CN101805999B - Method for fabricating imitated artificial leather by applying waterborne polyurethane - Google Patents
Method for fabricating imitated artificial leather by applying waterborne polyurethane Download PDFInfo
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Abstract
The invention relates to a method for fabricating dry-processing artificial leather SEMI-PU, in particular to a method for fabricating imitated artificial leather by applying waterborne polyurethane, which includes the four major steps of a material preparation stage (3), a main machine production stage (4), semi-finished product kneading procedure (9') and finished product trimming procedure (8), wherein the material preparation stage (3) includes the preparation of waterborne polyurethane fabric and PVC foam paste material; the main machine production stage mainly includes the processes that the main machine coats and scrapes the prepared waterborne polyurethane (41') for a first time by a coating arced cutter, the main machine coats and scrapes the PVC foam paste resin for a second time by the coating arced cutter, and the main machine coats and scrapes the waterborne polyurethane bonding material (43') for a third time by the coating arced cutter and then bonds a leather base fabric (5); the main machine production stage further includes drying procedure (6) and releasing procedure (7); and after the kneading procedure and the trimming and coiling treatments, a finished product can be obtained. The method applies waterborne polyurethane resin to the existing dry-processing artificial leather production equipment and takes water as the solvent, so the production process does not cause pollution to the environment; the artificial leather produced through the method neither has harm to the human body nor causes environmental pollution; and the grain of the artificial leather has the texture of authentic leather, so the artificial leather can satisfy the requirements of the market users.
Description
Technical field
The invention relates to the method for a kind of manufacturing dry method PU/PVC artificial leather (being also referred to as SEMI-PU), particularly applying waterborne polyurethane is made the method for emulation dermatoglyph passerby fabricate-leather.
Technical background
The polyurethane PU resin that present domestic dry method artificial leather SEMI-PU producer all adopts organic solvent type is as the basic lining of producing artificial leather basic unit and surface layer, and processes after diluting with organic solvent dissolution.This organic solvent is dimethyl formamide DMF, butanone MEK, acetone ACT, toluene TOL, xylene mostly, and this kind solvent all has certain toxicity, and is big to human harm, and the human respiratory tract is had intense stimulus property, seriously can cause stupor, death; Long-term contact can make nerve system of human body, kidney and liver sustain damage.Organic solvent not only endangered workman's health of workshop when this type artificial leather was produced; The river that also will be discharged into periphery through water and air is with day aerial; The environment that severe contamination is local, production, the life of giving people, the public's life and health constitutes significant threat.
As shown in Figure 1, the production procedure of known SEMI-PU artificial leather comprises: batching stage 3, main frame production phase 4; After finished product collates program and 8 is finished product, wherein, the batching stage comprises that prescription design 1 and lining prepare 2 liang of steps; The main frame production phase 4 mainly comprises being coated with for the first time successively scrapes solvent type resin 41; Be coated with for the second time and scrape PVC foaming paste resin 42, be coated with for the third time and scrape solvent borne polyurethane coating medium 43 3 steps, and base cloth fits 5; Drying 6, release 7 three additional step.
As shown in Figure 3, the composition of known SEMI-PU artificial leather comprises: solvent type polyurethane fabric 21, and foam polyvinyl chloride material 22, solvent borne polyurethane coating medium 23, leather is with base cloth 24.
In this production process; Organic solvent can all evaporate when dry in baking oven; A part is recovered, and some is discharged in the air, pollutes, gives local people's production, life and the public's life and health to constitute significant threat for factory's environment on every side.The residual organic solvent that part is arranged in the SEMI-PU artificial leather product of producing in use is prone to slowly evaporate, and brings harm for the public of end user's fabricate-leather product.
Present advocating environment protection, energy-conservation, reduce discharging, under the healthy background, people's an urgent demand increases friendly process in leather industry, produce and use non-harmful product.
Summary of the invention
The method that the purpose of this invention is to provide a kind of fabricating imitated artificial leather by applying waterborne polyurethane, it is the method that the environment-friendly type aqueous polyurethane material is applied to the manufacturing skin emulation effect of existing equipment artificial leather true to nature.In order to realize the object of the invention; The inventor provides following technical scheme: a kind of method of fabricating imitated artificial leather by applying waterborne polyurethane; It comprises four big steps, and these four steps are batching stage, main frame production phase, semi-finished product rubbing program, collate program until finished product, wherein:
The step 1 batching stage comprises preparation of aqueous polyurethane lining and foam polyvinyl chloride paste formulation, and following umber is weight portion, and is specific as follows:
Aqueous polyurethane lining preparation: select 100 parts of aqueous polyurethanes for use, 0.2~1 part of water-based levelling agent, 0.2~1 part of water-based thickener; 0.5~1.5 part of water-based antifoaming agent, 1~10 part of water-based hand feeling agent, 5~30 parts of light waters; 5~15 parts of aqueous color pastes, mixing time and speed can fully be sheared even dispersion with material and set, and are roughly 20~50 minutes time; Mixer rotating speed 500~1500rpm, the material viscosity Control is at 500~1500cps, and temperature is controlled at 20 ℃.This blending process organic solvent-free adds, in whipping process, and also organic solvent-free volatilization, the workman's that can not stimulate production respiratory system does not produce certain harm to human body, the environment around the factory is not polluted, and meets the ecological, environmental protective requirement.
Described water-based levelling agent is known modified dimethyl polysiloxane copolymer.
Described water-based thickener is known nonionic aqueous polyurethane compound.
Described water-based antifoaming agent is known modified siloxane copolymer, the modification castor oil polymer etc. of deriving.
Described water-based hand feeling agent is known water soluble wax emulsion, silicone emulsion etc.
Described aqueous polyurethane is environmentally friendly macromolecular material anion aqueous polyurethane; It is to disclose commercially availablely, and this type of aqueous polyurethane is to be that 1: 1: 2 polyether-type or polyester polyol, dihydromethyl propionic acid (DMPA), N-methyl-2 pyrrolidones (M-pyr01) and the catalyst (dibutyl tin laurate) that is about first three items component solid gross weight 0.05% are prepared from weight ratio.The aqueous polyurethane preparation method of said type prepares the prepolymer that contains hydrophilic radical and have a NCO end group earlier, and after in water, disperseing, utilization amino is realized chain growth and made.In this aqueous polyurethane system of production, not with an organic solvent, there is not the anxiety of poisoning, catching fire, compliance with environmental protection requirements.
Foam polyvinyl chloride paste formulation: at first; Temperature is controlled at 20 ℃; Utilize plasticizer phthalic acid dioctyl ester DOP, dibutyl phthalate DBP, chlorinated paraffin wax will be diluted to the thickener that viscosity number is 2000~3000cps by the PVC paste resin that emulsion polymerization makes, the weight portion of DOP, DBP, chlorinated paraffin wax is 60~150 parts altogether; Secondly, adding blowing agent, stabilizing agent, filler, polyvinyl chloride color stir.
Described blowing agent is for Celogen Az commonly used etc., and stabilizing agent is the compound zinc of liquid commonly used, barium salt etc., and filler is for calcium carbonate commonly used etc., and deal separately is according to required leather foam degrees, leather hand feeling, and cost control etc. require to confirm.
The step 2 main frame production phase mainly comprises three process, is followed successively by:
Main frame is coated with the arc cutter for the first time and is coated with and scrapes the aqueous polyurethane for preparing, foodstuff amount 50~150g/y, 120~150 ℃ down oven dry can get into next procedure after 2~3 minutes.
Main frame is coated with for the second time scrapes foam polyvinyl chloride paste resin: one of which; The foam polyvinyl chloride thickener that utilizes the coating apparatus of main frame production to prepare is evenly coated last accomplishing on the release liners of printing process of sending, and is 200~1000g/y according to required leather thickness adjustment coating weight; Its two, the release liners of coated foam polyvinyl chloride thickener is sent in the foaming furnace, got into subsequent processing after in 170~180 ℃, foaming 2~3 minutes.
The applying leather was used base cloth after main frame was coated with for the third time and scrapes the aqueous polyurethane coating medium, and the foodstuff amount can get into next procedure in oven dry under 140~160 ℃ after 2~3 minutes at 100~200g/y.Utilize the aqueous polyurethane coating medium to substitute the polyurethane solvent-borne type coating medium of existing use, guarantee the discharging of production process organic solvent-free, environmentally safe.
The step 2 main frame production phase, also comprise drying, release program.
The semi-finished product that step 4 will be accomplished the rubbing program at last take out the back arrangement in the boarding machine, rolling is finished product.
The above-mentioned processing technology of the present invention is that surface tension is big, and is particularly poor to low-surface-energy or hydrophobic base material wettability to base material because of evaporation of water latent heat in the waterborne polyurethane resin lining is high.As pressing existing production technology production, the aqueous polyurethane leather surface is prone to anomalies such as shrinkage pool, face flower, contraction, thereby needs to set special production temperature process.
Because when environmentally friendly macromolecular material anion aqueous polyurethane PU produces on existing artificial leather manufacturer production coating apparatus; This PU lining rolls on release liners; Very easily produce great amount of bubbles, cause crawling, strip occurring does not have phenomenons such as material; Also differ widely, cause producing and to carry out because of production technology and existing production technology.For this reason, existing equipment is carried out some improvement, the concrete improvement as follows: on the existing main frame first coating apparatus arc cutter front, release liners, increase a plate washer, be combined to form a little hopper with arc cutter and release liners, feeding in raw material in the hopper during production gets final product.It is fixed that the size of this little hopper is come by convenient for production and effectiveness, and roughly the gap is that distance is 1~7cm between arc cutter and the plate washer, and plate washer lower limb and release liners spacing are (to be as the criterion not leak material) about 0.1~1cm.The increase of little hopper; The contact-making surface of aqueous polyurethane and release liners is diminished; The PU lining significantly reduces because of the chance that produces great amount of bubbles of rolling on the paper that is blocked in that reaches cutter that moves of paper during production; Thereby be difficult for causing crawling, strip occurring does not have phenomenons such as material, makes environmentally friendly emulation dermatoglyph passerby fabricate-leather be able to steady production.The invention of this little hopper has solved the problem that aqueous polyurethane can not drop into processing in a large number.
Applying waterborne polyurethane resin of the present invention substitutes the organic solvent type polyurethane in existing dry method artificial leather production equipment, is solvent with water, and it is produced and does not pollute local environment; The artificial leather that is obtained is not because of containing organic solvent, low VOC (organic volatile) discharging, not harmful to human, also free from environmental pollution; Utilize rubbing technology to make the product lines have more kishke feel, can satisfy market user's requirement; And the present invention has also solved and has occurred anomalies such as great amount of bubbles causes that product appearance surface nothing material is scrapped in the production of aqueous polyurethane resin, makes environmentally friendly SEMI-PU artificial leather be able to steady production, satisfies the production demand.
Description of drawings
Fig. 1 is known SEMI-PU artificial leather flow sheet;
Fig. 2 is a SEMI-PU artificial leather production procedure sketch map of the present invention;
Fig. 3 is known SEMI-PU artificial leather generalized section;
Fig. 4 is the prepared SEMI-PU artificial leather of a present invention generalized section;
Fig. 5 is the manufacturing SEMI-PU artificial leather main frame first coating apparatus structural representation of the present invention.
Description of reference numerals:
The 1-design of filling a prescription, the 2-lining is prepared, and 3-prepares burden the stage, and the 4-main frame production phase, 41-is coated with for the first time and scrapes solvent type resin; 42-is coated with for the second time and scrapes PVC foaming paste resin, and 43-is coated with for the third time and scrapes the solvent borne polyurethane coating medium, and the 5-base cloth is fitted, and 6-is dry, and 7-is release; The 8-finished product collates program, and 41 '-for the first time is coated with and scrapes aqueous polyurethane, and 43 '-for the third time is coated with and scrapes the aqueous polyurethane coating medium, and 9 '-semi-finished product are crumpled program; The 21-solvent type polyurethane fabric, 22-foam polyvinyl chloride material, 23-solvent borne polyurethane coating medium, the 24-leather is used base cloth; 21 '-aqueous polyurethane lining, 23 '-aqueous polyurethane coating medium, 31-arc cutter, 32-release liners; The little hopper of 33-, 34-baffle plate, L-arc cutter and plate washer spacing, h-plate washer lower limb and release liners spacing.
Specific embodiments
Combine Figure of description that technical scheme of the present invention is done further explain at present.
Embodiment 1: as shown in Figure 2; The method of a kind of fabricating imitated artificial leather by applying waterborne polyurethane of the present invention; It comprises four big steps, and these four steps are batching stage 3, main frame production phase 4, semi-finished product rubbing program 9 ', collate program 8 until finished product, wherein:
Step 1 batching stage (umber is weight portion) comprises preparation of aqueous polyurethane lining and foam polyvinyl chloride paste formulation, and is specific as follows:
Aqueous polyurethane lining preparation: select 100 parts of aqueous polyurethanes for use, 0.2~0.3 part of water-based levelling agent, 0.2~0.5 part of water-based thickener; 0.5~1 part of water-based antifoaming agent, 1~5 part of water-based hand feeling agent, 5~10 parts of light waters; 5~8 parts of aqueous color pastes; Mixing time 20~40 minutes, mixing speed 500~800rpm, the material viscosity Control is at 500~1000cps (20 ℃).
Described water-based levelling agent is the modified dimethyl polysiloxane copolymer.
Described water-based thickener is a nonionic aqueous polyurethane compound.
Described water-based antifoaming agent is the modification castor oil polymer etc. of deriving.
Described water-based hand feeling agent is a silicone emulsion etc.
Described aqueous polyurethane is the environmentally friendly macromolecular material anion aqueous polyurethane of high temperature resistant type; It is that big chemical Science and Technology Ltd. provides in one of the producer Anqing by aqueous polyurethane, product type be among CTPU-500W, CPTU-600W, the ETPU-300W any one.
Foam polyvinyl chloride paste formulation: at first; Utilize plasticizer phthalic acid dioctyl ester DOP, dibutyl phthalate DBP, chlorinated paraffin wax etc. that PVC paste resin (emulsion polymerization) is diluted to the thickener that viscosity number is 2000~3000cps (20 ℃), the weight portion of DOP, DBP, chlorinated paraffin wax is 150 parts altogether; Secondly, 3 parts of adding blowing agent Celogen Azs, 3 parts on the compound zinc of stabilizing agent liquid, 60 parts in filler calcium carbonate, polyvinyl chloride color stir for 5 parts;
The step 2 main frame production phase mainly comprises three process, is followed successively by:
Main frame is coated with the arc cutter for the first time and is coated with and scrapes the aqueous polyurethane 41 ' for preparing, foodstuff amount 50~70g/y, 120~140 ℃ down oven dry can get into next procedure after 2~3 minutes.
Main frame is coated with for the second time scrapes polyvinylchloride foaming paste resin: one of which; The foam polyvinyl chloride thickener that utilizes the coating apparatus of main frame production to prepare is evenly coated last accomplishing on the release liners of printing process of sending, and is 200~1000g/y according to required leather thickness adjustment coating weight; Its two, the release liners of coated foam polyvinyl chloride thickener is sent in the foaming furnace, got into subsequent processing after in 170~180 ℃, foaming 2~3 minutes.
Main frame is coated with for the third time scrapes aqueous polyurethane coating medium 43 ' back applying leather with base cloth 5, and the foodstuff amount can get into next procedure in oven dry under 140~160 ℃ after 2~3 minutes at 100~120g/y.
The step 2 main frame production phase also comprises dry 6, release 7 programs, and wherein release program is: the leather that will dry coating medium is peeled off clot afterwards from release liners and can be obtained semi-finished product.
The semi-finished product that step 4 will be accomplished the rubbing program at last take out the back arrangement in the boarding machine, rolling is finished product.
As shown in Figure 4, the composition of the SEMI-PU artificial leather that is obtained comprises: aqueous polyurethane lining 21 ', and foam polyvinyl chloride material 22, aqueous polyurethane coating medium 23 ', leather is with base cloth 24.
At the main frame that carries out above-mentioned steps two in the production phase; As shown in Figure 5; Increase a plate washer 34 on step 2 main frame production phase employed equipment-main frame first coating apparatus arc cutter 31 fronts, the release liners 32; Baffle plate 34 is combined to form a small powder groove 33 with arc cutter 31 and release liners 32, and the gap L of this little hopper is to be 1~3cm apart from L between arc cutter and the plate washer, and plate washer lower limb and release liners spacing h (expect to be as the criterion not leak) about 0.1~0.2cm.The aqueous polyurethane for preparing adds in the hopper and gets final product.
Embodiment 2: a kind of method of fabricating imitated artificial leather by applying waterborne polyurethane, and different with embodiment 1 is:
The step 1 batching stage:
The preparation of aqueous polyurethane lining is different: select 100 parts of aqueous polyurethanes for use, 0.3 part of water-based levelling agent, 0.5 part of water-based thickener; 1 part of water-based antifoaming agent, 5 parts of water-based hand feeling agents, 10 parts of light waters; 8 parts of aqueous color pastes; Mixing time is 40 minutes, mixing speed 800rpm, and the material viscosity Control is at 1000cps (20 ℃).
Described water-based antifoaming agent replaces with the modified siloxane copolymer.
Described water-based hand feeling agent replaces with the water soluble wax emulsion.
The foam polyvinyl chloride paste formulation is different: at first, the weight portion of plasticizer phthalic acid dioctyl ester DOP, dibutyl phthalate DBP, chlorinated paraffin wax is 100 parts altogether; Secondly, 3 parts of adding blowing agent Celogen Azs, 3 parts of stabilizing agent liquid barium salts, 80 parts in filler calcium carbonate, polyvinyl chloride color stir for 5 parts.
The step 2 main frame production phase is different:
Main frame is coated with the arc cutter for the first time and is coated with and scrapes the aqueous polyurethane for preparing, foodstuff amount 70g/y, 140 ℃ down oven dry get into next procedure after 2 minutes.
The applying leather was used base cloth after main frame was coated with for the third time and scrapes the aqueous polyurethane coating medium, and the foodstuff amount gets into next procedure in oven dry under 140~160 ℃ after 2~3 minutes at 120g/y.
In embodiment 2, apart from being 3cm, plate washer lower limb and release liners spacing are about 0.2cm between arc cutter and the plate washer.
Embodiment 3: a kind of method of fabricating imitated artificial leather by applying waterborne polyurethane, and different with embodiment 1 is:
The step 1 batching stage:
The preparation of aqueous polyurethane lining is different: select 100 parts of aqueous polyurethanes for use, 0.3~1 part of water-based levelling agent, 0.5~1 part of water-based thickener; 1~1.5 part of water-based antifoaming agent, 5~10 parts of water-based hand feeling agents, 10~30 parts of light waters; 8~15 parts of aqueous color pastes; Mixing time and speed can fully be sheared even dispersion with material and set 40~50 minutes time of being roughly, mixer rotating speed 800~1500rpm, and the material viscosity Control is at 1000~1500cps (20 ℃).
Described water-based antifoaming agent replaces with the modified siloxane copolymer.
The foam polyvinyl chloride paste formulation is different: at first, utilize the weight portion of plasticizer phthalic acid dioctyl ester DOP, dibutyl phthalate DBP, chlorinated paraffin wax to be 60 parts altogether; Secondly, 3 parts of adding blowing agent Celogen Azs, 3 parts on the compound zinc of stabilizing agent liquid, 120 parts in filler calcium carbonate, polyvinyl chloride color stir for 5 parts.
The step 2 main frame production phase is different:
Main frame is coated with the arc cutter for the first time and is coated with and scrapes the aqueous polyurethane for preparing, foodstuff amount 70~150g/y, 140~150 ℃ down oven dry can get into next procedure after 2~3 minutes.
The applying leather was used base cloth after main frame was coated with for the third time and scrapes the aqueous polyurethane coating medium, and the foodstuff amount gets into next procedure in oven dry under 140~160 ℃ after 2~3 minutes at 120~200g/y.
In embodiment 3, apart from being 3~7cm, plate washer lower limb and release liners spacing are about 0.2~1cm between arc cutter and the plate washer.
In the foregoing description 1~3, the applying waterborne polyurethane resin is solvent in existing dry method artificial leather production equipment with water, and it is produced and does not pollute local environment; The SEMI-PU artificial leather that is obtained does not contain organic solvent, low VOC discharging, not harmful to human, yet free from environmental pollution; The final product lines that obtains has more kishke feel than the existing artificial leather, and the emulation dermatoglyph passerby fabricate-leather SEMI-PU of this applying waterborne polyurethane production has good stability.
Claims (4)
1. the method for a fabricating imitated artificial leather by applying waterborne polyurethane is characterized in that this method comprises four big steps, and these four steps are batching stage, main frame production phase, semi-finished product rubbing program, collate program until finished product, wherein:
The step 1 batching stage comprises preparation of aqueous polyurethane lining and foam polyvinyl chloride paste formulation, and following umber is weight portion, and is specific as follows:
Aqueous polyurethane lining preparation: select 100 parts of aqueous polyurethanes for use, 0.2~1 part of water-based levelling agent, 0.2~1 part of water-based thickener; 0.5~1.5 part of water-based antifoaming agent, 1~10 part of water-based hand feeling agent, 5~30 parts of light waters; 5~15 parts of aqueous color pastes, mixing time and speed can fully be sheared even dispersion with material and set, and mixing time is 20~50 minutes; Mixing speed is 500~1500rpm, and the material viscosity Control is at 500~1500cps, and temperature is controlled at 20 ℃;
Foam polyvinyl chloride paste formulation: at first; Temperature is controlled at 20 ℃; Utilize plasticizer phthalic acid dioctyl ester DOP, dibutyl phthalate DBP, chlorinated paraffin wax will be diluted to the thickener that viscosity number is 2000~3000cps by the PVC paste resin that emulsion polymerization makes, the weight portion of DOP, DBP, chlorinated paraffin wax is 60~150 parts altogether; Secondly, adding blowing agent, stabilizing agent, filler, polyvinyl chloride color stir;
The step 2 main frame production phase mainly comprises three process, is followed successively by:
Main frame is coated with the arc cutter for the first time and is coated with and scrapes the aqueous polyurethane for preparing, foodstuff amount 50~150g/y, 120~150 ℃ down oven dry get into next procedure after 2~3 minutes;
Main frame is coated with for the second time scrapes foam polyvinyl chloride paste resin: one of which; The foam polyvinyl chloride thickener that utilizes the coating apparatus of main frame production to prepare is evenly coated last accomplishing on the release liners of printing process of sending, and coating weight is adjusted into 200~1000g/y according to required leather thickness; Its two, the release liners of coated foam polyvinyl chloride thickener is sent in the foaming furnace, got into subsequent processing after in 170~180 ℃, foaming 2~3 minutes;
The applying leather was used base cloth after main frame was coated with for the third time and scrapes the aqueous polyurethane coating medium, and the foodstuff amount gets into next procedure in oven dry under 140~160 ℃ after 2~3 minutes at 100~200g/y;
The step 2 main frame production phase, also comprise drying, release program;
Step 3 rubbing process: it is in 70 ℃ the boarding machine that the semi-finished product that obtain are placed temperature, rubs line half an hour, promptly accomplishes the rubbing program;
The semi-finished product that step 4 will be accomplished the rubbing program at last take out the back arrangement in the boarding machine, rolling is finished product.
2. the method for fabricating imitated artificial leather by applying waterborne polyurethane according to claim 1 is characterized in that the aqueous polyurethane of selecting for use in the described aqueous polyurethane lining preparation is environmentally friendly macromolecular material anion aqueous polyurethane.
3. the method for fabricating imitated artificial leather by applying waterborne polyurethane according to claim 1; The main frame that it is characterized in that step 2 is in the production phase; Increase a plate washer on step 2 main frame production phase employed equipment-main frame first coating apparatus arc cutter front, the release liners; Be combined to form a little hopper with arc cutter and release liners, during production in the hopper reinforced getting final product.
4. the method for fabricating imitated artificial leather by applying waterborne polyurethane according to claim 3, it is characterized in that gap that arc cutter and release liners are combined to form a little hopper be between arc cutter and the plate washer apart from being 1~7cm, plate washer lower limb and release liners spacing 0.1~1cm.
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CN108193511A (en) * | 2018-01-29 | 2018-06-22 | 嘉善威尔尼绒业有限公司 | A kind of processing method of aqueous polyurethane synthetic fabric |
CN109881494A (en) * | 2019-03-14 | 2019-06-14 | 加通汽车内饰(常熟)有限公司 | A kind of pliability is high, the automobile-used artificial leather of hydrolysis and preparation method thereof |
CN110028776A (en) * | 2019-04-23 | 2019-07-19 | 福建宝利特科技股份有限公司 | A kind of antifouling solvent-free artificial leather |
CN114457200B (en) * | 2022-03-04 | 2023-06-09 | 江西省九泓科技有限公司 | Preparation process of polyurethane leather |
CN114808468A (en) * | 2022-05-19 | 2022-07-29 | 陕西科技大学 | Preparation method of waterborne polyurethane microporous coating for microfiber leather |
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CN101054776A (en) * | 2007-05-16 | 2007-10-17 | 李勇 | Method for manufacturing leatheroid |
CN101121869A (en) * | 2007-09-21 | 2008-02-13 | 北京市化学工业研究院 | Method for preparing water polyurethane binder for shoe |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101054776A (en) * | 2007-05-16 | 2007-10-17 | 李勇 | Method for manufacturing leatheroid |
CN101121869A (en) * | 2007-09-21 | 2008-02-13 | 北京市化学工业研究院 | Method for preparing water polyurethane binder for shoe |
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