CN104674564A - Method for producing crease-free synthetic leather - Google Patents

Method for producing crease-free synthetic leather Download PDF

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Publication number
CN104674564A
CN104674564A CN201510111519.1A CN201510111519A CN104674564A CN 104674564 A CN104674564 A CN 104674564A CN 201510111519 A CN201510111519 A CN 201510111519A CN 104674564 A CN104674564 A CN 104674564A
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China
Prior art keywords
base cloth
parts
cloth fabric
synthetic leather
material component
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Granted
Application number
CN201510111519.1A
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Chinese (zh)
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CN104674564B (en
Inventor
刘超
李苏
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Anta China Co Ltd
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Anta China Co Ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/06Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
    • D06N3/08Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products with a finishing layer consisting of polyacrylates, polyamides or polyurethanes or polyester
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/14Printing or colouring

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention discloses a method for producing crease-free synthetic leather. The method comprises the following steps: 1, preparing the following first material components: 80-100 parts of polyamide resin, 1-10 parts of organic montmorillonite and 0.2-0.8 part of an antioxidant; 2, preparing modified polyamide resin from the first material components; 3, preparing the following components in parts by weight: 100 parts of polyamide resin and 25-35 parts of modified polyamide resin; 4, processing and forming a base cloth fabric; 5, preparing the base cloth fabric, and dipping in polyving alcohol; 6, preparing 100 parts of polyester type polyurethane of which the solid content is 40%, 100-120 parts of dimethyl formamide, 10-15 parts of a pore-foaming agent, 1-4 parts of a surfactant, 5-10 parts of a solvent color material and 2-5 parts of a fluoride-containing high polymer; 7, taking out the base cloth fabric dipped in the step 5, and dipping into a solution of the step 6; 8, taking out the base cloth fabric dipped in the step 7, and washing with water; 9, drying and shaping; 10, adhering one pattern layer to the base cloth fabric treated in the step 8 through an adhesive layer. The synthetic leather produced by using the method is relatively good in crease resistance.

Description

A kind of production method without folding line synthetic leather
Technical field
The present invention relates to synthetic leather field, particularly, relate to a kind of method without folding line synthetic leather.
Background technology
Synthetic leather is widely used in shoe-making industry, and synthetic leather has excellent physical property and higher cost performance compared with corium, and originates unrestricted thus be widely used.Traditional synthetic leather is because itself manufacture craft and material limited, and in use after repeatedly bending, the surface of synthetic leather can form folding line, and then greatly affects attractive in appearance.
Repeatedly being bent to form the problem of folding line in order to improve conventional synthesis leather, in industry, a lot of research having been carried out to the folding quality of synthetic leather.The current method improved the folding quality of synthetic leather is mainly at dry method TPU film coating process, but this technique can increase the hardness of synthetic leather, reduces flexibility and the comfort property of synthetic leather, increases cost in addition because pasting the increase of TPU membrane operation on synthetic leather.Thus need to provide a kind of new solution.
Summary of the invention
The invention provides a kind of production method without folding line synthetic leather, comprise following steps: S1: prepare the first material component, with parts by weight, described first material component comprises polyamide 80 ~ 100 parts, organo montmorillonite 1 ~ 10 part, antioxidant 0.2-0.8 part; S2: by the blended granulation of described first material component, forms modified polyamide resin; S3: prepare the second material component, described second material component comprises the modified polyamide resin of polyamide and step S2 formation, and with parts by weight, modified polyamide resin is 100 parts, polyamide is 25 ~ 35 parts; S4: be base cloth fabric by described second material component machine-shaping; S5: prepare the base cloth fabric that described step S4 is formed, and described base cloth fabric be impregnated in polyvinyl alcohol; S6: prepare the 3rd material component, with parts by weight, described 3rd material component comprise solid content be 40% PAUR 100 parts, dimethyl formamide 100-120 part, pore-foaming agent 10-15 part, surfactant 1-4 part, solvent borne colorant 5-10 part, fluorine element high polymer 2-5 part; S7: take out in step S5 through the base cloth fabric of dipping, and impregnated in the solution comprising the 3rd material component; S8: take out the base cloth fabric after step S7 dipping, and it is washed; S9: the base cloth fabric after step S8 washing is dried and shaped; S10: one patterned layer is fitted on the base cloth fabric after step S9 process by an adhesive linkage; Described adhesive linkage is that one first solution evaporation solute precipitation forms, and described first solution, with parts by weight, comprises EU 25 ~ 45 parts, solid content 60% thermoplastic polyester 55 ~ 75 parts that solid content is 40%; Described patterned layer is that one second solution evaporation solute precipitation forms, and described second solution is the polyurethane solutions that solid content is greater than 65%.
Further, the polyamide model in described step S1 is PA6 or PA66, and described antioxidant is the four seasons defend four alcohol esters.
Further, the treatment temperature of described step S2 is 75 DEG C ~ 125 DEG C.
Further, described step S2 by double screw extruder by the blended granulation of described first material component.
Further, described second material component machine-shaping is base cloth fabric by the shaping or shaping technique that punctures of weaving by described step S4.
Further, the fibre fineness of the base cloth fabric of described step S5 preparation is less than 0.ldtex.
Further, the PAUR model of described step S6 is A-7030, and pore-foaming agent model is carboxymethyl cellulose or diatomite, and surfactant model is S-7, and solvent borne colorant model is EK-048, and fluorine element high polymer model is F-3D.
Further, described step S10 solid content be 40% EU model be A-1065G, solid content 60% thermoplastic polyester model is M-530.
Further, by an adhesive linkage one patterned layer fitted on the base cloth fabric after step S9 process in described step S10 and comprise following steps: S11: described patterned layer is formed on a release layer; S12: form described adhesive linkage between described patterned layer and the base cloth fabric after step S9 process; S13: peel off described release layer.
Prepared by the present invention improves from the base cloth fabric of synthetic leather, adhesive linkage and patterned layer without folding line synthetic leather simultaneously.Adopt nano imvite to carry out intercalation modifying to synthetic leather scrim material, improve modulus and the rebound performance of synthetic leather base cloth fabric; Adopt low viscosity thermoplastic polyurethane blends as the adhesive linkage of synthetic leather, improve resilience and the modulus of synthetic leather, make synthetic leather have better folding quality; Adopt high solid content polyurethane as synthetic leather patterned layer, reduce the hole because solvent evaporation is formed at surface layer, make synthetic leather be not easy to form folding line in bending rear surface.
Accompanying drawing explanation
Figure 1A depicts the schematic diagram that one embodiment of the invention forms patterned layer on base cloth fabric;
Figure 1B depicts the schematic diagram that one embodiment of the invention peels off release layer;
Detailed description of the invention
For understanding technical scheme of the present invention better, elaborate below with reference to concrete diagram.Should be understood that following specific embodiment is not used to limit the concrete enforcement aspect of technical scheme of the present invention, it is only the adoptable enforcement aspect of technical solution of the present invention.
The invention provides a kind of production method without folding line synthetic leather, comprise following steps: S1: prepare the first material component, with parts by weight, the first material component comprises polyamide 80 ~ 100 parts, organo montmorillonite 1 ~ 10 part, antioxidant 0.2-0.8 part; S2: by the blended granulation of the first material component, forms modified polyamide resin; S3: prepare the second material component, the second material component comprises the modified polyamide resin of polyamide and step S2 formation, and with parts by weight, modified polyamide resin is 100 parts, and polyamide is 25 ~ 35 parts; S4: be base cloth fabric by the second material component machine-shaping; S5: the preparation process S4 base cloth fabric formed, and base cloth fabric be impregnated in polyvinyl alcohol; S6: prepare the 3rd material component, with parts by weight, the 3rd material component comprise solid content be 40% PAUR 100 parts, dimethyl formamide 100-120 part, pore-foaming agent 10-15 part, surfactant 1-4 part, solvent borne colorant 5-10 part, fluorine element high polymer 2-5 part; S7: take out in step S5 through the base cloth fabric of dipping, and impregnated in the solution comprising the 3rd material component; S8: take out the base cloth fabric after step S7 dipping, and it is washed; S9: the base cloth fabric after step S8 washing is dried and shaped; S10: one patterned layer is fitted on the base cloth fabric after step S9 process by an adhesive linkage; Adhesive linkage is that one first solution evaporation solute precipitation forms, and the first solution, with parts by weight, comprises EU 25 ~ 45 parts, solid content 60% thermoplastic polyester 55 ~ 75 parts that solid content is 40%; Patterned layer is that one second solution evaporation solute precipitation forms, and the second solution is the polyurethane solutions that solid content is greater than 65%.
It should be noted that, the relation of " with parts by weight " its based material each component relative mass, as the first material component comprises polyamide 80 ~ 100g, organo montmorillonite 1 ~ 10g, antioxidant 0.2-0.8g.The statement that each material component is similar herein also can be understood according to this, and hereinafter similar description repeats no more.
Easy understand, the first solution evaporation solute precipitation as herein described and the second solution evaporation solute are separated out and are meant the solution comprising specific solute, in the process of part solution by solute precipitation at least partly after thermal evaporation.
Compared with existing use for synthetic leather base cloth fabric, base cloth fabric provided by the invention has the following advantages: adopt organic imvite modified polyamide, makes polyamide have higher modulus, and has higher impact resistance and tensile elongation.
In one embodiment, the polyamide model in step S1 is PA6 or PA66, and antioxidant is the four seasons defend four alcohol esters.
In one embodiment, the treatment temperature of step S2 is 75 DEG C ~ 125 DEG C.
In one embodiment, step S2 by double screw extruder by the blended granulation of the first material component.
In one embodiment, the second material component machine-shaping is base cloth fabric by the shaping or shaping technique that punctures of weaving by step S4.
In one embodiment, the fibre fineness of the base cloth fabric of step S5 preparation is less than 0.ldtex.
In one embodiment, the PAUR model of step S6 is A-7030, and pore-foaming agent model is carboxymethyl cellulose or diatomite, and surfactant model is S-7, and solvent borne colorant model is EK-048, and fluorine element high polymer model is F-3D.
In one embodiment, step S10 solid content be 40% EU model be A-1065G, solid content 60% thermoplastic polyester model is M-530.
In one embodiment, by an adhesive linkage one patterned layer fitted on the base cloth fabric after step S9 process in step S10 and comprise following steps: S11: patterned layer is formed on a release layer; S12: form adhesive linkage between patterned layer and the base cloth fabric after step S9 process; S13: peel off release layer.
The concrete production technology of synthetic leather of the present invention will be described by specific embodiment below.
Embodiment one:
Table 1.1 modified polyamide resin formula
Material component Weight
Polyamide 100kg
Organo montmorillonite 5kg
Antioxidant (four seasons defend four alcohol esters) 0.35kg
Table 1.2 floods fluid,matching formula:
Material component Weight
Solid content is the PAUR (A-7030) of 40% 100kg
Dimethyl formamide (DMF) 110kg
Pore-foaming agent (diatomite) 15kg
Surfactant (S-7) 2kg
Solvent borne colorant (EK-048) 8kg
Fluorine element high polymer (F-3D) 2.5kg
Table 1.3 adhesive linkage polyurethane formulation liquid formulation by weight:
First, prepare respective material by the formula of table 1.1 to 1.3, and the polyurethane solutions that solid content is greater than 65%.
Further, carry out blended process, realize fusion intercalation, granulation by double screw extruder to the first material component, the treatment temperature of this process is 75 DEG C ~ 125 DEG C; Modified polyamide resin is obtained by this step.
Further, prepare the modified polyamide resin 100kg of aforementioned formation and polyamide 30kg is blended spins, and the shaping or traditional handicraft such as shaping that punctures forms base cloth fabric by weaving.
Further, the base cloth fabric of aforementioned formation be impregnated in polyvinyl alcohol (being called for short PVA).Through dipping scrim material tearing strength and bursting strength higher.
Further, base cloth fabric can be rolled out, and pressing is carried out to it arrange (can by instruments such as ironing rollers), make its positive surface evenness be applicable to processing.
Further, the material component of table 1.2 is mixed to form maceration extract, and impregnated in through the base cloth fabric arranged that plates in the maceration extract of formation.In dipping process, base cloth fabric fully can be flooded by compression roller.The time of dipping need guarantee that mixed material component can fully condense on base cloth fabric.
Further, take out the scrim material through dipping, and base cloth fabric to be washed, guarantee that the dimethyl formamide after dipping can fully be replaced, dimethyl formamide injured skin remaining during to avoid that base cloth fabric is follow-up to be used.Specifically, washing time can be controlled in 38min-45min; Washing extrusion passes can be controlled in 12 times; Washing temperature can be controlled in 85 DEG C; After washing, rinsing bowl dimethyl formamide concentration is lower than 0.2%.
Further, the scrim material after washing can be dried and be shaped.
Further, can with reference to Figure 1A, Figure 1A depicts the schematic diagram that one embodiment of the invention forms patterned layer on base cloth fabric, in this step, polyurethane solutions evaporative crystallization formation patterned layer 20 on release layer 10 that solid content is greater than 65%, the solution evaporative crystallization simultaneously table 1.3 component formed forms adhesive linkage 30, and adhesive linkage 30 is configured at patterned layer 20 and between aforementioned oven dry and the scrim material 40 after shaping, fits with by both.Easy understand, adhesive linkage 30 can first be formed on patterned layer 20 or scrim material 40 any layer, then both is fitted, and other embodiment follow-up also can sequentially be fitted according to this, repeats no more.
Further, can depict with reference to Figure 1B, Figure 1B the schematic diagram that one embodiment of the invention peels off release layer, after completing abovementioned steps, release layer 10 can be peeled off.
Embodiment two:
Table 2.1 modified polyamide resin formula
Material component Weight
Polyamide 100kg
Organo montmorillonite 8kg
Antioxidant 0.6kg
Table 2.2 floods fluid,matching formula:
Material component Weight
Solid content is the PAUR (A-7030) of 40% 100kg
Dimethyl formamide (DMF) 100kg
Pore-foaming agent (diatomite) 14kg
Surfactant (S-7) 2kg
Solvent borne colorant (EK-048) 6kg
Fluorine element high polymer (F-3D) 2.5kg
Table 2.3 adhesive linkage polyurethane formulation liquid formulation by weight:
First, prepare respective material by the formula of table 2.1 to 2.3, and the polyurethane solutions that solid content is greater than 65%.
Further, carry out blended process, realize fusion intercalation, granulation by double screw extruder to the first material component, the treatment temperature of this process is 75 DEG C ~ 125 DEG C; Modified polyamide resin is obtained by this step.
Further, prepare the modified polyamide resin 100kg of aforementioned formation and polyamide 26kg is blended spins, and the shaping or traditional handicraft such as shaping that punctures forms base cloth fabric by weaving.
Further, the base cloth fabric of aforementioned formation be impregnated in polyvinyl alcohol (being called for short PVA).Through dipping scrim material tearing strength and bursting strength higher.
Further, base cloth fabric can be rolled out, and pressing is carried out to it arrange (can by instruments such as ironing rollers), make its positive surface evenness be applicable to processing.
Further, the material component of table 2.2 is mixed to form maceration extract, and impregnated in through the base cloth fabric arranged that plates in the maceration extract of formation.In dipping process, base cloth fabric fully can be flooded by compression roller.The time of dipping need guarantee that mixed material component can fully condense on base cloth fabric.
Further, take out the scrim material through dipping, and base cloth fabric to be washed, guarantee that the dimethyl formamide after dipping can fully be replaced, dimethyl formamide injured skin remaining during to avoid that base cloth fabric is follow-up to be used.Specifically, washing time can be controlled in 38min-45min; Washing extrusion passes can be controlled in 12 times; Washing temperature can be controlled in 85 DEG C; After washing, rinsing bowl dimethyl formamide concentration is lower than 0.2%.
Further, the scrim material after washing can be dried and be shaped.
Further, can with reference to Figure 1A, Figure 1A depicts the schematic diagram that one embodiment of the invention forms patterned layer on base cloth fabric, in this step, polyurethane solutions evaporative crystallization formation patterned layer 20 on release layer 10 that solid content is greater than 65%, the solution evaporative crystallization simultaneously table 2.3 component formed forms adhesive linkage 30, and adhesive linkage 30 is configured at patterned layer 20 and between aforementioned oven dry and the scrim material 40 after shaping, fits with by both.
Further, can depict with reference to Figure 1B, Figure 1B the schematic diagram that one embodiment of the invention peels off release layer, after completing abovementioned steps, release layer 10 can be peeled off.
Embodiment three:
Table 3.1 modified polyamide resin formula
Material component Weight
Polyamide 80kg
Organo montmorillonite 1kg
Antioxidant 0.2kg
Table 3.2 floods fluid,matching formula:
Material component Weight
Solid content is the PAUR (A-7030) of 40% 100kg
Dimethyl formamide (DMF) 100kg
Pore-foaming agent (diatomite) 10kg
Surfactant (S-7) 1kg
Solvent borne colorant (EK-048) 5kg
Fluorine element high polymer (F-3D) 2kg
Table 3.3 adhesive linkage polyurethane formulation liquid formulation by weight:
First, prepare respective material by the formula of table 3.1 to 3.3, and the polyurethane solutions that solid content is greater than 65%.
Further, carry out blended process, realize fusion intercalation, granulation by double screw extruder to the first material component, the treatment temperature of this process is 75 DEG C; Modified polyamide resin is obtained by this step.
Further, prepare the modified polyamide resin 100kg of aforementioned formation and polyamide 25kg is blended spins, and the shaping or traditional handicraft such as shaping that punctures forms base cloth fabric by weaving.
Further, the base cloth fabric of aforementioned formation be impregnated in polyvinyl alcohol (being called for short PVA).Through dipping scrim material tearing strength and bursting strength higher.
Further, base cloth fabric can be rolled out, and pressing is carried out to it arrange (can by instruments such as ironing rollers), make its positive surface evenness be applicable to processing.
Further, the material component of table 3.2 is mixed to form maceration extract, and impregnated in through the base cloth fabric arranged that plates in the maceration extract of formation.In dipping process, base cloth fabric fully can be flooded by compression roller.The time of dipping need guarantee that mixed material component can fully condense on base cloth fabric.
Further, take out the scrim material through dipping, and base cloth fabric to be washed, guarantee that the dimethyl formamide after dipping can fully be replaced, dimethyl formamide injured skin remaining during to avoid that base cloth fabric is follow-up to be used.Specifically, washing time can be controlled in 38min-45min; Washing extrusion passes can be controlled in 12 times; Washing temperature can be controlled in 85 DEG C; After washing, rinsing bowl dimethyl formamide concentration is lower than 0.2%.
Further, the scrim material after washing can be dried and be shaped.
Further, can with reference to Figure 1A, Figure 1A depicts the schematic diagram that one embodiment of the invention forms patterned layer on base cloth fabric, in this step, polyurethane solutions evaporative crystallization formation patterned layer 20 on release layer 10 that solid content is greater than 65%, the solution evaporative crystallization simultaneously table 3.3 component formed forms adhesive linkage 30, and adhesive linkage 30 is configured at patterned layer 20 and between aforementioned oven dry and the scrim material 40 after shaping, fits with by both.
Further, can depict with reference to Figure 1B, Figure 1B the schematic diagram that one embodiment of the invention peels off release layer, after completing abovementioned steps, release layer 10 can be peeled off.
Embodiment four:
Table 4.1 modified polyamide resin formula
Material component Weight
Polyamide 100kg
Organo montmorillonite 10kg
Antioxidant 0.8kg
Table 4.2 floods fluid,matching formula:
Material component Weight
Solid content is the PAUR (A-7030) of 40% 100kg
Dimethyl formamide (DMF) 120kg
Pore-foaming agent (diatomite) 15kg
Surfactant (S-7) 4kg
Solvent borne colorant (EK-048) 10kg
Fluorine element high polymer (F-3D) 5kg
Table 4.3 adhesive linkage polyurethane formulation liquid formulation by weight:
First, prepare respective material by the formula of table 4.1 to 4.3, and the polyurethane solutions that solid content is greater than 65%.
Further, carry out blended process, realize fusion intercalation, granulation by double screw extruder to the first material component, the treatment temperature of this process is 125 DEG C; Modified polyamide resin is obtained by this step.
Further, prepare the modified polyamide resin 100kg of aforementioned formation and polyamide 35kg is blended spins, and the shaping or traditional handicraft such as shaping that punctures forms base cloth fabric by weaving.
Further, the base cloth fabric of aforementioned formation be impregnated in polyvinyl alcohol (being called for short PVA).Through dipping scrim material tearing strength and bursting strength higher.
Further, base cloth fabric can be rolled out, and pressing is carried out to it arrange (can by instruments such as ironing rollers), make its positive surface evenness be applicable to processing.
Further, the material component of table 4.2 is mixed to form maceration extract, and impregnated in through the base cloth fabric arranged that plates in the maceration extract of formation.In dipping process, base cloth fabric fully can be flooded by compression roller.The time of dipping need guarantee that mixed material component can fully condense on base cloth fabric.
Further, take out the scrim material through dipping, and base cloth fabric to be washed, guarantee that the dimethyl formamide after dipping can fully be replaced, dimethyl formamide injured skin remaining during to avoid that base cloth fabric is follow-up to be used.Specifically, washing time can be controlled in 38min-45min; Washing extrusion passes can be controlled in 12 times; Washing temperature can be controlled in 85 DEG C; After washing, rinsing bowl dimethyl formamide concentration is lower than 0.2%.
Further, the scrim material after washing can be dried and be shaped.
Further, can with reference to Figure 1A, Figure 1A depicts the schematic diagram that one embodiment of the invention forms patterned layer on base cloth fabric, in this step, polyurethane solutions evaporative crystallization formation patterned layer 20 on release layer 10 that solid content is greater than 65%, the solution evaporative crystallization simultaneously table 4.3 component formed forms adhesive linkage 30, and adhesive linkage 30 is configured at patterned layer 20 and between aforementioned oven dry and the scrim material 40 after shaping, fits with by both.
Further, can depict with reference to Figure 1B, Figure 1B the schematic diagram that one embodiment of the invention peels off release layer, after completing abovementioned steps, release layer 10 can be peeled off.
Embodiment five
Table 5.1 modified polyamide resin formula
Material component Weight
Polyamide 90kg
Organo montmorillonite 10kg
Antioxidant 0.8kg
Table 5.2 floods fluid,matching formula:
Table 5.3 adhesive linkage polyurethane formulation liquid formulation by weight:
First, prepare respective material by the formula of table 5.1 to 5.3, and the polyurethane solutions that solid content is greater than 65%.
Further, carry out blended process, realize fusion intercalation, granulation by double screw extruder to the first material component, the treatment temperature of this process is 90 DEG C; Modified polyamide resin is obtained by this step.
Further, prepare the modified polyamide resin 100kg of aforementioned formation and polyamide 35kg is blended spins, and the shaping or traditional handicraft such as shaping that punctures forms base cloth fabric by weaving.
Further, the base cloth fabric of aforementioned formation be impregnated in polyvinyl alcohol (being called for short PVA).Through dipping scrim material tearing strength and bursting strength higher.
Further, base cloth fabric can be rolled out, and pressing is carried out to it arrange (can by instruments such as ironing rollers), make its positive surface evenness be applicable to processing.
Further, the material component of table 5.2 is mixed to form maceration extract, and impregnated in through the base cloth fabric arranged that plates in the maceration extract of formation.In dipping process, base cloth fabric fully can be flooded by compression roller.The time of dipping need guarantee that mixed material component can fully condense on base cloth fabric.
Further, take out the scrim material through dipping, and base cloth fabric to be washed, guarantee that the dimethyl formamide after dipping can fully be replaced, dimethyl formamide injured skin remaining during to avoid that base cloth fabric is follow-up to be used.Specifically, washing time can be controlled in 38min-45min; Washing extrusion passes can be controlled in 12 times; Washing temperature can be controlled in 85 DEG C; After washing, rinsing bowl dimethyl formamide concentration is lower than 0.2%.
Further, the scrim material after washing can be dried and be shaped.
Further, can with reference to Figure 1A, Figure 1A depicts the schematic diagram that one embodiment of the invention forms patterned layer on base cloth fabric, in this step, polyurethane solutions evaporative crystallization formation patterned layer 20 on release layer 10 that solid content is greater than 65%, the solution evaporative crystallization simultaneously table 5.3 component formed forms adhesive linkage 30, and adhesive linkage 30 is configured at patterned layer 20 and between aforementioned oven dry and the scrim material 40 after shaping, fits with by both.
Further, can depict with reference to Figure 1B, Figure 1B the schematic diagram that one embodiment of the invention peels off release layer, after completing abovementioned steps, release layer 10 can be peeled off.
The each embodiment physical property contrast of table 6:
Known by table 6, the synthetic leather that the inventive method is formed has good resistance to gauffer, therefore can avoid the existence effectively avoiding folding line.
It should be noted that, the present invention's polyurethane used is Xu Chuan chemical company product; The trade mark is the fluorine element high polymer of F-3D and the trade mark be the surfactant of S-7 is Shanghai Shen Chemical Co., Ltd. product; Modified silicone high polymer BYK-9520 is German Bi Ke chemistry Products; Solvent borne colorant EK-048 is TKC Products; Diatomite is Co., Ltd's product in Celite; Organo montmorillonite is marine origin Science and Technology Ltd. of Shenzhen product; Solid content 60% thermoplastic polyester M-530 is Shandong Mei Rui Materials Co., Ltd product, and the polyurethane that solid content is greater than 65% is Bayer Material Science Co., Ltd product.
Prepared by the present invention improves from the base cloth fabric of synthetic leather, adhesive linkage and patterned layer without folding line synthetic leather simultaneously.Adopt nano imvite to carry out intercalation modifying to synthetic leather scrim material, improve modulus and the rebound performance of synthetic leather base cloth fabric; Adopt low viscosity thermoplastic polyurethane blends as the adhesive linkage of synthetic leather, improve resilience and the modulus of synthetic leather, make synthetic leather have better folding quality; Adopt high solid content polyurethane as synthetic leather patterned layer, reduce the hole because solvent evaporation is formed at surface layer, make synthetic leather be not easy to form folding line in bending rear surface.
Below be only the preferred embodiment of the present invention, it should be pointed out that under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (9)

1. without a production method for folding line synthetic leather, it is characterized in that, comprise following steps:
S1: prepare the first material component, with parts by weight, described first material component comprises polyamide 80 ~ 100 parts, organo montmorillonite 1 ~ 10 part, antioxidant 0.2-0.8 part;
S2: by the blended granulation of described first material component, forms modified polyamide resin;
S3: prepare the second material component, described second material component comprises the modified polyamide resin of polyamide and step S2 formation, and with parts by weight, modified polyamide resin is 100 parts, and polyamide is 25 ~ 35 parts;
S4: be base cloth fabric by described second material component machine-shaping;
S5: prepare the base cloth fabric that described step S4 is formed, and described base cloth fabric be impregnated in polyvinyl alcohol;
S6: prepare the 3rd material component, with parts by weight, described 3rd material component comprise solid content be 40% PAUR 100 parts, dimethyl formamide 100-120 part, pore-foaming agent 10-15 part, surfactant 1-4 part, solvent borne colorant 5-10 part, fluorine element high polymer 2-5 part;
S7: take out in step S5 through the base cloth fabric of dipping, and impregnated in the solution comprising the 3rd material component;
S8: take out the base cloth fabric after step S7 dipping, and it is washed;
S9: the base cloth fabric after step S8 washing is dried and shaped;
S10: one patterned layer is fitted on the base cloth fabric after step S9 process by an adhesive linkage; Described adhesive linkage is that one first solution evaporation solute precipitation forms, and described first solution, with parts by weight, comprises EU 25 ~ 45 parts, solid content 60% thermoplastic polyester 55 ~ 75 parts that solid content is 40%; Described patterned layer is that one second solution evaporation solute precipitation forms, and described second solution is the polyurethane solutions that solid content is greater than 65%.
2. the production method without folding line synthetic leather according to claim 1, is characterized in that, the polyamide model in described step S1 is PA6 or PA66, and described antioxidant is the four seasons defend four alcohol esters.
3. the production method without folding line synthetic leather according to claim 1, is characterized in that, the treatment temperature of described step S2 is 75 DEG C ~ 125 DEG C.
4. the production method without folding line synthetic leather according to claim 1, is characterized in that, described step S2 by double screw extruder by the blended granulation of described first material component.
5. the production method without folding line synthetic leather according to claim 1, is characterized in that, described second material component machine-shaping is base cloth fabric by the shaping or shaping technique that punctures of weaving by described step S4.
6. the production method without folding line synthetic leather according to claim 1, is characterized in that, the fibre fineness of the base cloth fabric that described step S5 prepares is less than 0.ldtex.
7. the production method without folding line synthetic leather according to claim 1, it is characterized in that, the PAUR model of described step S6 is A-7030, pore-foaming agent model is carboxymethyl cellulose or diatomite, surfactant model is S-7, solvent borne colorant model is EK-048, and fluorine element high polymer model is F-3D.
8. the production method without folding line synthetic leather according to claim 1, is characterized in that, described step S10 solid content be 40% EU model be A-1065G, solid content 60% thermoplastic polyester model is M-530.
9. the production method without folding line synthetic leather according to claim 1, is characterized in that, one patterned layer to be fitted on the base cloth fabric after step S9 process comprise following steps in described step S10 by an adhesive linkage:
S11: described patterned layer is formed on a release layer;
S12: form described adhesive linkage between described patterned layer and the base cloth fabric after step S9 process;
S13: peel off described release layer.
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CN106087450A (en) * 2016-08-23 2016-11-09 福建宝利特科技股份有限公司 A kind of manufacture method of artificial leather without base fabric
CN109652994A (en) * 2018-11-30 2019-04-19 安徽安利材料科技股份有限公司 Two-sided no folding line no-solvent polyurethane luggage synthetic leather of one kind and preparation method thereof
CN110254003A (en) * 2019-06-04 2019-09-20 浙江锦尚合成革有限公司 A kind of formula and manufacturing method of the anti-corrosion-resistant high-strength synthetic leather of folding
CN111676709A (en) * 2020-06-19 2020-09-18 广东玉兰集团股份有限公司 Folding-resistant and anti-wrinkle base material, preparation method and wall cloth
CN112795355A (en) * 2020-12-25 2021-05-14 上海邦中高分子材料股份有限公司 Special bonding resin for steel-plastic composite pipe and preparation method thereof
CN116065408A (en) * 2023-02-20 2023-05-05 清远市齐力合成革有限公司 Crease-free synthetic leather and preparation method thereof

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CN106087450A (en) * 2016-08-23 2016-11-09 福建宝利特科技股份有限公司 A kind of manufacture method of artificial leather without base fabric
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CN111676709B (en) * 2020-06-19 2023-08-18 广东玉兰集团股份有限公司 Folding-resistant and crease-resistant base material, preparation method and wall cloth
CN112795355A (en) * 2020-12-25 2021-05-14 上海邦中高分子材料股份有限公司 Special bonding resin for steel-plastic composite pipe and preparation method thereof
CN116065408A (en) * 2023-02-20 2023-05-05 清远市齐力合成革有限公司 Crease-free synthetic leather and preparation method thereof

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