demoulding after 5 minutes, after 1 minute, begin the unhairing limit with the bamboo chip that speckles with organic solvent (mixed solvents of methyl ethyl ketone 50 weight %, ethyl acetate 20 weight % and naphtha 30 weight %), measure the required time of all burr that removal is adhered at about 50% pore position, it is removed the yardstick of performance as estimating burr.Its mean value is obtained in same powder operation five times, judges according to following evaluation criterion.
[metewand]
◎: the used time of unhairing limit is in 2 minutes
Zero: the used time of unhairing limit is 2 in above 4 minutes
*: the used time of unhairing limit is more than 4 minutes
B. anti-fissility
After estimating unhairing limit performance, around the air bag pore position of observation formed body, investigate the place whether air bag and foamed plastics are peeled off.This is operated with five samples, obtains the mean value of the position number of peeling off, and judges according to following metewand.
[metewand]
Zero: peel off the position and be less than a place
*: peel off the position more than a place
Table 2
| The embodiment sequence number | Adhesion amount (the g/m of powder etc. 2) | Unhairing limit performance | Anti-fissility |
| I-1 | 10～15 | ○ | ○ |
| I-2 | 10～15 | ◎ | ○ |
| I-3 | 10～15 | ◎ | ○ |
| I-4 | 15～20 | ○ | ○ |
| I-5 | 20～30 | ◎ | ○ |
| I-6 | 10～15 | ◎ | ○ |
| Comparative Example I-1 | Do not have | × | ○ |
| I-2 | 10～15 | ◎ | × |
By the result shown in the table 2 as can be known, example I-1 is to the unhairing limit performance of example I-6 gained sole, and it is good especially to compare with Comparative Example I-1, and anti-stripping performance might as well.
On the other hand, because phenomenon has also taken place to peel off Comparative Example I-2, anti-fissility is poor under the situation of having used releasing agent (dimethicone) as can be known.
Example II-1～example II-8 and Comparative Example I I-1～Comparative Example I I-2
The prescription of the polyurethane foam plastics that employing and example I-1～I-5 and Comparative Example I-1～I-2 are same, investigate the unhairing limit property of the air bag that is attached with the polyurethane-reinforcement reaction promoter shown in the table 3 according to following test method, investigate anti-fissility equally with example I-1～I-5 and Comparative Example I-1～I-2.Its result is shown in the table 4.
Table 3
| The embodiment sequence number | The composition (weight portion) of polyurethane-reinforcement reaction promoter etc. |
| II-1 | 1,2-methylimidazole (100) |
| II-2 | 1,2-methylimidazole (100), silicone surfactant *1(0.1) |
| II-3 | Triethylenediamine (40), ethylene glycol (60) |
| II-4 | Triethylenediamine (40), ethylene glycol (60), fluorine-containing surfactant *2(0.1) |
| II-5 | Poly-tertiary amine glycol *3(100) |
| II-6 | Diethylene glycol (DEG) (100), silicone surfactant *1(0.1) |
| II-7 | Diethyl toluene diamine (100) |
| II-8 | Potassium octanoate (60), diethylene glycol (DEG) (40) |
| Comparative Example I I-1 | Do not have |
| II-2 | Dimethicone *4 |
(notes) * 1: the organosiloxane of modified side chain [SHIN-ETSU HANTOTAI's chemical industry (strain) system, commodity KF640 by name]; * 2: perfluoroalkyl ethanol ethoxy-ethanol salt [Network ラ リ ア Application ト ジ ャ パ Application (strain) system, commodity Fluowet OTN by name]; * 3: flower king (strain) system, commodity カ オ one ラ イ ザ one P200 by name; * 4: releasing agent.
C. unhairing limit performance
(every side has the air bag of two about 8mm * 20mm to use pore as pattern to be ready to the sole finishing die, have corresponding to be about 300mm, the about 110mm of Breadth Maximum, minimum widith is about 90mm, following metal mould for formation, the material of the interior shape of sole among the about 50mm of heel maximum height is iron), releasing agent [flower king (strain) system, commodity プ ラ パ ワ 1 by name] is sprayed on the inner face of finishing die, after wiping with wasted ends, the temperature of mould is transferred to 60 ± 2 ℃.
Then, polyurethane-reinforcement reaction promoter shown in the table 3 is sticked to air bag behind the pore position of air bag packs in the finishing die with the amount shown in the table 4, then, polyurethane solutions (mixed solution of polyhydric alcohol solutions and polyisocyanate compounds) is injected in the finishing die along the direction straight line from the heel to the tiptoe, and matched moulds is made the polyurethane foam plastics sole that air bag is housed.
Inject beginning demoulding after 5 minutes, after 1 minute with speckling with organic solvent (methyl ethyl ketone 50 weight %, ethyl acetate 20 weight % and naphtha 30 weight %) bamboo chip begin the unhairing limit, measure all burr attached to about 50% pore position have been removed required time, with its standard as evaluation unhairing limit performance.With same polyurethane-reinforcement reaction promoter operation five times, ask its mean value, judge according to following metewand then.
[metewand]
◎: the used time of unhairing limit is in 2 minutes
Zero: the used time of unhairing limit is in more than 2 minutes 4 minutes
*: the used time of unhairing limit is more than 4 minutes
Table 4
| The embodiment sequence number | Adhesion amount (the g/m of polyurethane-reinforcement reaction promoter etc. 2) | Unhairing limit performance | Anti-fissility |
| II-1 | 15～20 | ○ | ○ |
| II-2 | 10～15 | ◎ | ○ |
| II-3 | 15～20 | ○ | ○ |
| II-4 | 10～15 | ◎ | ○ |
| II-5 | 15～20 | ○ | ○ |
| II-6 | 15～20 | ○ | ○ |
| II-7 | 10～15 | ◎ | ○ |
| II-8 | 10～15 | ○ | ○ |
| Comparative Example I I-1 | Do not have | × | ○ |
| II-2 | 10～15 | ◎ | × |
By the result shown in the table 4 as can be known, example II-1 is to the unhairing limit performance of example II-8 gained sole, and it is good especially to compare with Comparative Example I I-1, and anti-stripping performance might as well.
On the other hand, because phenomenon has also taken place to peel off Comparative Example I I-2, anti-fissility is poor under the situation of having used releasing agent (dimethicone) as can be known.
When adopting manufacture method of the present invention to make sole, peeling off between the polyurethane foam plastics of air bag and shaping can not taken place, after being shaped, can easily remove the burr in the formation of the edge, pore position of air bag simultaneously.
Claims (8)
1. the manufacture method at the bottom of the polyurethane foam plastics shoemaking of air bag is housed, described air bag contains in sole, its part is exposed to the outside in the side of sole, it is characterized in that, make powder adherence behind the pore position of air bag, described air bag is packed in the finishing die, in finishing die, form the polyurethane foam plastics sole then.
2. the manufacture method of sole as claimed in claim 1, its feature is that also the average grain diameter of powder is below 50 μ m.
3. the manufacture method of sole as claimed in claim 1 or 2, its feature also is, powder disperseed and to being dissolved in the solvent and behind the pore position that decomposed solution that forms or solution stick to air bag, dry described dispersion liquid or solution make the pore position of powder adherence at air bag.
4. the manufacture method of sole as claimed in claim 3, its feature also is, contains surfactant in dispersion liquid or the solution.
5. the manufacture method at the bottom of the polyurethane foam plastics shoemaking of air bag is housed, described air bag contains in sole, its part is exposed to the outside in the side of sole, it is characterized in that, after making the polyurethane-reinforcement reaction promoter stick to the pore position of air bag, described air bag is packed in the finishing die, in finishing die, form the polyurethane foam plastics sole then.
6. the manufacture method of sole as claimed in claim 5, its feature is that also the polyurethane-reinforcement reaction promoter is the low molecular weight compound that contains two above reactive hydrogens in polyurethane-reinforcement catalyst or the molecule.
7. as the manufacture method of claim 5 or 6 described soles, its feature also is, the polyurethane-reinforcement reaction promoter is sticked to the pore position of air bag with surfactant.
8. the manufacture method of sole as claimed in claim 7, its feature also be, surfactant is to be selected from silicone surfactant and fluorine-containing surfactant at least a kind.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP017748/2001 | 2001-01-26 | ||
| JP2001017750 | 2001-01-26 | ||
| JP017748/01 | 2001-01-26 | ||
| JP017750/2001 | 2001-01-26 | ||
| JP2001017748A JP2002219005A (en) | 2001-01-26 | 2001-01-26 | Production method of shoes sole |
| JP017750/01 | 2001-01-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1368426A CN1368426A (en) | 2002-09-11 |
| CN1197696C true CN1197696C (en) | 2005-04-20 |
Family
ID=26608317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021028427A Expired - Fee Related CN1197696C (en) | 2001-01-26 | 2002-01-25 | Method for making sole of shoe |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20020063115A (en) |
| CN (1) | CN1197696C (en) |
-
2002
- 2002-01-21 KR KR1020020003378A patent/KR20020063115A/en not_active Application Discontinuation
- 2002-01-25 CN CNB021028427A patent/CN1197696C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1368426A (en) | 2002-09-11 |
| KR20020063115A (en) | 2002-08-01 |
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