CN102517918A - Manufacturing method of water-proof and air-permeable ultrafine fiber safety shoe leather - Google Patents
Manufacturing method of water-proof and air-permeable ultrafine fiber safety shoe leather Download PDFInfo
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Abstract
The invention relates to a manufacturing method of water-proof and air-permeable superfine fiber safety shoe leather. The method comprises the following process steps of: (1) preparing superfine sea-island fibers; (2) making a non-woven fabric; (3) impregnating with a wet process; (4) decreasing with toluene; (5) performing after-finishing on a polyamide leather substrate; (6) performing flame retardant treatment; (7) veneering with a dry process; (8) aligning and laminating release paper obtained in the step (7) with the polyamide leather substrate obtained in the step (6), drying, and stripping the release paper and the polyamide leather substrate to obtain semi-finished safety shoe leather; and (9) washing the semi-finished safety shoe leather in a flowing water groove with water to obtain the safety shoe leather, wherein the water temperature is 30-60 DEG C, the speed of water current is 4-6 m/min, and the flow of water is 0.1-0.5 m<3>/min. According to the manufacturing method, the aims of permeating and resisting water can be fulfilled by using the safety shoe leather; and the problem of poor air permeability caused by superfine fiber leather manufacturing is solved, and the safety shoe leather has good handfeel, waterproofness, high stripping property and electric insulation.
Description
Technical field
The present invention relates to a kind of manufacturing approach of labour protection footwear leather, especially a kind of manufacturing approach of superfine fibre labour protection footwear leather of waterproof and breathable.
Background technology
Corium has good waterproof and breathable performance, but receives restriction and the people of its output, the price increase day by day to the leather demand, along with the fast development of superfine fibre; Superfine fiber leather is more and more by people's approval, but behind superfine fibre nonwoven cloth impregnation polyurethane, the base of polyamide leather (Base) itself has gas permeability preferably; The base of polyamide leather (Base) is behind the dry method veneer; The surface has been coated with one deck polyurethane uniformly, has excellent waterproofness, but the gas permeability extreme difference.
Summary of the invention
The objective of the invention is to overcome the deficiency that exists in the prior art; A kind of manufacturing approach of superfine fibre labour protection footwear leather of waterproof and breathable is provided; Not only solved the difficult problem of the gas permeability difference that the superfine fibre process hides brought, had also that good hand feeling, water proofing property, height are peeled off, electric insulation.
According to technical scheme provided by the invention, the manufacturing approach of the superfine fibre labour protection footwear of said waterproof and breathable leather, characteristic is to comprise following processing step:
(1) preparation super fine denier islands-in-sea type fibre: polyamide 6 is as island component; Low density polyethylene (LDPE) is as extra large component; Is 40: 60～60: 40 mixing and stirring with polyamide 6 and low density polyethylene (LDPE) according to mass ratio, and mixing speed is 30～50 rev/mins, and mixing time is 15～20 minutes; Stir entering fabric of island-in-sea type spinning pack through single extruder type spinning machine fusion, extrude the formation tow through distribution plate and spinnerets, the temperature of single extruder type spinning machine is 90～295 ℃; The tow that obtains carries out drawing-off through three road drawing roller again, and the draw ratio of three road drawing roller is 1: 2.2～2.8: 3.5～4; Spinning oil in oil bath; After crimping machine curls, 50～75 ℃ of oven dry 5～10 minutes; It is that 50～55mm, fiber number are the staple fibre of 5.0～7.0dtex that cut-out makes length;
(2) make nonwoven fabric: the staple fibre that step (1) is obtained carries out thick shredding on thick opener; By blower fan the staple fibre of thick shredding is delivered to big bin mixing then; Carry out smart shredding through five roller refined openers again, again through extreme trace hopper, air pressure face case feeding fiber, after the electronic scale weighing; After carrying out combing by carding machine, on the lapping machine, carry out lapping; On needing machine, puncture at last, obtain nonwoven fabric; The nonwoven fabric that obtains is neat with the nonwoven fabric cutting through bead cutter, carries out thermal contraction fixation, and temperature is 80～140 ℃, and the nonwoven fabric speed of a motor vehicle is 5～10m/min, and the gap of shaping roller tube is: nonwoven fabric cloth thickness/1.1～1.5;
(3) wet method impregnation: the nonwoven fabric that step (2) is obtained is through containing immersion liquid, pushes impregnation repeatedly through roller repeatedly, will contain immersion liquid evenly extruding infiltrate through in the nonwoven fabric, the coating weight that contains immersion liquid on the nonwoven fabric is 2.0～3.0 times of nonwoven fabric grammes per square metre; Again with scraper with nonwoven fabric double-edged contain immersion liquid scrape clean after; The aqueous solution through containing dimethyl formamide solidifies foaming; Setting time is 40～60 minutes, and setting temperature is 25～45 ℃, and the mass percentage concentration of the aqueous solution of dimethyl formamide is 22～28%; Then nonwoven fabric is washed through rinsing bowl, dimethyl formamide residual on the nonwoven fabric is washed off, obtain porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base;
(4) toluene decrement: the porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base that step (3) is obtained passes through 6～8 toluene grooves, and the temperature of toluene groove is 80～95 ℃; Pass through the residual toluene of rinsing bowl flush away again, the water temperature of rinsing bowl is 95～100 ℃, obtains polyamide leather base; The speed of a motor vehicle of said porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base is 3～8m/min;
(5) put in order behind the polyamide leather base: the polyamide leather base that step (4) is obtained is through the prebake of seven layers of trawlnet formula baking oven, and temperature of oven is 70～100 ℃; Again polyamide leather base is drawn fully impregnation in the liquid bath that contains the leather softening agent, the impregnation time is 4～8 minutes; Squeeze the unnecessary leather softening agent of polyamide leather substrate surface through rubber rollers then, the hydraulic fluid rate is 85～90%; Through the expanding dryer polyamide leather base is dried tentering again, bake out temperature is 130～160 ℃; After rub the skin machine continuously polyamide leather base is rubbed skin, the dental lamina gap of rubbing the skin machine continuously is 3～6cm, and the dental lamina hunting frequency is 200～300 rev/mins; The speed of a motor vehicle of said polyamide leather base is 3～8m/min;
(6) flame treatment: step (5) is handled the polyamide leather base obtain through containing the oil groove of fire-retardant treatment liquid; Push through squeezer roll again; Pick-up rate is 70～90%, and again 130～160 ℃ oven for drying, the speed of a motor vehicle of said polyamide leather base is 3～8 meters/minute;
(7) dry method veneer: successively be coated in release liners on by order from the bottom up investment precoat, middle coating intermediate, tack coat coating; Said investment precoat makes surface layer at 80～130 ℃ of oven dry 15～20s; Said middle coating intermediate makes the middle level at 80～130 ℃ of oven dry 25～45s, and said tack coat coating makes tack coat at 60～100 ℃ of oven dry 25～35s;
(8) the polyamide leather base alignment and congruence that release liners that step (7) is obtained and step (6) obtain; After oven dry, release liners and polyamide leather base are peeled off, bake out temperature is 120～150 ℃ again; The speed of a motor vehicle is 4～8m/min, obtains described labour protection footwear leather semi-finished product;
(9) the labour protection footwear leather semi-finished product that step (8) obtained place mobile tank to wash, and water temperature is 30～60 ℃, and the speed of current is 4～6m/min, and the flow of water is 0.1～0.5m
3/ min; The washing back is in 120～140 ℃ of oven dry, and the speed of a motor vehicle is 6～8m/min, obtains described labour protection footwear leather.
In the step (7), said investment precoat comprises following component, and the component ratio is counted by weight: polyurethane resin is 100 parts, N, and dinethylformamide is: 10～20 parts, toluene is: 50～60 parts; The solid content of said polyurethane resin is 28～32%, and the modulus during said polyurethane resin 100% percentage elongation is 100～200kg/cm
2
In the step (7), said middle coating intermediate comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 5～10 parts, toluene is: 10～20 parts; The solid content of said polyurethane resin is 60～90%, and the modulus during said polyurethane resin 100% percentage elongation is 12～25kg/cm
2
In the step (7), said adhesive linkage coating comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts; N, dinethylformamide is: 10～18 parts, toluene is: 30～50 parts; Crosslinking agent is: 3～10 parts, promoter is: 1～5 part; The solid content of said polyurethane resin is 35～50%, and the modulus during said polyurethane resin 100% percentage elongation is 10～15kg/cm
2
In the step (7), the viscosity during 25 ℃ of said lining coating is 2000～4000Pa.s.
In the step (7), the viscosity during 25 ℃ of said middle coating intermediates is 5000～8000Pa.s.
In the step (7), the viscosity during 25 ℃ of said adhesive linkage coating is 4500～6000Pa.s.
In the step (5), said leather softening agent is that mass percentage concentration is 10～15% leather softener solution.
In the step (3), saidly contain immersion liquid and comprise following component, the component ratio is counted by weight: 100 parts of EUs, 20～50 parts of dimethyl formamides, 0.5～3 part of emulsifying agent, 0.1～0.5 part of levelling agent, 1～3 part of bleeding agent, 0.5～3 part of abscess conditioning agent; The elastic modelling quantity that said EU contains immersion liquid is 70～100kg/cm
2, the said solid content that contains immersion liquid is 18～25%.
The manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable of the present invention leather, can so that to labour protection footwear leather reach the purpose of air permeable waterproof; Not only solved the difficult problem of the gas permeability difference that the superfine fibre process hides brought, had also that good hand feeling, water proofing property, height are peeled off, electric insulation.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further.
The present invention adopts superfine fibre nonwoven cloth wet method impregnation polyurethane, and the solvent of polyurethane is dimethyl formamide (DMF), and DMF is very easily water-soluble; The nonwoven fabric of the good polyurethane of impregnation is passed through in the tank; Because polyurethane is water insoluble, and DMF and water can dissolve each other, make that the DMF in water and the polyurethane replaces; After the water drying, on polyurethane film, form micropore, reach ventilative effect; Its key point is to control well the big or small uniformity of abscess, if in pure water, solidify, the DMF replacement rate can be too fast; The surface can be replaced earlier and solidify; DMF like this just cannot replace, and just is prone to dissolving polyurethane on every side during oven dry, thereby destroys the foam structure of polyurethane; The present invention is through pol, the temperature of allotment water-setting solid-liquid, and (pol is: 18.5～23%), delay the speed of its displacement, reach displacement evenly, form uniform abscess, improved feel, folding line, also improved gas permeability in the water coagulating basin, to add certain DMF.
The key point of the present invention's control is the water treatment behind the dry method veneer; Polyurethane itself is to be insoluble to after whose dry method veneer makes; The surface forms the closely knit film of one deck and plays waterproof effect, and the dry method veneer is selected special waterproof and breathable type polyurethane for use, contains in this polyurethane and contains hydrophilic component and part salinity on hydrophilic radical or the molecular backbone; Finished product labour protection behind the face of posting leather is put into the tank that can flow; Owing to there is concentration difference, the salinity of activity such as potassium chloride, sodium chloride dissociate out and are dissolved in the water in the surface layer polyurethane, and oven dry forms superfine microcellular structure; Thereby play water-proof breathable properties preferably, its water-proof breathable properties has reached Europe (EN20345) standard.
Labour protection footwear leather generally is applied in special industry or post, and superfine denier polyamide short fibre system labour protection footwear are removed from office general required thickness at 1.8～2.2mm, and is very high to the requirement of the comfort type worn, water-proof breathable properties, intensity.The present invention has solved these difficult problems one by one, has played good effect, can compare favourably with corium.The present technology that is in a leading position in the whole industry of this technology, its formed foam structure and shape be other technology can't form.
The relative viscosity of polyamide 6 used in the present invention is 2.2～2.4, and density is 1.08g/cm
3, fusing point is 215～225 ℃; The poly relative viscosity of low viscosity is 2.4～2.6, and density is 0.92g/cm
3, fusing point is 98～110 ℃.
Employed emulsifying agent, levelling agent, bleeding agent, abscess conditioning agent are commercially available among the present invention, and emulsifying agent can adopt soap commonly used, Arabic gum or sodium alkyl benzene sulfonate; The levelling agent that levelling agent can adopt Shenzhen rent land bodyguard chemical industry Co., Ltd to produce; The weaving bleeding agent that bleeding agent can adopt grand Shen, Nantong chemical industry Co., Ltd to produce; The abscess conditioning agent has been the chemical substance of froth breaking effect, is added in the foam mixture with independent or compound form, as the counteracting agent of foam stabiliser; Make that abscess is all or part of to be lost stablely, be generally the methyl polysiloxane compounds, be used to prepare the special construction foams; As having the foam of natural sponge shape, the model that adopts Jiande City Shunfa Chemical Additive Co., Ltd. to produce in the embodiment of the invention is the abscess conditioning agent of SF-318, can improve the permeability of slurry; Accelerate the replacing velocity of water and dimethyl formamide, can obviously improve the one-tenth flesh property of product, increase the film forming abscess; Can make PU layer film forming cell size even, become vertical, can improve the breathable moisture permeability of base; Can improve and combine rerum naturas such as fastness, the peel strength of stable prod between PU layer and the base cloth.
Crosslinking agent used in the present invention and promoter all can be adopted commercially available crosslinking agent and promoter, and the model that can adopt Shanghai Huide Resin Co., Ltd to produce like crosslinking agent is the crosslinking agent of HDN-75, and solid content is 75 ± 2%; Viscosity is 200～6,000,000; NCO%=13 ± 1% generally can be used as bridging agent, and solvent is ETAC; Chemical name is: 6 '-[ethyl (4-aminomethyl phenyl) amino]-3 '-methyl-2 '-(phenyl amino)-spiral shell [isobenzofuran-1 (3H), 9 '-(9H) xanthenes]-3-ketone;
Promoter used in the present invention is that adhesive for polyurethane is used promoter; Like methyl diethanolamine, triethanolamine, inositol hexaphosphate or triethylamine; The model of producing for Shanghai Huide Resin Co., Ltd that adopts in the embodiment of the invention is the promoter of HDC-02; Solid content is 0 ± 2%, generally can be used as promoter, and solvent is ETAC.
Leather softener used in the present invention is commercially available leather softener.
Embodiment one: a kind of manufacturing approach of superfine fibre labour protection footwear leather of waterproof and breathable comprises following processing step:
(1) preparation super fine denier islands-in-sea type fibre: polyamide 6 is as island component, and low density polyethylene (LDPE) is 40: 60 mixing and stirring with polyamide 6 and low density polyethylene (LDPE) according to mass ratio as extra large component, and mixing speed is 30 rev/mins, and mixing time is 15 minutes; Stir entering fabric of island-in-sea type spinning pack through single extruder type spinning machine fusion; Extruding the temperature that forms tow screw extruder first district through distribution plate and spinnerets is 90 ℃, and the temperature in second district is 180 ℃, and the temperature in the 3rd district is 250 ℃; The temperature in the 4th district is 280 ℃; The temperature in the 5th district is 280 ℃, and the temperature in the 6th district is 285 ℃, and the temperature of SECTOR-SEVEN is 285 ℃; The tow that obtains carries out drawing-off through three road drawing roller again, and the draw ratio of three road drawing roller is 1: 2.2: 3.5; Spinning oil in oil bath; After crimping machine curls, 50 ℃ of oven dry 10 minutes; It is that 50mm, fiber number are the staple fibre of 5.0dtex that cut-out makes length;
(2) make nonwoven fabric: the staple fibre that step (1) is obtained carries out thick shredding on thick opener; By blower fan the staple fibre of thick shredding is delivered to big bin mixing then; Carry out smart shredding through five roller refined openers again, again through extreme trace hopper, air pressure face case feeding fiber, after the electronic scale weighing; After carrying out combing by carding machine, on the lapping machine, carry out lapping; On needing machine, puncture at last, obtain nonwoven fabric; The nonwoven fabric that obtains is neat with the nonwoven fabric cutting through bead cutter, carries out thermal contraction fixation, and the temperature in thermal contraction fixation first district is 80 ℃; The temperature in second district is 100 ℃; The temperature in the 3rd district is 120 ℃, and the temperature in the 4th district is 130 ℃, and the temperature in the 5th district is 140 ℃; The nonwoven fabric speed of a motor vehicle is 5m/min, and the gap of shaping roller tube is: nonwoven fabric cloth thickness/1.1;
(3) wet method impregnation: the nonwoven fabric that step (2) is obtained is through containing immersion liquid, pushes impregnation repeatedly through roller repeatedly, will contain immersion liquid evenly extruding infiltrate through in the nonwoven fabric; The coating weight that contains immersion liquid on the nonwoven fabric is 2.0 times of nonwoven fabric grammes per square metre, saidly contains immersion liquid and comprises following component, and the component ratio is counted by weight: 100 parts of EUs; 20 parts of dimethyl formamides, 0.5 part of emulsifying agent, 0.1 part of levelling agent; 1 part of bleeding agent, 0.5 part of abscess conditioning agent; The elastic modelling quantity that said EU contains immersion liquid is 70kg/cm
2, the said solid content that contains immersion liquid is 18%; Again with scraper with nonwoven fabric double-edged contain immersion liquid scrape clean after, solidify foaming through the aqueous solution that contains dimethyl formamide, setting time is 40 minutes, setting temperature is 25 ℃, the mass percentage concentration of the aqueous solution of dimethyl formamide is 22%; Then nonwoven fabric is washed through rinsing bowl, dimethyl formamide residual on the nonwoven fabric is washed off, obtain porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base;
(4) toluene decrement: the porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base that step (3) is obtained passes through 6 toluene grooves, and the temperature of toluene groove is 80 ℃; Pass through the residual toluene of rinsing bowl flush away again, the water temperature of rinsing bowl is 95 ℃, obtains polyamide leather base; The speed of a motor vehicle of said porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base is 3m/min;
(5) put in order behind the polyamide leather base: the polyamide leather base that step (4) is obtained is through the prebake of seven layers of trawlnet formula baking oven, and temperature of oven is 70 ℃; Again polyamide leather base is drawn fully impregnation in the liquid bath that contains the leather softening agent, the impregnation time is 4 minutes, and said leather softening agent is that mass percentage concentration is 10% leather softener solution; Squeeze the unnecessary leather softening agent of polyamide leather substrate surface through rubber rollers then, the hydraulic fluid rate is 85%; Through the expanding dryer polyamide leather base is dried tentering again, bake out temperature is 130 ℃; After rub the skin machine continuously polyamide leather base is rubbed skin, the dental lamina gap of rubbing the skin machine continuously is 3cm, and the dental lamina hunting frequency is 200 rev/mins; The speed of a motor vehicle of said polyamide leather base is 3m/min;
(6) flame treatment: step (5) is handled the polyamide leather base obtain through containing the oil groove of fire-retardant treatment liquid, and through the squeezer roll extruding, pick-up rate is 70% again, and again 130 ℃ oven for drying, the speed of a motor vehicle of said polyamide leather base is 3 meters/minute;
(7) dry method veneer: successively be coated in release liners on by order from the bottom up investment precoat, middle coating intermediate, tack coat coating; Said investment precoat makes surface layer at 80 ℃ of oven dry 15s; Said middle coating intermediate makes the middle level at 80 ℃ of oven dry 25s, and said tack coat coating makes tack coat at 60 ℃ of oven dry 25s;
Said investment precoat comprises following component, and the component ratio is counted by weight: polyurethane resin is 100 parts, N, and dinethylformamide is: 10 parts, toluene is: 50 parts; The solid content of said polyurethane resin is 28%, and the modulus during said polyurethane resin 100% percentage elongation is 100kg/cm
2, the viscosity during 25 ℃ of said lining coating is 2000Pa.s;
Said middle coating intermediate comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 5 parts, toluene is: 10 parts; The solid content of said polyurethane resin is 60%, and the modulus during said polyurethane resin 100% percentage elongation is 12kg/cm
2, the viscosity during 25 ℃ of said middle coating intermediates is 5000Pa.s;
Said adhesive linkage coating comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 10 parts, toluene is: 30 parts, crosslinking agent is: 3 parts, promoter is: 1 part; The solid content of said polyurethane resin is 35%, and the modulus during said polyurethane resin 100% percentage elongation is 10kg/cm
2, the viscosity during 25 ℃ of said adhesive linkage coating is 4500Pa.s;
(8) the polyamide leather base alignment and congruence that release liners that step (7) is obtained and step (6) obtain after oven dry, is peeled off release liners and polyamide leather base again, and bake out temperature is 120 ℃, and the speed of a motor vehicle is 4m/min, obtains described labour protection footwear and removes from office semi-finished product;
(9) the labour protection footwear leather semi-finished product that step (8) obtained place mobile tank to wash, and water temperature is 30 ℃, and the speed of current is 4m/min, and the flow of water is 0.1m
3/ min; The washing back is in 120 ℃ of oven dry, and the speed of a motor vehicle is 6m/min, obtains described labour protection footwear leather.
Embodiment two: a kind of manufacturing approach of superfine fibre labour protection footwear leather of waterproof and breathable comprises following processing step:
(1) preparation super fine denier islands-in-sea type fibre: polyamide 6 is as island component, and low density polyethylene (LDPE) is 50: 50 mixing and stirring with polyamide 6 and low density polyethylene (LDPE) according to mass ratio as extra large component, and mixing speed is 40 rev/mins, and mixing time is 16 minutes; Stir entering fabric of island-in-sea type spinning pack through single extruder type spinning machine fusion, extrude the formation tow through distribution plate and spinnerets, the temperature in screw extruder first district is 95 ℃; The temperature in second district is 185 ℃; The temperature in the 3rd district is 255 ℃, and the temperature in the 4th district is 285 ℃, and the temperature in the 5th district is 285 ℃; The temperature in the 6th district is 290 ℃, and the temperature of SECTOR-SEVEN is 295 ℃; The tow that obtains carries out drawing-off through three road drawing roller again, and the draw ratio of three road drawing roller is 1: 2.3: 3.6; Spinning oil in oil bath; After crimping machine curls, 55 ℃ of oven dry 8 minutes; It is that 51mm, fiber number are the staple fibre of 6.0dtex that cut-out makes length;
(2) make nonwoven fabric: the staple fibre that step (1) is obtained carries out thick shredding on thick opener; By blower fan the staple fibre of thick shredding is delivered to big bin mixing then; Carry out smart shredding through five roller refined openers again, again through extreme trace hopper, air pressure face case feeding fiber, after the electronic scale weighing; After carrying out combing by carding machine, on the lapping machine, carry out lapping; On needing machine, puncture at last, obtain nonwoven fabric; The nonwoven fabric that obtains is neat with the nonwoven fabric cutting through bead cutter, carries out thermal contraction fixation, and the temperature in thermal contraction fixation first district is 85 ℃; The temperature in second district is 105 ℃; The temperature in the 3rd district is 125 ℃, and the temperature in the 4th district is 135 ℃, and the temperature in the 5th district is 140 ℃; The nonwoven fabric speed of a motor vehicle is 6m/min, and the gap of shaping roller tube is: nonwoven fabric cloth thickness/1.2;
(3) wet method impregnation: the nonwoven fabric that step (2) is obtained is through containing immersion liquid, pushes impregnation repeatedly through roller repeatedly, will contain immersion liquid evenly extruding infiltrate through in the nonwoven fabric; The coating weight that contains immersion liquid on the nonwoven fabric is 2.5 times of nonwoven fabric grammes per square metre, saidly contains immersion liquid and comprises following component, and the component ratio is counted by weight: 100 parts of EUs; 30 parts of dimethyl formamides, 0.59 part of emulsifying agent, 0.2 part of levelling agent; 2 parts of bleeding agents, 0.6 part of abscess conditioning agent; The elastic modelling quantity that said EU contains immersion liquid is 80kg/cm
2, the said solid content that contains immersion liquid is 19%; Again with scraper with nonwoven fabric double-edged contain immersion liquid scrape clean after, solidify foaming through the aqueous solution that contains dimethyl formamide, setting time is 50 minutes, setting temperature is 26 ℃, the mass percentage concentration of the aqueous solution of dimethyl formamide is 23%; Then nonwoven fabric is washed through rinsing bowl, dimethyl formamide residual on the nonwoven fabric is washed off, obtain porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base;
(4) toluene decrement: the porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base that step (3) is obtained passes through 7 toluene grooves, and the temperature of toluene groove is 85 ℃; Pass through the residual toluene of rinsing bowl flush away again, the water temperature of rinsing bowl is 96 ℃, obtains polyamide leather base; The speed of a motor vehicle of said porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base is 4m/min;
(5) put in order behind the polyamide leather base: the polyamide leather base that step (4) is obtained is through the prebake of seven layers of trawlnet formula baking oven, and temperature of oven is 80 ℃; Again polyamide leather base is drawn fully impregnation in the liquid bath that contains the leather softening agent, the impregnation time is 5 minutes, and said leather softening agent is that mass percentage concentration is 11% leather softener solution; Squeeze the unnecessary leather softening agent of polyamide leather substrate surface through rubber rollers then, the hydraulic fluid rate is 86%; Through the expanding dryer polyamide leather base is dried tentering again, bake out temperature is 140 ℃; After rub the skin machine continuously polyamide leather base is rubbed skin, the dental lamina gap of rubbing the skin machine continuously is 4cm, and the dental lamina hunting frequency is 250 rev/mins; The speed of a motor vehicle of said polyamide leather base is 4m/min;
(6) flame treatment: step (5) is handled the polyamide leather base obtain through containing the oil groove of fire-retardant treatment liquid, and through the squeezer roll extruding, pick-up rate is 80% again, and again 140 ℃ oven for drying, the speed of a motor vehicle of said polyamide leather base is 4 meters/minute;
(7) dry method veneer: successively be coated in release liners on by order from the bottom up investment precoat, middle coating intermediate, tack coat coating; Said investment precoat makes surface layer at 90 ℃ of oven dry 16s; Said middle coating intermediate makes the middle level at 90 ℃ of oven dry 30s, and said tack coat coating makes tack coat at 70 ℃ of oven dry 30s;
Said investment precoat comprises following component, and the component ratio is counted by weight: polyurethane resin is 100 parts, N, and dinethylformamide is: 15 parts, toluene is: 55 parts; The solid content of said polyurethane resin is 29%, and the modulus during said polyurethane resin 100% percentage elongation is 150kg/cm
2, the viscosity during 25 ℃ of said lining coating is 3000Pa.s;
Said middle coating intermediate comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 6 parts, toluene is: 15 parts; The solid content of said polyurethane resin is 70%, and the modulus during said polyurethane resin 100% percentage elongation is 20kg/cm
2, the viscosity during 25 ℃ of said middle coating intermediates is 6000Pa.s;
Said adhesive linkage coating comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 12 parts, toluene is: 40 parts, crosslinking agent is: 5 parts, promoter is: 2 parts; The solid content of said polyurethane resin is 40%, and the modulus during said polyurethane resin 100% percentage elongation is 12kg/cm
2, the viscosity during 25 ℃ of said adhesive linkage coating is 5000Pa.s;
(8) the polyamide leather base alignment and congruence that release liners that step (7) is obtained and step (6) obtain; After oven dry, release liners and polyamide leather base are peeled off, bake out temperature is 120～150 ℃ again; The speed of a motor vehicle is 4～8m/min, obtains described labour protection footwear leather semi-finished product;
(9) the labour protection footwear leather semi-finished product that step (8) obtained place mobile tank to wash, and water temperature is 50 ℃, and the speed of current is 5m/min, and the flow of water is 0.2m
3/ min; The washing back is in 140 ℃ of oven dry, and the speed of a motor vehicle is 8m/min, obtains described labour protection footwear leather.
Embodiment three: a kind of manufacturing approach of superfine fibre labour protection footwear leather of waterproof and breathable comprises following processing step:
(1) preparation super fine denier islands-in-sea type fibre: polyamide 6 is as island component, and low density polyethylene (LDPE) is 60: 40 mixing and stirring with polyamide 6 and low density polyethylene (LDPE) according to mass ratio as extra large component, and mixing speed is 50 rev/mins, and mixing time is 20 minutes; Stir entering fabric of island-in-sea type spinning pack through single extruder type spinning machine fusion, extrude the formation tow through distribution plate and spinnerets, the temperature in screw extruder first district is 90 ℃; The temperature in second district is 190 ℃; The temperature in the 3rd district is 245 ℃, and the temperature in the 4th district is 275 ℃, and the temperature in the 5th district is 280 ℃; The temperature in the 6th district is 285 ℃, and the temperature of SECTOR-SEVEN is 285 ℃; The tow that obtains carries out drawing-off through three road drawing roller again, and the draw ratio of three road drawing roller is 1: 2.8: 4; Spinning oil in oil bath; After crimping machine curls, 75 ℃ of oven dry 5 minutes; It is that 55mm, fiber number are the staple fibre of 7.0dtex that cut-out makes length;
(2) make nonwoven fabric: the staple fibre that step (1) is obtained carries out thick shredding on thick opener; By blower fan the staple fibre of thick shredding is delivered to big bin mixing then; Carry out smart shredding through five roller refined openers again, again through extreme trace hopper, air pressure face case feeding fiber, after the electronic scale weighing; After carrying out combing by carding machine, on the lapping machine, carry out lapping; On needing machine, puncture at last, obtain nonwoven fabric; The nonwoven fabric that obtains is neat with the nonwoven fabric cutting through bead cutter, carries out thermal contraction fixation, and the temperature in thermal contraction fixation first district is 80 ℃; The temperature in second district is 110 ℃; The temperature in the 3rd district is 130 ℃, and the temperature in the 4th district is 135 ℃, and the temperature in the 5th district is 140 ℃; The nonwoven fabric speed of a motor vehicle is 10m/min, and the gap of shaping roller tube is: nonwoven fabric cloth thickness/1.5;
(3) wet method impregnation: the nonwoven fabric that step (2) is obtained is through containing immersion liquid, pushes impregnation repeatedly through roller repeatedly, will contain immersion liquid evenly extruding infiltrate through in the nonwoven fabric; The coating weight that contains immersion liquid on the nonwoven fabric is 3.0 times of nonwoven fabric grammes per square metre, saidly contains immersion liquid and comprises following component, and the component ratio is counted by weight: 100 parts of EUs; 50 parts of dimethyl formamides, 3 parts of emulsifying agents, 0.5 part of levelling agent; 3 parts of bleeding agents, 3 parts of abscess conditioning agents; The elastic modelling quantity that said EU contains immersion liquid is 100kg/cm
2, the said solid content that contains immersion liquid is 25%; Again with scraper with nonwoven fabric double-edged contain immersion liquid scrape clean after, solidify foaming through the aqueous solution that contains dimethyl formamide, setting time is 60 minutes, setting temperature is 45 ℃, the mass percentage concentration of the aqueous solution of dimethyl formamide is 28%; Then nonwoven fabric is washed through rinsing bowl, dimethyl formamide residual on the nonwoven fabric is washed off, obtain porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base;
(4) toluene decrement: the porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base that step (3) is obtained passes through 8 toluene grooves, and the temperature of toluene groove is 95 ℃; Pass through the residual toluene of rinsing bowl flush away again, the water temperature of rinsing bowl is 100 ℃, obtains polyamide leather base; The speed of a motor vehicle of said porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base is 8m/min;
(5) put in order behind the polyamide leather base: the polyamide leather base that step (4) is obtained is through the prebake of seven layers of trawlnet formula baking oven, and temperature of oven is 100 ℃; Again polyamide leather base is drawn fully impregnation in the liquid bath that contains the leather softening agent, the impregnation time is 8 minutes, and said leather softening agent is that mass percentage concentration is 15% leather softener solution; Squeeze the unnecessary leather softening agent of polyamide leather substrate surface through rubber rollers then, the hydraulic fluid rate is 90%; Through the expanding dryer polyamide leather base is dried tentering again, bake out temperature is 160 ℃; After rub the skin machine continuously polyamide leather base is rubbed skin, the dental lamina gap of rubbing the skin machine continuously is 6cm, and the dental lamina hunting frequency is 300 rev/mins; The speed of a motor vehicle of said polyamide leather base is 8m/min;
(6) flame treatment: step (5) is handled the polyamide leather base obtain through containing the oil groove of fire-retardant treatment liquid, and through the squeezer roll extruding, pick-up rate is 90% again, and again 160 ℃ oven for drying, the speed of a motor vehicle of said polyamide leather base is 8 meters/minute;
(7) dry method veneer: successively be coated in release liners on by order from the bottom up investment precoat, middle coating intermediate, tack coat coating; Said investment precoat makes surface layer at 130 ℃ of oven dry 20s; Said middle coating intermediate makes the middle level at 130 ℃ of oven dry 45s, and said tack coat coating makes tack coat at 100 ℃ of oven dry 35s;
Said investment precoat comprises following component, and the component ratio is counted by weight: polyurethane resin is 100 parts, N, and dinethylformamide is: 20 parts, toluene is: 60 parts; The solid content of said polyurethane resin is 32%, and the modulus during said polyurethane resin 100% percentage elongation is 200kg/cm
2, the viscosity during 25 ℃ of said lining coating is 4000Pa.s;
Said middle coating intermediate comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 10 parts, toluene is: 20 parts; The solid content of said polyurethane resin is 90%, and the modulus during said polyurethane resin 100% percentage elongation is 25kg/cm
2, the viscosity during 25 ℃ of said middle coating intermediates is 8000Pa.s;
Said adhesive linkage coating comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N, dinethylformamide is: 18 parts, toluene is: 50 parts, crosslinking agent is: 10 parts, promoter is: 5 parts; The solid content of said polyurethane resin is 50%, and the modulus during said polyurethane resin 100% percentage elongation is 15kg/cm
2, the viscosity during 25 ℃ of said adhesive linkage coating is 6000Pa.s;
(8) the polyamide leather base alignment and congruence that release liners that step (7) is obtained and step (6) obtain after oven dry, is peeled off release liners and polyamide leather base again, and bake out temperature is 150 ℃, and the speed of a motor vehicle is 8m/min, obtains described labour protection footwear and removes from office semi-finished product;
(9) the labour protection footwear leather semi-finished product that step (8) obtained place mobile tank to wash, and water temperature is 60 ℃, and the speed of current is 6m/min, and the flow of water is 0.5m
3/ min; The washing back is in 130 ℃ of oven dry, and the speed of a motor vehicle is 7m/min, obtains described labour protection footwear leather.
The performance parameter of the labour protection footwear leather that the present invention obtains is as shown in table 1.
Table 1
Claims (9)
1. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable leather is characterized in that, comprises following processing step:
(1) preparation super fine denier islands-in-sea type fibre: polyamide 6 is as island component; Low density polyethylene (LDPE) is as extra large component; Is 40:60 ~ 60:40 mixing and stirring with polyamide 6 and low density polyethylene (LDPE) according to mass ratio, and mixing speed is 30 ~ 50 rev/mins, and mixing time is 15 ~ 20 minutes; Stir entering fabric of island-in-sea type spinning pack through single extruder type spinning machine fusion, extrude the formation tow through distribution plate and spinnerets, the temperature of single extruder type spinning machine is 90 ~ 295 ℃; The tow that obtains carries out drawing-off through three road drawing roller again, and the draw ratio of three road drawing roller is 1:2.2 ~ 2.8:3.5 ~ 4; Spinning oil in oil bath; After crimping machine curls, 50 ~ 75 ℃ of oven dry 5 ~ 10 minutes; It is that 50 ~ 55mm, fiber number are the staple fibre of 5.0 ~ 7.0dtex that cut-out makes length;
(2) make nonwoven fabric: the staple fibre that step (1) is obtained carries out thick shredding on thick opener; By blower fan the staple fibre of thick shredding is delivered to big bin mixing then; Carry out smart shredding through five roller refined openers again, again through extreme trace hopper, air pressure face case feeding fiber, after the electronic scale weighing; After carrying out combing by carding machine, on the lapping machine, carry out lapping; On needing machine, puncture at last, obtain nonwoven fabric; The nonwoven fabric that obtains is neat with the nonwoven fabric cutting through bead cutter, carries out thermal contraction fixation, and temperature is 80 ~ 140 ℃, and the nonwoven fabric speed of a motor vehicle is 5 ~ 10m/min, and the gap of shaping roller tube is: nonwoven fabric cloth thickness/1.1 ~ 1.5;
(3) wet method impregnation: the nonwoven fabric that step (2) is obtained is through containing immersion liquid, pushes impregnation repeatedly through roller repeatedly, will contain immersion liquid evenly extruding infiltrate through in the nonwoven fabric, the coating weight that contains immersion liquid on the nonwoven fabric is 2.0 ~ 3.0 times of nonwoven fabric grammes per square metre; Again with scraper with nonwoven fabric double-edged contain immersion liquid scrape clean after; The aqueous solution through containing dimethyl formamide solidifies foaming; Setting time is 40 ~ 60 minutes, and setting temperature is 25 ~ 45 ℃, and the mass percentage concentration of the aqueous solution of dimethyl formamide is 22 ~ 28%; Then nonwoven fabric is washed through rinsing bowl, dimethyl formamide residual on the nonwoven fabric is washed off, obtain porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base;
(4) toluene decrement: the porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base that step (3) is obtained passes through 6 ~ 8 toluene grooves, and the temperature of toluene groove is 80 ~ 95 ℃; Pass through the residual toluene of rinsing bowl flush away again, the water temperature of rinsing bowl is 95 ~ 100 ℃, obtains polyamide leather base; The speed of a motor vehicle of said porous matter elastomeric polyethers type polyurethane nonwoven fabric wet method base is 3 ~ 8m/min;
(5) put in order behind the polyamide leather base: the polyamide leather base that step (4) is obtained is through the prebake of seven layers of trawlnet formula baking oven, and temperature of oven is 70 ~ 100 ℃; Again polyamide leather base is drawn fully impregnation in the liquid bath that contains the leather softening agent, the impregnation time is 4 ~ 8 minutes; Squeeze the unnecessary leather softening agent of polyamide leather substrate surface through rubber rollers then, the hydraulic fluid rate is 85 ~ 90%; Through the expanding dryer polyamide leather base is dried tentering again, bake out temperature is 130 ~ 160 ℃; After rub the skin machine continuously polyamide leather base is rubbed skin, the dental lamina gap of rubbing the skin machine continuously is 3 ~ 6cm, and the dental lamina hunting frequency is 200 ~ 300 rev/mins; The speed of a motor vehicle of said polyamide leather base is 3 ~ 8m/min;
(6) flame treatment: step (5) is handled the polyamide leather base obtain through containing the oil groove of fire-retardant treatment liquid; Push through squeezer roll again; Pick-up rate is 70 ~ 90%, and again 130 ~ 160 ℃ oven for drying, the speed of a motor vehicle of said polyamide leather base is 3 ~ 8 meters/minute;
(7) dry method veneer: successively be coated in release liners on by order from the bottom up investment precoat, middle coating intermediate, tack coat coating; Said investment precoat makes surface layer at 80 ~ 130 ℃ of oven dry 15 ~ 20s; Said middle coating intermediate makes the middle level at 80 ~ 130 ℃ of oven dry 25 ~ 45s, and said tack coat coating makes tack coat at 60 ~ 100 ℃ of oven dry 25 ~ 35s;
(8) the polyamide leather base alignment and congruence that release liners that step (7) is obtained and step (6) obtain; After oven dry, release liners and polyamide leather base are peeled off, bake out temperature is 120 ~ 150 ℃ again; The speed of a motor vehicle is 4 ~ 8m/min, obtains described labour protection footwear leather semi-finished product;
(9) the labour protection footwear leather semi-finished product that step (8) obtained place mobile tank to wash, and water temperature is 30 ~ 60 ℃, and the speed of current is 4 ~ 6m/min, and the flow of water is 0.1 ~ 0.5m
3/ min; The washing back is in 120 ~ 140 ℃ of oven dry, and the speed of a motor vehicle is 6 ~ 8m/min, obtains described labour protection footwear leather.
2. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather; It is characterized in that: in the step (7); Said investment precoat comprises following component, and the component ratio is counted by weight: polyurethane resin is 100 parts, N; Dinethylformamide is: 10 ~ 20 parts, toluene is: 50 ~ 60 parts; The solid content of said polyurethane resin is 28 ~ 32%, and the modulus during said polyurethane resin 100% percentage elongation is 100 ~ 200kg/cm
2
3. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather; It is characterized in that: in the step (7); Said middle coating intermediate comprises following component, and the component ratio is counted by weight: polyurethane resin is: 100 parts, and N; Dinethylformamide is: 5 ~ 10 parts, toluene is: 10 ~ 20 parts; The solid content of said polyurethane resin is 60 ~ 90%, and the modulus during said polyurethane resin 100% percentage elongation is 12 ~ 25kg/cm
2
4. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather, it is characterized in that: in the step (7), said adhesive linkage coating comprises following component; The component ratio is counted by weight: polyurethane resin is: 100 parts; N, dinethylformamide is: 10 ~ 18 parts, toluene is: 30 ~ 50 parts; Crosslinking agent is: 3 ~ 10 parts, promoter is: 1 ~ 5 part; The solid content of said polyurethane resin is 35 ~ 50%, and the modulus during said polyurethane resin 100% percentage elongation is 10 ~ 15kg/cm
2
5. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather is characterized in that: in the step (7), the viscosity during 25 ℃ of said lining coating is 2000 ~ 4000Pa.s.
6. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather is characterized in that: in the step (7), the viscosity during 25 ℃ of said middle coating intermediates is 5000 ~ 8000 Pa.s.
7. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather is characterized in that: in the step (7), the viscosity during 25 ℃ of said adhesive linkage coating is 4500 ~ 6000Pa.s.
8. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather, it is characterized in that: in the step (5), said leather softening agent is that mass percentage concentration is 10 ~ 15% leather softener solution.
9. the manufacturing approach of the superfine fibre labour protection footwear of waterproof and breathable as claimed in claim 1 leather is characterized in that: in the step (3), saidly contain immersion liquid and comprise following component; The component ratio is counted by weight: 100 parts of EUs; 20 ~ 50 parts of dimethyl formamides, 0.5 ~ 3 part of emulsifying agent, 0.1 ~ 0.5 part of levelling agent; 1 ~ 3 part of bleeding agent, 0.5 ~ 3 part of abscess conditioning agent; The elastic modelling quantity that said EU contains immersion liquid is 70 ~ 100 kg/cm
2, the said solid content that contains immersion liquid is 18 ~ 25%.
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