WO2008077270A1 - Solvent-free polyurethane, its preparation and application - Google Patents

Solvent-free polyurethane, its preparation and application Download PDF

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Publication number
WO2008077270A1
WO2008077270A1 PCT/CN2006/003548 CN2006003548W WO2008077270A1 WO 2008077270 A1 WO2008077270 A1 WO 2008077270A1 CN 2006003548 W CN2006003548 W CN 2006003548W WO 2008077270 A1 WO2008077270 A1 WO 2008077270A1
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WIPO (PCT)
Prior art keywords
solventless polyurethane
polyurethane
impregnated film
solventless
mold
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PCT/CN2006/003548
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French (fr)
Chinese (zh)
Inventor
Jinhe Lin
Original Assignee
Jinhe Lin
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Priority to PCT/CN2006/003548 priority Critical patent/WO2008077270A1/en
Publication of WO2008077270A1 publication Critical patent/WO2008077270A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/721Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202Two or more polyesters of different physical or chemical nature

Definitions

  • the present invention relates to the field of polyurethanes, and more particularly to a novel solventless polyurethane and a process for the preparation thereof, and to the use of the solventless polyurethane in the manufacture of impregnated film articles.
  • the invention relates to the use of the solventless polyurethane in the manufacture of gloves. Background technique
  • a solventless polyurethane is a polymer material obtained by polycondensing a component such as an isocyanate and a hydroxyl group-containing compound in the absence of a solvent, which retains not only the excellent properties inherent in the conventional polyurethane materials, but also the materials themselves. Containing any solvent, it has received a lot of attention in many fields today, as environmental protection calls are getting louder and louder.
  • USP 5,151,484 discloses a solventless polyurethane which has good flexibility and elasticity.
  • the prior art solvent-free polyurethanes are mainly used in the industrial fields of construction, wood, machinery, etc., and therefore most of the components are free of free isocyanate and heavy metal catalysts, etc., but due to the impregnation of the film products In close contact with the human body, the residue of these components will make the prior art solvent-free polyurethane disadvantageous in the application of the impregnated film product, that is, the safety is poor.
  • the prior art solvent-free polyurethane is generally required to be sprayed under high temperature and high pressure due to high viscosity. Therefore, the spraying process is relatively complicated compared to the dipping method, and especially In the case of a complex shaped film such as a glove, the spraying process is difficult to effectively realize its shape, and the operation is difficult.
  • the present invention relates to the following aspects:
  • the solventless polyurethane of aspect 1 characterized in that the solventless polyurethane has a residual NCO group content of from 1 to 12% by weight based on the total weight of the solventless polyurethane.
  • the solventless polyurethane of aspect 2 characterized in that the solventless polyurethane has a residual NCO group content of from 3 to 5% by weight based on the total weight of the solventless polyurethane.
  • the solventless polyurethane of aspect 1 characterized in that in the binary diisocyanate mixture, the molar ratio of the isophorone diisocyanate to the diphenyldecane diisocyanate is 99:1 1:99.
  • the solventless polyurethane of aspect 1 characterized in that the molar ratio of the NCO group of the component (a) to the total OH functional group of the components (b) and (c) is 1 to 2 :1.
  • the solventless polyurethane of aspect 10 characterized in that the molar ratio of the NCO group of the component (a) to the total OH functional group of the components (b) and (c) is 1-1. 5 :1 .
  • the solventless polyurethane of aspect 11 characterized in that the molar ratio of the NCO group of the component (a) to the total OH functional group of the components (b) and (c) is 1-1.2:1.
  • the solventless polyurethane of aspect 1 characterized in that the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is from 1 to 5:1.
  • the solventless polyurethane of aspect 13 characterized in that the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is from 1 to 3.5:1.
  • the solventless polyurethane of aspect 14 characterized in that the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is 1-2:1.
  • a method for producing a solventless polyurethane comprising the step of subjecting the above components (a), (b) and (c) to a polycondensation reaction in the absence of a solvent in the presence of a polycondensation catalyst.
  • organotin compound is selected from the group consisting of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyltin and dibutyltin diacetate.
  • An impregnated film article characterized in that it is produced by a dipping method using the solventless polyurethane of any one of aspects 1-15.
  • a method of making an impregnated film article comprising the steps of:
  • a method of producing an impregnated film article comprising the steps of:
  • the invention manufactures the impregnated film product by adopting a specific solventless polyurethane, which avoids the complicated process that the prior art must face in manufacturing the impregnated film product (in order to improve the smoothness, the finishing step must be increased or not Powder or powder processing steps), environmental pollution and waste of resources.
  • the polyurethane-impregnated film product of the present invention has a marked improvement in various properties such as slipperiness, mechanical properties and elasticity as compared with the prior art latex-type impregnated film product. detailed description
  • polyurethane means a polymer containing a urethane group, and the polymer may further contain a urea group or the like.
  • the present invention relates to a solventless polyurethane characterized in that it is a polycondensation reaction product of the following components:
  • the solventless polyurethane of the present invention has a low viscosity suitable for the production of impregnated film products (especially gloves) in practical use.
  • the solventless polyurethane is soft waxy or waxy at normal temperature, it is not practical to characterize the viscosity at normal temperature.
  • the solventless polyurethane is generally used at 95 ° C, so when characterizing it, the viscosity at 95 ° C is used. Degree.
  • the solventless polyurethane of the present invention has a viscosity at 95 ° C of generally 30 mPa.s - 500 mPa.s, preferably 50 mPa.s - 230 mPa.s.
  • the residual NCO content of the solventless polyurethane is generally from 1 to 12% by weight, preferably from 2 to 5% by weight, based on the total weight of the solventless polyurethane.
  • the residual NCO content is generally determined by titration.
  • the content of the free isocyanate monomer is as low as 0.12 to 0.25 wt%, and does not contain any solvent. Therefore, the solventless polyurethane is an environmentally friendly material with high safety.
  • the content of the free isocyanate monomer is generally determined by spectrophotometry using diterpene aminobenzaldehyde as a color developing solution.
  • the isocyanate component (a) In the preparation of the solventless polyurethane of the present invention by a polycondensation method, a mixture of a diisocyanate composed of MDI and IPDI is used as the isocyanate component (a). In the present invention, other isocyanate compounds other than MDI and IPDI are not employed.
  • the MDI is MDI which is liquid at room temperature (i.e., has a melting point of less than 25 ⁇ ), and various liquefied modified MDIs can be exemplified.
  • liquefaction-modified MDI refers to chemical liquefaction modification obtained by introducing a carbamate, carbodiimide or other chemical group in 4,4,-MDI (pure MDI, solid at room temperature).
  • MDI-50, 2,4' MDI blended MDI, modified with carbodiimide, uretonimine, polyol, allophanate, carbamate, etc. 4, 4, - MDI and so on is well known in the prior art, and can be produced by a known method or a commercially available product.
  • MP- 3 of Yantai Wanhua Polyurethane Co., Ltd., Isonatel 4 3 L of Dow Chemical Co., Cosmonate LK of Mitsui Takeda, and Desmodur PF of Bayer can be cited.
  • the liquefied modified MDI generally has an NCO content of 18% to 33.5%, and a viscosity at 25 Torr is generally 30 to 300 mPa.s, which is measured by a rotational viscometer.
  • the NDI content of the IPDI is generally from 37.5 % to 37.8%, and the viscosity at 20 ° C is generally 15 mPa ⁇ s, which is measured by a rotational viscometer.
  • Specific examples thereof include polyadipate-based polyester polyols, polycaprolactone-based polyester polyols, and polycarbonate-based polyester polyols satisfying the above conditions. One or more.
  • Such a polyol component (b) is known per se in the prior art, and can be produced by a known method or a commercially available product.
  • PBA-580 of Yantai Synthetic Leather Factory and CAPA2125 of Solvay Interox Company of the United Kingdom can be cited.
  • the polyol component (c) is also used, which has a melting point of 30-35'C and a molecular weight of 300-1500.
  • a polyester polyol having a functionality greater than two Specifically, one or more of a polyadipate-based polyester polyol, a polycaprolactone-based polyester polyol, and a polycarbonate-based polyester polyol satisfying the above conditions can be given.
  • Such a polyol component (c) is known per se in the prior art, and can be produced by a known method or a commercially available product.
  • a commercial item CAPA3050, 3091, etc. of Solvay Intero, UK are mentioned.
  • the viscosity of the polycondensation reaction system can be lowered, the polycondensation reaction can be uniformly performed, and the isocyanate component can be sufficiently reacted with little residue.
  • the molar ratio of the IPDI to the MDI is from 99:1 to 1:99, preferably from 1 to 10:1, further preferably from 1 to 5:1, still more preferably from 1 to 1. 4:1.
  • the molar ratio of the NCO group of the component (a) (referring to the total content of the NCO groups of MDI and IPDI) to the total OH functional groups of the components (b) and (c) is 1-2: 1, preferably 1-1.5:1, further preferably 1-1.2:1.
  • the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is from 1 to 5:1, preferably from 1 to 3.5:1, further preferably from 1 to 2:1.
  • the solventless polyurethane obtained by the present invention is not only safe, but also has low environmental pollution, and is very suitable for producing an impregnated film product.
  • the present invention relates to a process for producing a solventless polyurethane as described above, which comprises subjecting the above-mentioned components in the absence of a solvent in the presence of a polycondensation catalyst ( a), (b) and (c) are the steps of carrying out the polycondensation reaction.
  • the method for producing the solventless polyurethane of the present invention can be carried out in a manner conventionally employed in the art for preparing a solventless polyurethane.
  • a reaction condition for example, The temperature is generally from 50 ° C to 100 ° C, the reaction time is usually from 3 to 8 hours, and the stirring speed is from 100 to 170 rpm.
  • the catalyst used is selected from organotin which is less toxic. Class of compounds.
  • organotin compound include dibutyltin dilaurate, stannous octoate, dibutyltin didodecyltin, and dibutyltin diacetate, and particularly preferably stannous octoate which is less toxic and suitable for use in medical products. .
  • the specific amount of the catalyst is preferably from 0. 01% to 0.06% by weight based on the total weight of the components (a), (b) and (c), further preferably 0.03%-0.05%.
  • the solventless polyurethane of the present invention is very suitable for use in the manufacture of impregnated film articles.
  • the present invention in a further embodiment, relates to a immersion film product.
  • the impregnated film product is produced by the impregnation method using the solventless polyurethane of the present invention.
  • the impregnated film article is a glove.
  • the impregnation may be carried out according to a conventional addition amount in the art.
  • Additives commonly used in the manufacture of impregnated film products such as antifoaming agents, antioxidants, ultraviolet absorbers, etc., are added to the solventless polyurethane of the present invention before or during the manufacture of the film product. Therefore, the impregnated film product of the present invention may be produced directly from the solventless polyurethane of the present invention, or may be produced by adding an appropriate additive to the solventless polyurethane.
  • the impregnated film product made of the solventless polyurethane of the present invention has a simple manufacturing process (no need to increase the coating step or the powder-free or powder-processing step to improve its coolness). Slip), no environmental pollution, and no waste of resources, the final product has obvious improvement in various performances such as smoothness, strength, comfort and elasticity.
  • the safety is also poorly overcome (for example, a large amount of toxic free isocyanate is present in the manufacturing process, and heavy metals remain in the manufactured product. The problem is even harmful to the human body, and there are also significant improvements in the performance of the smoothness, strength, comfort and elasticity.
  • the impregnated film product of the present invention is impregnated by the solventless polyurethane of the present invention.
  • the present invention also relates to a method for producing the above-mentioned impregnated film product (manufacturing method 1), characterized in that it comprises the following steps:
  • the method of producing the impregnated film article of the present invention is a continuous manufacturing method (manufacturing method 2), that is, it comprises the following steps:
  • the step of producing the solventless polyurethane that is, the step (1) in the production method 2
  • the step of producing the impregnated film product using the solventless polyurethane that is, the production
  • the steps (2) and (3) in the method 2 are combined and integrated.
  • the continuous manufacturing method can eliminate the steps of transportation, storage and heating of the solventless polyurethane, thereby simplifying the manufacturing method of the film product, saving energy and resources, and reducing the manufacturing cost of the film product.
  • the impregnated film product which meets the expected requirements can be directly obtained online, and therefore the method has high process flexibility and high adaptability.
  • the continuous manufacturing method can reduce the complexity and size of the industrial production line by integrating the steps of manufacturing the solventless polyurethane and the step of manufacturing the impregnated film product using the solventless polyurethane, thereby reducing the equipment cost. And maintenance costs and the like, thereby further reducing the manufacturing cost of the impregnated film product, which is very advantageous for industrial applications.
  • the production step of the solventless polyurethane i.e., the step (1) in the production method 2 is applied to the entire contents of the solventless polyurethane production method described in the present invention.
  • the mold may be subjected to an external release agent treatment as needed before performing the impregnation step.
  • the external mold release agent used in the present invention is not particularly limited, and those which are commonly used in the field of polyurethane elastomer production can be used, and examples thereof include silicone, paraffin (including liquid paraffin), polyethylene wax, talc, and higher fatty acid metal salts. Or a mixture of one or more thereof, or an aqueous emulsion or the like comprising one or more of these external release agents.
  • the mold is preferably preheated to 95 to 100 ° C before the impregnation step, as needed.
  • the solventless polyurethane is also preferably preheated to 95 to 100 Torr before the impregnation step; and in the production method 2, by the solventless polyurethane produced by the step (1)
  • the impregnation step can be carried out by adjusting the temperature to 95-100 °C.
  • the immersion time is not particularly limited, but is usually from 1 to 10 seconds.
  • the heat treatment temperature is generally 150 ⁇ 180 ⁇ , preferably 160 ° C to 170 ° C
  • the heat treatment time is generally 5-15 minutes, preferably 7-12 minutes, thereby curing the solventless polyurethane, thereby The impregnated film product of the present invention is obtained.
  • the obtained impregnated film product can be peeled off from the mold.
  • the impregnated film product obtained by the present invention there are no bright spots, flow marks, water marks, and the like on the surface, and the blocking resistance is also good. Moreover, compared with the prior art latex-type impregnated film products, there are significant improvements in various performance properties such as smoothness, strength, comfort and elasticity.
  • the type of the impregnated film product produced by the present invention is not particularly limited, but is generally a film type product, and the impregnated film product of the present invention is preferably a glove. Therefore, the mold used at this time is a hand mold.
  • the present invention relates to a method of producing a glove, the preparation of which is specifically exemplified below, but the method of manufacturing the glove of the present invention is not limited thereto.
  • the hand mold which has been surface-cleaned and heated to 95 °C is immersed in the outer mold release agent component, and then gently rubbed until the fingertips of the hand mold are no longer suspended. Then, the treated hand mold is immersed in the solvent-free polyurethane of the present invention at a temperature of 95-100 3-5 for 3-5 seconds, lifted, and gently smeared, and the surface is covered when the fingertip is no longer suspended by the fingertip. A handful of solvent-free polyurethane was placed in an oven and heated at 150 ° C for 10 minutes and then taken out. Next, cool the hand mold to 100 °C and roll the glove cover into a ring port. Then, the hand mold is cooled to below 90 ° C, and the glove is removed from the hand mold to obtain a glove product.
  • the hand mold is generally made of ceramic or silicon aluminum alloy.
  • the dumbbell type specimen is cut on the manufactured film product sample (the total length L of the sample is 115 mm, the distance between the clamps is 80 mm, and the length of the middle parallel strip is 1 mm is 33 mm, the gauge length L Q is 25mm, the width W of the end is 25mm, and the width W of the narrow part is 6mm. According to GB/T1040, it is stretched at 300mm/min on the tensile machine (manufactured by Shenzhen New Sansi Co., model CMT4204). Tensile strength and elongation at break were measured.
  • Appearance test Check the surface of the sample of the film product for bright spots, flow marks and water marks. No Film products with bright spots, flow marks and water marks were evaluated as qualified.
  • the viscosity is measured by a rotational viscometer method at 95 Torr, the residual NCO content is determined by titration, the free isocyanate content is determined spectrophotometrically, and the residual catalyst content and solvent content are determined. It is determined by the calculated value.
  • the metered polyol component (b) (polyadipate diol, grade PBA- 580 0, Yantai Wanhua Polyurethane Group Co., Ltd., having a hydroxyl value of 205.00 mgKOH/g and a molecular weight of 580, Viscosity (75 ° C) is 50-150 mPa.s, melting point is 30-40 ° C) and polyol component (c) (polycaprolactone triol, grade CAPA-30 5 0, Solvay lnterox, UK, The hydroxyl value is 310.00 mgKOH/g, the molecular weight is 540, the viscosity (60 ° C) is 160 mPa ⁇ s, the melting point is 0-10 ° C), and the distillation is carried out under vacuum conditions (vacuum degree -0.09 MPa) at 100 ° C: After 1 hour, and then cooled to 50 ° C, IPDI and L-MDI (liquefaction modified
  • the metered polyol component (b) (polyadipate diol, grade MX-355, Yantai Wanhua Polyurethane Group Co., Ltd., hydroxyl value 118.00 mgKOH/g, molecular weight 1000, viscosity (75 ° C) is 100-300 mPa.s, melting point is 20-30 ° C) and polyol component (c) (polycaprolactone triol, grade CAPA3091, Solvay Interox, UK, hydroxyl value 183.00 mgKOH /g, molecular weight 900, viscosity (60 ⁇ ) 165 mPa.s, melting point 0-10 ° C) steamed under 110 ⁇ , vacuum conditions (vacuum degree -0.09 MPa) Distillation treatment for 3 hours, then cooling to 60 ° C, IPDI and L-MDI as component (a) (carbodiimide modified MDI, grade MDI-100HL, Yantai
  • the metered polyol component (b) (polycaprolactone diol, grade CAPA2125A, Solvay Interox, UK, hydroxyl value 90.00 mgKOH / g, molecular weight 1250, viscosity (60 ° C ) is 175 mPa.s, melting point is 34-45 ° C) and polyol component (c) (polycaprolactone tetraol, grade CAPA4101, Solvay Interox, UK, hydroxyl value 218.00 mgKOH/g, molecular weight 1000, Viscosity (60 ° C) is 260 mPa.s, melting point is 10-20 ⁇ ) Distilled at 120 ° C under vacuum conditions (vacuum degree -0.09 MPa) for 6 hours, then cooled to 70 ° C temperature conditions, will be used as Component) EPDI and L-MDI (carbodiimide modified MDI, grade ISonatel 43L, Dow Chemical, NCO
  • Example 1 the method for producing a glove will be specifically described, and the impregnated film product of the present invention and the method for producing the same will be specifically described.
  • the present invention is not limited to gloves, and other impregnated film products can be similarly produced by the following methods.
  • the temperature is adjusted after the production. It is 95 ⁇ and keep the temperature ready for use).
  • a hand mold high alumina content ceramic hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT
  • an external release agent liquid paraffin, Beijing Yanlan
  • Chemical Factory Co., Ltd. The fingertips are no longer suspended with droplets.
  • the treated hand mold is immersed in the solventless polyurethane for 2 seconds, then lifted up, and gently rubbed.
  • the hand mold When the fingertip is no longer suspended by the fingertip, the hand mold is sent to the oven and uniformly heated to 165 °C. , take it out after 10 minutes. Cool the hand mold to 100 and then roll the glove cover into a ring port. The hand mold is cooled to below 90 ° C, and the glove is removed from the hand mold to obtain a glove product.
  • a commercially available nitrile latex (manufactured by Lanzhou Petrochemical Co., Ltd.) was preheated to 95 Torr.
  • a hand mold high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yan) In Lanhua Factory Co., Ltd., it is lightly swayed after lifting, and no droplets are suspended from the fingertips of the hand mold.
  • the treated hand mold is immersed in the nitrile latex for 2 seconds, then lifted up, gently rubbed, and when the fingertip is no longer suspended with a drop, the hand mold is sent to the oven and uniformly heated to 180 ° C. Take it out after 15 minutes.
  • the hand mold is cooled to 110 ° C, and then immersed in water-based polyurethane emulsion (brand LS122) for 3 seconds, then lifted, gently smashed, when the fingertips are no longer hanging with drops, the hand mold is sent into the oven evenly Heat to 180 ° C, take it for 5 minutes and take it out. Cool the hand mold to 100 ⁇ and then roll the glove cover into a ring port.
  • the hand mold is cooled to below 90 , and removed from the hand mold to obtain a glove product.
  • the hand mold is cooled to 110 ° C, and then immersed in water-based polyurethane emulsion (brand LS120) for 3 seconds, then lifted, gently smashed, when the fingertips are no longer hanging with drops, the hand mold is sent to the oven evenly Heat to 180 ° C, take it out after 15 minutes. Cool the hand mold to 100 ⁇ and then roll the glove cover into a ring port. The hand mold is cooled to below 90 ° C and taken off from the hand mold to obtain a glove product.
  • water-based polyurethane emulsion brand LS120
  • a commercially available nitrile latex (manufactured by Lanzhou Petrochemical Co., Ltd.) was preheated to 95 °C.
  • a hand mold high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yan) In Lanhua Factory Co., Ltd., it is lightly swayed after lifting, and no droplets are suspended from the fingertips of the hand mold.
  • the treated hand mold was immersed in the nitrile latex for 2 seconds, then lifted, and gently rubbed. When the fingertips were no longer suspended by the fingertips, the hand mold was sent to the oven and uniformly heated to 180.
  • the hand mold takes it out after 15 minutes.
  • the hand mold is cooled to 110 ° C, and then immersed in a modified starch aqueous dispersion (Linyi City Modified Starch Factory, surface sizing starch) for 3 seconds, then lifted, scorned, and the fingertips are no longer suspended.
  • a modified starch aqueous dispersion Li City Modified Starch Factory, surface sizing starch
  • the hand mold is sent to an oven and uniformly heated to 180 ° C for 15 minutes and then taken out.
  • the hand mold was cooled to 100 ° C, and then the glove sleeve was rolled into a ring port.
  • the hand mold is cooled to below 90 °C, and the glove is removed from the hand mold to obtain a glove product.
  • a commercially available nitrile latex (manufactured by Lanzhou Petrochemical Co., Ltd.) was preheated to 95 °C.
  • a hand mold high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yan) Lanhua Factory Co., Ltd.), scorned after lifting, until the fingertips of the hand model no longer hangs.
  • the treated hand mold is immersed in the nitrile latex for 2 seconds, then lifted up, gently rubbed, and when the fingertip is no longer suspended with a drop, the hand mold is sent to the oven and uniformly heated to 180 ° C.

Abstract

A solvent-free polyurethane is a polycondensation product of following components: (a) a binary diisocyanate mixture of diphenylmethane diisocyanate and isophorone diisocyanate, (b) a polyester polyol having a melting point of 30-35°C, a molecular weight of 300-1500 and a functionality of 2, and (c) a polyester polyol having a melting point of 30-35°C, a molecular weight of 300-1500 and a functionality of more than 2. A process of preparing the solvent-free polyurethane, and the application of the solvent-free polyurethane in preparation of film products by an impregnating method The polyurethane film product produced by the impregnating method has some improved performances such as slippery property, mechanical property and elastic property, as compared to the corresponding product of the prior art. The application of the solvent-free polyurethane in preparation of glove.

Description

一种无溶剂型聚氨酯、 其制备方法及其应用 技术领域  Solvent-free polyurethane, preparation method thereof and application thereof
本发明涉及聚氨酯领域, 更具体地说, 本发明涉及一种新型的无 溶剂型聚氨酯及其制备方法、 以及该无溶剂型聚氨酯在浸渍法膜制品 的制造中的应用。 在一个优选的实施方案中, 本发明涉及该无溶剂型 聚氨酯在手套制造中的应用。 背景技术  The present invention relates to the field of polyurethanes, and more particularly to a novel solventless polyurethane and a process for the preparation thereof, and to the use of the solventless polyurethane in the manufacture of impregnated film articles. In a preferred embodiment, the invention relates to the use of the solventless polyurethane in the manufacture of gloves. Background technique
众所周知, 在通过浸渍工艺制造的浸渍法膜制品中, 天然胶乳和 合成胶乳均有着广泛的应用。 作为该浸渍法膜制品的实例, 比如可以 举出手套(包括测试手套和医用手套等) 、 安全套和器官袋等。 这些 制品作为一种保护性体系, 无论是在职业环境还是在家庭环境中, 都 起到了阻隔微生物侵害、 防止化学药品损伤和防止液体接触等积极作 用。  It is well known that natural latex and synthetic latex have a wide range of applications in impregnated film products produced by the impregnation process. As examples of the impregnated film product, for example, gloves (including test gloves and medical gloves, etc.), condoms and organ bags, and the like can be cited. As a protective system, these products play an active role in blocking microbial attack, preventing chemical damage and preventing liquid contact, both in the occupational environment and in the home environment.
但是, 这些浸渍法膜制品在使用过程中广泛存在以下问题。 首先, 无论是由天然胶乳还是合成胶乳制造的手套, 为了提高其爽滑性而有 利于穿戴, 在其制造过程中普遍采用了无粉处理和有粉处理两种工 艺。 其中, 有粉处理工艺中使用的粉体是滑石粉或者淀粉。 从 USP 7045573 可知, 穿戴经过这种有粉处理的手套后, 使用者中大约 1% 的人会存在过敏问题。 在无粉处理工艺中, 普遍采用的是氯化工艺或 者硅油处理工艺。 但是, 氯化工艺中残留的氯对人体有害, 而且易引 起环境污染, 硅油处理工艺同样也不能达到令人满意的效果, 因为硅 油处理的手套油滑但不干爽, 因此手感不好。  However, these impregnated film products have the following problems widely in use. First of all, gloves made of natural latex or synthetic latex are beneficial for wear in order to improve their smoothness. Both powder-free and powder-treated processes are commonly used in the manufacturing process. Among them, the powder used in the powder treatment process is talc or starch. It is known from USP 7045573 that after wearing such powdered gloves, about 1% of the users have allergies. In the powder-free process, a chlorination process or a silicone oil treatment process is commonly used. However, the residual chlorine in the chlorination process is harmful to the human body and is liable to cause environmental pollution. The silicone oil treatment process also fails to achieve satisfactory results because the silicone-treated gloves are slippery but not dry, so the hand feel is not good.
为了解决上述问题, 人们尝试了采用聚合物作为涂饰层以提高爽 滑性的处理方法。 该方法所常用的聚合物是溶剂型聚氨酯或者水性聚 氨酯。 然而这种现行技术仍然存在诸如下列的缺点。 首先, 溶剂型聚 氨酯在使用过程中会挥发大量溶剂, 由此导致环境污染和资源浪费。 其次, 无论是采用溶剂型聚氨酯, 还是采用水性聚氨酯作为涂饰层, 在制造浸渍法膜制品时, 都必须特别地在天然胶乳或者合成胶乳浸渍 成膜制品之前或者之后进行该聚合物的涂饰步骤, 这样无疑又增加了 浸渍法的工艺步驟。 因此, 现有技术在通过浸渍法制造膜制品时, 普遍存在着工艺步 骤复杂, 或者资源浪费、 环境污染大等问题。 另外, 现有技术所制得 的浸渍法膜制品, 在爽滑性(手感) 、 强度、 舒适感和弹性等方面也 不是完全令人满意的。 In order to solve the above problems, a treatment method using a polymer as a coating layer to improve the slipperiness has been attempted. The polymers commonly used in this process are solvent based polyurethanes or aqueous polyurethanes. However, this prior art still has disadvantages such as the following. First, solvent-based polyurethanes volatilize large amounts of solvent during use, resulting in environmental pollution and waste of resources. Secondly, whether solvent-based polyurethane or water-based polyurethane is used as the coating layer, in the manufacture of the impregnated film product, the coating step of the polymer must be carried out before or after the natural latex or the synthetic latex is impregnated into the film-forming product. This undoubtedly increases the process steps of the impregnation method. Therefore, in the prior art, when a film product is produced by the dipping method, there are generally problems such as complicated process steps, waste of resources, and large environmental pollution. Further, the impregnated film product obtained by the prior art is not entirely satisfactory in terms of smoothness (feel), strength, comfort and elasticity.
无溶剂型聚氨酯是一种在不存在溶剂的情况下使异氰酸酯和含羟 基化合物等组分发生缩聚而获得的聚合物材料, 其不但保留了以往聚 氨酯材料固有的那些优异性能, 而且其材料本身不含有任何溶剂, 因 此在环保呼声越来越高的今天, 在很多领域都受到了很高的关注。 比 如, USP 5151484 就公开了一种无溶剂型聚氨酯, 该聚氨酯具有良好 的柔顺性和弹性。  A solventless polyurethane is a polymer material obtained by polycondensing a component such as an isocyanate and a hydroxyl group-containing compound in the absence of a solvent, which retains not only the excellent properties inherent in the conventional polyurethane materials, but also the materials themselves. Containing any solvent, it has received a lot of attention in many fields today, as environmental protection calls are getting louder and louder. For example, USP 5,151,484 discloses a solventless polyurethane which has good flexibility and elasticity.
因此, 本发明人认为, 如果采用这种无溶剂型聚氨酯来制造浸渍 法膜制品, 就有可能解决现有技术中目前存在的那些问题。 但本发明 人通过具体研究发现, 虽然这种无溶剂型聚氨酯所具有的优异的强度 和弹性等性能是浸渍法膜制品所期望的, 但是, 现有技术的无溶剂型 聚氨酯因为以下因素在浸渍法膜制品领域还无法直接获得应用。 第 一, 现有技术的无溶剂型聚氨酯由于主要用于建筑、 木器、 机械等工 业领域, 因此在其组成中大多残留毒性大的游离异氰酸酯和重金属催 化剂等组分, 但由于浸渍法膜制品一般与人体紧密接触, 所以这些组 分的残留将使得现有技术的无溶剂型聚氨酯在浸渍法膜制品应用时存 在不利之处, 即安全性差。 笫二, 现有技术的无溶剂型聚氨酯由于粘 度过高, 一般需要在高温高压的条件下进行喷涂施工, 因此, 相对于 浸渍法来说, 该喷涂法的工艺设备比较复杂, 而且对于尤其是手套这 类形状复杂的膜制品来说, 喷涂工艺难以有效地实现其形状, 操作比 较困难。  Accordingly, the inventors believe that if such a solventless polyurethane is used to produce an impregnated film article, it is possible to solve the problems currently existing in the prior art. However, the inventors have found through specific studies that although the excellent strength and elasticity properties of such a solventless polyurethane are desirable for impregnated film products, the prior art solventless polyurethanes are impregnated by the following factors. The field of film products is not directly available for application. First, the prior art solvent-free polyurethanes are mainly used in the industrial fields of construction, wood, machinery, etc., and therefore most of the components are free of free isocyanate and heavy metal catalysts, etc., but due to the impregnation of the film products In close contact with the human body, the residue of these components will make the prior art solvent-free polyurethane disadvantageous in the application of the impregnated film product, that is, the safety is poor. Secondly, the prior art solvent-free polyurethane is generally required to be sprayed under high temperature and high pressure due to high viscosity. Therefore, the spraying process is relatively complicated compared to the dipping method, and especially In the case of a complex shaped film such as a glove, the spraying process is difficult to effectively realize its shape, and the operation is difficult.
因此, 现有技术中到目前为止还未曾有成功地采用无溶剂型聚氨 酯来制造浸渍法膜制品 (尤其是手套) 的任何报道。  Therefore, there have been no reports in the prior art on the successful use of solventless polyurethanes to make impregnated film articles, especially gloves.
鉴于以上现有技术的发展状况, 需要开发一种适合用于制造浸渍 法膜制品 (比如手套) 的无溶剂型聚氨酯, 并且该无溶剂型聚氨酯不 含有机溶剂和有毒的重金属催化剂, 其制造工艺简单(无需增加涂饰 步骤或者无粉或有粉处理步骤, 以提高其爽滑性) 、 无环境污染, 并 且无资源浪费。 而且, 由该无溶剂型聚氨酯制造的浸渍法膜制品表现 出比现有技术浸渍法膜制品更为优异的爽滑性、 强度、 舒适感和弹性。 本发明即以此为目的。 发明内容 In view of the above state of the art, there is a need to develop a solventless polyurethane suitable for use in the manufacture of impregnated film products such as gloves, and the solventless polyurethane is free of organic solvents and toxic heavy metal catalysts, and a process for the production thereof Simple (no need to add finishing steps or no powder or powder processing steps to improve its smoothness), no environmental pollution, and no waste of resources. Further, the impregnated film product produced from the solventless polyurethane exhibits superior smoothness, strength, comfort and elasticity than the prior art impregnated film product. The present invention is directed to this purpose. Summary of the invention
为了解决以往技术中存在的那些问题, 本发明人通过刻苦的研究 发现, 通过选用特定的起始组分来制造无溶剂型聚氨酯, 就可以实现 本发明的上述目的, 从而完成本发明。  In order to solve the problems existing in the prior art, the inventors have found through diligent research that the above object of the present invention can be attained by selecting a specific starting component to produce a solventless polyurethane, thereby completing the present invention.
因此, 本发明涉及以下方面的内容:  Accordingly, the present invention relates to the following aspects:
1. 一种无溶剂型聚氨酯, 其特征在于, 它是以下组分的缩聚反 应产物:  A solventless polyurethane characterized in that it is a polycondensation reaction product of the following components:
( a ) 由二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯构成的二 元二异氰酸酯混合物,  (a) a diisocyanate mixture consisting of diphenylmethane diisocyanate and isophorone diisocyanate,
( b )熔点为 30-35Ό、 分子量为 300-1500并且官能度为 2 的聚 酯多元醇, 和  (b) a polyester polyol having a melting point of 30-35 Å, a molecular weight of 300-1500 and a functionality of 2, and
( c )熔点为 30-35°C、 分子量为 300-1500并且官能度大于 2的聚 酯多元醇。  (c) a polyester polyol having a melting point of 30 to 35 ° C, a molecular weight of 300 to 1,500 and a functionality of more than 2.
2. 方面 1 的无溶剂型聚氨酯, 其特征在于, 以该无溶剂型聚氨 酯的总重量为计, 所述无溶剂型聚氨酯的残余 NCO基团含量为 1-12 重量%。  2. The solventless polyurethane of aspect 1, characterized in that the solventless polyurethane has a residual NCO group content of from 1 to 12% by weight based on the total weight of the solventless polyurethane.
3. 方面 2 的无溶剂型聚氨酯, 其特征在于, 以该无溶剂型聚氨 酯的总重量为计, 所述无溶剂型聚氨酯的残余 NCO基团含量为 3-5 重量%。  3. The solventless polyurethane of aspect 2, characterized in that the solventless polyurethane has a residual NCO group content of from 3 to 5% by weight based on the total weight of the solventless polyurethane.
4. 方面 1 的无溶剂型聚氨酯, 其特征在于, 所述二苯基甲烷二 异氰酸酯在 25 下为液态。  4. The solventless polyurethane of aspect 1, wherein the diphenylmethane diisocyanate is in a liquid state at 25.
5. 方面 1 的无溶剂型聚氨酯, 其特征在于, 在所述二元二异氰 酸酯混合物中, 所述异佛尔酮二异氰酸酯与所述二苯基 ψ烷二异氰酸 酯的摩尔比为 99:1-1:99。  5. The solventless polyurethane of aspect 1, characterized in that in the binary diisocyanate mixture, the molar ratio of the isophorone diisocyanate to the diphenyldecane diisocyanate is 99:1 1:99.
6. 方面 5 的无溶剂型聚氨酯, 其特征在于, 所述异佛尔酮二异 氰酸酯与所述二苯基甲綻二异氰酸酯的摩尔比为 1-10:1。  6. The solventless polyurethane of aspect 5, wherein the molar ratio of the isophorone diisocyanate to the diphenylmethane diisocyanate is from 1 to 10:1.
7. 方面 6 的无溶剂型聚氨酯, 其特征在于, 所述异佛尔酮二异 氰酸酯与所述二苯基甲烷二异氰酸酯 7的摩尔比为 1-4:1。  7. The solventless polyurethane of aspect 6, wherein the molar ratio of the isophorone diisocyanate to the diphenylmethane diisocyanate 7 is from 1 to 4:1.
8. 方面 1 的无溶剂型聚氨酯, 其特征在于, 所述组分(b )选自 聚己二酸系聚酯多元醇、 聚己内酯系聚酯多元醇和聚碳酸酯系聚酯多 元醇中的一种或多种。 8. The solventless polyurethane of aspect 1, characterized in that the component (b) is selected from the group consisting of polyadipate polyester polyols, polycaprolactone polyester polyols, and polycarbonate polyesters. One or more of the alcohols.
9. 方面 1 的无溶剂型聚氨酯, 其特征在于, 所述组分(c)选自 聚己二酸系聚酯多元醇、 聚己内酯系聚酯多元醇和聚碳酸酯系聚酯多 元醇中的一种或多种。  9. The solventless polyurethane of aspect 1, characterized in that the component (c) is selected from the group consisting of polyadipate polyester polyols, polycaprolactone polyester polyols, and polycarbonate polyester polyols. One or more of them.
10. 方面 1 的无溶剂型聚氨酯, 其特征在于, 所述组分(a) 的 NCO基团与组分(b)和(c) 的总 OH官能团的摩尔比为 1_2:1。 10. The solventless polyurethane of aspect 1, characterized in that the molar ratio of the NCO group of the component (a) to the total OH functional group of the components (b) and (c) is 1 to 2 :1.
11. 方面 10 的无溶剂型聚氨酯, 其特征在于, 所述组分(a) 的 NCO基团与组分(b)和(c) 的总 OH官能团的摩尔比为 1-1.5:1。 11. The solventless polyurethane of aspect 10, characterized in that the molar ratio of the NCO group of the component (a) to the total OH functional group of the components (b) and (c) is 1-1. 5 :1 .
12. 方面 11 的无溶剂型聚氨酯, 其特征在于, 所述组分(a) 的 NCO基团与组分(b)和(c) 的总 OH官能团的摩尔比为 1-1.2:1。  12. The solventless polyurethane of aspect 11, characterized in that the molar ratio of the NCO group of the component (a) to the total OH functional group of the components (b) and (c) is 1-1.2:1.
13. 方面 1 的无溶剂型聚氨酯, 其特征在于, 所述组分(a) 的 NCO基团与组分(b) 的 OH官能团的摩尔比为 1-5:1。  13. The solventless polyurethane of aspect 1, characterized in that the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is from 1 to 5:1.
14. 方面 13 的无溶剂型聚氨酯, 其特征在于, 所述组分(a) 的 NCO基团与组分(b) 的 OH官能团的摩尔比为 1-3.5:1。  14. The solventless polyurethane of aspect 13, characterized in that the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is from 1 to 3.5:1.
15. 方面 14 的无溶剂型聚氨酯, 其特征在于, 所述组分(a) 的 NCO基团与组分(b) 的 OH官能团的摩尔比为 1-2:1。  15. The solventless polyurethane of aspect 14, characterized in that the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is 1-2:1.
16. 一种无溶剂型聚氨酯的制造方法, 包含在缩聚催化剂的存在 下, 在不存在溶剂的情况下, 使上述组分(a) 、 (b) 和 (c) 进行 缩聚反应的步骤。  A method for producing a solventless polyurethane comprising the step of subjecting the above components (a), (b) and (c) to a polycondensation reaction in the absence of a solvent in the presence of a polycondensation catalyst.
17. 方面 16 的无溶剂型聚氨酯的制造方法, 其特征在于, 所述 缩聚催化剂选自有机锡类化合物。  17. The method of producing a solventless polyurethane according to aspect 16, characterized in that the polycondensation catalyst is selected from the group consisting of organotin compounds.
18. 方面 17 的无溶剂型聚氨酯的制造方法, 其特征在于, 所述 有机锡类化合物选自二月桂酸二丁基锡、 辛酸亚锡、 二十二烷基硫二 丁基锡和二醋酸二丁基锡。  18. The method of producing a solventless polyurethane according to aspect 17, wherein the organotin compound is selected from the group consisting of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyltin and dibutyltin diacetate.
19. 方面 18 的无溶剂型聚氨酯的制造方法, 其特征在于, 所述 有机锡类化合物为辛酸亚锡。  19. The method of producing a solventless polyurethane according to aspect 18, wherein the organotin compound is stannous octoate.
20. 方面 16 的无溶剂型聚氨酯的制造方法, 其特征在于, 按照 重量计, 所述缩聚催化剂的用量为所述组分(a) 、 (b) 和 (c) 总 重量的 0.01%-0.06%。  20. The method of producing a solventless polyurethane according to aspect 16, characterized in that the polycondensation catalyst is used in an amount of from 0.01% to 0.06 by weight based on the total of the components (a), (b) and (c). %.
21. 方面 20 的无溶剂型聚氨酯的制造方法, 其特征在于, 按照 重量计, 所述缩聚催化剂的用量为所述组分(a) 、 (b) 和 (c) 总 重量的 0.03%-0.05%。 22. 方面 16 的无溶剂型聚氨酯的制造方法, 其特征在于, 所述 的缩聚反应的温度为 50'C-100°C, 反应时间为 3-8小时。 21. The method for producing a solventless polyurethane according to aspect 20, characterized in that the polycondensation catalyst is used in an amount of 0.03% to 0.05 by weight based on the total weight of the components (a), (b) and (c). %. 22. The method for producing a solventless polyurethane according to aspect 16, wherein the polycondensation reaction has a temperature of from 50 ° C to 100 ° C and a reaction time of from 3 to 8 hours.
23. 一种浸渍法膜制品, 其特征在于, 它是采用方面 1-15任一项 的无溶剂型聚氨酯通过浸渍法制造的。  An impregnated film article characterized in that it is produced by a dipping method using the solventless polyurethane of any one of aspects 1-15.
24. 方面 23的浸渍法膜制品, 其特征在于, 它是手套。  24. The impregnated film article of aspect 23, characterized in that it is a glove.
25. 一种浸渍法膜制品的制造方法, 其特征在于, 包含以下步骤: 25. A method of making an impregnated film article, comprising the steps of:
( 1 )将浸溃法膜制品制造用模具浸渍在方面 1-15任一项所述的 无溶剂型聚氨酯中的浸渍步骤; 和 (1) an impregnation step of immersing a mold for producing a impregnated film product in the solventless polyurethane according to any one of aspects 1 to 15;
( 2 )将步驟(1 )获得的被覆了所述无溶剂型聚氨酯的所述模具 进行热处理, 以使所述无溶剂型聚氨酯固化的热处理步骤。  (2) a heat treatment step of heat-treating the mold coated with the solventless polyurethane obtained in the step (1) to cure the solventless polyurethane.
26. —种浸渍法膜制品的制造方法, 其特征在于, 包含以下步骤: 26. A method of producing an impregnated film article, comprising the steps of:
( 1 )在缩聚催化剂的存在下, 在不存在溶剂的情况下, 使上述 组分(a ) 、 ( b ) 和 (c )进行缩聚反应以制备无溶剂型聚氨酯的步 骤; (1) a step of subjecting the above components (a), (b) and (c) to a polycondensation reaction in the absence of a solvent in the presence of a polycondensation catalyst to prepare a solventless polyurethane;
( 2 )将浸渍法膜制品制造用模具浸渍在步骤(1 )制备的无溶剂 型聚氨酯中的浸渍步骤; 和  (2) an impregnation step of immersing the mold for producing an impregnated film product in the solventless polyurethane prepared in the step (1);
( 3 )将步骤(2 )获得的被覆了所述无溶剂型聚氨酯的所述模具 进行热处理, 以使所述无溶剂型聚氨酯固化的热处理步骤。  (3) a heat treatment step of heat-treating the mold coated with the solvent-free polyurethane obtained in the step (2) to cure the solvent-free polyurethane.
27. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 所 述模具在进行所述浸渍步骤之前经外脱模剂处理。  27. The method of producing an impregnated film article of aspect 25 or 26, wherein the mold is treated with an external release agent prior to performing the impregnating step.
28. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 所 述模具在进行所述浸渍步骤之前被预热至 95-100°C。  28. The method of producing an impregnated film article of aspect 25 or 26, wherein the mold is preheated to 95-100 ° C prior to performing the impregnating step.
29. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 所 述浸渍步驟中的浸渍时间为 1-10秒。  29. The method of producing an impregnated film article of aspect 25 or 26, characterized in that the immersion time in the impregnation step is from 1 to 10 seconds.
30. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 所 述热处理步骤中的热处理温度为 150°C-18(TC, 热处理时间为 5-15分 钟。  30. The method of producing an impregnated film article of aspect 25 or 26, characterized in that the heat treatment temperature in the heat treatment step is 150 ° C - 18 (TC, and the heat treatment time is 5-15 minutes.
31. 方面 30 的浸渍法膜制品的制造方法, 其特征在于, 所述热 处理温度为 160°C -170°C, 所述热处理时间为 5-15分钟。  The method of producing an impregnated film product according to aspect 30, wherein the heat treatment temperature is from 160 ° C to 170 ° C, and the heat treatment time is from 5 to 15 minutes.
32. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 在 进行所述浸渍步骤之前, 所述无溶剂型聚氨酯的温度被调节为 95-100 32. The method of producing an impregnated film article of aspect 25 or 26, wherein the temperature of the solventless polyurethane is adjusted to 95-100 before the impregnating step.
°C。 33. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 还 包括从所述模具上剥离所获得的浸渍法膜制品的步骤。 °C. 33. The method of producing an impregnated film article of aspect 25 or 26, further comprising the step of peeling the obtained impregnated film product from the mold.
34. 方面 25或 26的浸渍法膜制品的制造方法, 其特征在于, 所 述模具为手模。  34. The method of producing an impregnated film article of aspect 25 or 26, wherein the mold is a hand mold.
35. 一种浸渍法膜制品, 其特征在于, 它是采用方面 25-34任一 项的浸渍法膜制品的制造方法制造的。 发明效果  An impregnated film article, which is produced by the method for producing an impregnated film article according to any of aspects 25-34. Effect of the invention
本发明通过采用一种特定的无溶剂型聚氨酯来制造浸渍法膜制 品, 避免了现有技术在制造浸渍法膜制品时必须面对的工艺复杂 (为 了提高爽滑性, 必须增加涂饰步驟或者无粉或有粉处理步驟) 、 环境 污染和资源浪费等问题。 同时, 与现有技术的胶乳型浸渍法膜制品相 比, 本发明的聚氨酯浸渍法膜制品在爽滑性、 力学性能和弹性等各项 使用性能方面均有明显的改善。 具体实施方式  The invention manufactures the impregnated film product by adopting a specific solventless polyurethane, which avoids the complicated process that the prior art must face in manufacturing the impregnated film product (in order to improve the smoothness, the finishing step must be increased or not Powder or powder processing steps), environmental pollution and waste of resources. At the same time, the polyurethane-impregnated film product of the present invention has a marked improvement in various properties such as slipperiness, mechanical properties and elasticity as compared with the prior art latex-type impregnated film product. detailed description
以下对本发明进行具体的说明。  The invention is specifically described below.
在本发明的上下文中, "聚氨酯" 一词表示含有氨基甲酸酯基团 的聚合物, 该聚合物还可以包含脲基团等。  In the context of the present invention, the term "polyurethane" means a polymer containing a urethane group, and the polymer may further contain a urea group or the like.
在第一个实施方案中, 本发明涉及一种无溶剂型聚氨酯, 其特征 在于, 它是以下组分的缩聚反应产物:  In a first embodiment, the present invention relates to a solventless polyurethane characterized in that it is a polycondensation reaction product of the following components:
( a ) 由二苯基甲烷二异氰酸酯 (MDI ) 和异佛尔酮二异氰酸酯 ( IPDI )构成的二元二异氰酸酯混合物,  (a) a mixture of diisocyanates consisting of diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI),
( b )熔点为 30-35°C、 分子量为 300-1500并且官能度为 2 的聚 酯多元醇, 和  (b) a polyester polyol having a melting point of 30-35 ° C, a molecular weight of 300-1500 and a functionality of 2, and
( c )熔点为 30-35°C、 分子量为 300-1500并且官能度大于 2的聚 酯多元醇。  (c) a polyester polyol having a melting point of 30 to 35 ° C, a molecular weight of 300 to 1,500 and a functionality of more than 2.
本发明的无溶剂型聚氨酯在实际应用中具有适合制造浸渍法膜制 品 (特别是手套) 的低粘度。  The solventless polyurethane of the present invention has a low viscosity suitable for the production of impregnated film products (especially gloves) in practical use.
由于该无溶剂型聚氨酯在常温下为软蜡状或者蜡状, 因此表征其 常温条件下的粘度不具有实际意义。 在本发明中, 该无溶剂型聚氨酯 一般在 95°C条件下使用, 因此本文在表征其时, 使用 95°C条件下的粘 度。 在采用旋转粘度计测定时, 本发明的无溶剂聚氨酯在 95°C条件下 粘度一般为 30 mPa.s - 500 mPa.s, 优选 50 mPa.s-230 mPa.s. Since the solventless polyurethane is soft waxy or waxy at normal temperature, it is not practical to characterize the viscosity at normal temperature. In the present invention, the solventless polyurethane is generally used at 95 ° C, so when characterizing it, the viscosity at 95 ° C is used. Degree. When measured by a rotational viscometer, the solventless polyurethane of the present invention has a viscosity at 95 ° C of generally 30 mPa.s - 500 mPa.s, preferably 50 mPa.s - 230 mPa.s.
以该无溶剂型聚氨酯的总重量为计, 该无溶剂型聚氨酯的残余 NCO含量一般为 1-12重量%, 优选 2 - 5重量%。 该残余 NCO含量 一般是采用滴定法测定的。  The residual NCO content of the solventless polyurethane is generally from 1 to 12% by weight, preferably from 2 to 5% by weight, based on the total weight of the solventless polyurethane. The residual NCO content is generally determined by titration.
在该无溶剂型聚氨酯中, 游离异氰酸酯单体的含量较低, 为 0.12- 0.25 重量%, 并且不含有任何溶剂。 因此, 该无溶剂型聚氨酯是一种 安全性高的环保型材料。 该游离异氰酸酯单体的含量一般是采用二曱 氨基苯甲醛为显色液, 用分光光度法测定的。  In the solventless polyurethane, the content of the free isocyanate monomer is as low as 0.12 to 0.25 wt%, and does not contain any solvent. Therefore, the solventless polyurethane is an environmentally friendly material with high safety. The content of the free isocyanate monomer is generally determined by spectrophotometry using diterpene aminobenzaldehyde as a color developing solution.
在通过缩聚法制备本发明的无溶剂型聚氨酯时, 采用由 MDI 和 IPDI构成的二元二异氰酸酯混合物作为异氰酸酯组分(a ) 。 在本发 明中, 不采用除 MDI和 IPDI以外的其他异氰酸酯化合物。  In the preparation of the solventless polyurethane of the present invention by a polycondensation method, a mixture of a diisocyanate composed of MDI and IPDI is used as the isocyanate component (a). In the present invention, other isocyanate compounds other than MDI and IPDI are not employed.
所述 MDI为在室温下呈液态的 MDI (即, 熔点低于 25Ό ) , 比 如可以举出各种液化改性 MDI。 在本文中, 液化改性 MDI是指通过 在 4,4,-MDI (纯 MDI, 常温下是固体) 中引入氨基甲酸酯、 碳化二 亚胺或其他化学基团而得到的化学液化改性 MDI, 或者在 4,4,-MDI 中增加异构体 2,4,-MDI含量而获得的物理液化改性 MDI, 这些液化 改性 MDI在以下有时均简称为 MDI。 具体比如可以举出 MDI-50、 2,4' MDI掺混 MDI, 用碳化二亚胺、 脲酮亚胺、 多元醇、 脲基甲酸 酯、 氨基甲酸酯等改性的 4,4,- MDI等。 这种液化改性 MDI在现有技 术中是公知的, 可以利用公知的方法进行制备, 也可以采用市售产品。 作为这类液化改性 MDI 的市售品, 可以举出烟台万华聚氨酯股份有 限公司的 MP-35, Dow 化学公司的 Isonatel43L , 三井武田的 CosmonateLK, 以及 Bayer的 DesmodurPF等。 The MDI is MDI which is liquid at room temperature (i.e., has a melting point of less than 25 Å), and various liquefied modified MDIs can be exemplified. In this context, liquefaction-modified MDI refers to chemical liquefaction modification obtained by introducing a carbamate, carbodiimide or other chemical group in 4,4,-MDI (pure MDI, solid at room temperature). MDI, or physical liquefaction-modified MDI obtained by adding isomer 2,4,-MDI content to 4,4,-MDI. These liquefied modified MDIs are sometimes referred to as MDI hereinafter. Specifically, for example, MDI-50, 2,4' MDI blended MDI, modified with carbodiimide, uretonimine, polyol, allophanate, carbamate, etc. 4, 4, - MDI and so on. Such liquefied modified MDI is well known in the prior art, and can be produced by a known method or a commercially available product. As a commercial product of such liquefied modified MDI, MP- 3 of Yantai Wanhua Polyurethane Co., Ltd., Isonatel 4 3 L of Dow Chemical Co., Cosmonate LK of Mitsui Takeda, and Desmodur PF of Bayer can be cited.
该液化改性 MDI的 NCO含量一般为 18%-33.5%, 在 25Ό下的 粘度一般为 30-300mPa.s, 该粘度是通过旋转粘度计测定的。  The liquefied modified MDI generally has an NCO content of 18% to 33.5%, and a viscosity at 25 Torr is generally 30 to 300 mPa.s, which is measured by a rotational viscometer.
所述 IPDI的 NCO含量一般为 37.5 % - 37.8 %, 在 20°C下的粘度 一般为 15mPa.s, 该粘度是通过旋转粘度计测定的。  The NDI content of the IPDI is generally from 37.5 % to 37.8%, and the viscosity at 20 ° C is generally 15 mPa·s, which is measured by a rotational viscometer.
作为熔点为 30-35 C;、 分子量为 300-1500并且官能度为 2的聚酯 多元醇组分(b ) , 只要是熔点、 分子量和官能度满足该要求的聚酯 多元醇, 就没有特别的限制。 具体可以举出满足该条件的聚己二酸系 聚酯多元醇、 聚己内酯系聚酯多元醇和聚碳酸酯系聚酯多元醇等中的 一种或多种。 As the polyester polyol component (b) having a melting point of 30-35 C; a molecular weight of 300-1500 and a functionality of 2, as long as it is a polyester polyol having a melting point, a molecular weight and a functionality satisfying the requirements, there is no particular limits. Specific examples thereof include polyadipate-based polyester polyols, polycaprolactone-based polyester polyols, and polycarbonate-based polyester polyols satisfying the above conditions. One or more.
这类多元醇组分(b )本身在现有技术中是公知的, 可以利用公 知的方法进行制备, 也可以采用市售产品。 作为其市售品, 可以举出 烟台合成革厂的 PBA-580和英国 Solvay Interox公司的 CAPA2125 等。  Such a polyol component (b) is known per se in the prior art, and can be produced by a known method or a commercially available product. As a commercial item, PBA-580 of Yantai Synthetic Leather Factory and CAPA2125 of Solvay Interox Company of the United Kingdom can be cited.
为了进一步提高浸渍法膜制品的机械强度, 在制备本发明的无溶 剂型聚氨酯时, 还采用了多元醇组分(c ) , 它是熔点在 30-35'C之间、 分子量为 300-1500并且官能度大于 2的聚酯多元醇。 具体可以举出满 足该条件的聚己二酸系聚酯多元醇、 聚己内酯系聚酯多元醇和聚碳酸 酯系聚酯多元醇等中的一种或多种。  In order to further improve the mechanical strength of the impregnated film product, in preparing the solventless polyurethane of the present invention, the polyol component (c) is also used, which has a melting point of 30-35'C and a molecular weight of 300-1500. And a polyester polyol having a functionality greater than two. Specifically, one or more of a polyadipate-based polyester polyol, a polycaprolactone-based polyester polyol, and a polycarbonate-based polyester polyol satisfying the above conditions can be given.
这类多元醇组分(c )本身在现有技术中是公知的, 可以利用公 知的方法进行制备, 也可以采用市售产品。 作为其市售品, 可以举出 英国 Solvay Intero 公司的 CAPA3050, 3091等。  Such a polyol component (c) is known per se in the prior art, and can be produced by a known method or a commercially available product. As a commercial item, CAPA3050, 3091, etc. of Solvay Intero, UK are mentioned.
如上所述, 通过选择低熔点和低粘度的起始组分来制备本发明的 无溶剂型聚氨酯, 可以降低缩聚反应体系的粘度, 使得缩聚反应均匀 进行, 使异氰酸酯组分充分反应而少残留, 从而有利于制备低粘度、 游离异氰酸酯组分极低的聚氨酯, 最终有利于制造浸渍法膜制品时浸 渍工艺的实施。  As described above, by selecting the low-melting-point and low-viscosity starting component to prepare the solvent-free polyurethane of the present invention, the viscosity of the polycondensation reaction system can be lowered, the polycondensation reaction can be uniformly performed, and the isocyanate component can be sufficiently reacted with little residue. Thereby, it is advantageous to prepare a polyurethane having a low viscosity and a very low free isocyanate component, which is ultimately advantageous for the implementation of the impregnation process in the production of the impregnated film product.
在制备本发明的无溶剂型聚氨酯时, 所述 IPDI与所述 MDI的摩 尔比为 99:1-1:99,优选 1-10:1,进一步优选 1-5:1,更进一步优选 1-4:1。 另外, 所述组分( a ) 的 NCO基团 (指的是 MDI和 IPDI的 NCO基 团的总含量)与组分(b )和(c ) 的总 OH官能团的摩尔比为 1-2:1, 优选 1-1.5:1, 进一步优选 1-1.2:1。 而且, 所述组分(a ) 的 NCO基 团与组分(b ) 的 OH官能团的摩尔比为 1-5:1, 优选 1-3.5:1, 进一步 优选 1-2:1。  In preparing the solventless polyurethane of the present invention, the molar ratio of the IPDI to the MDI is from 99:1 to 1:99, preferably from 1 to 10:1, further preferably from 1 to 5:1, still more preferably from 1 to 1. 4:1. Further, the molar ratio of the NCO group of the component (a) (referring to the total content of the NCO groups of MDI and IPDI) to the total OH functional groups of the components (b) and (c) is 1-2: 1, preferably 1-1.5:1, further preferably 1-1.2:1. Further, the molar ratio of the NCO group of the component (a) to the OH functional group of the component (b) is from 1 to 5:1, preferably from 1 to 3.5:1, further preferably from 1 to 2:1.
本发明所获得的无溶剂型聚氨酯, 不但安全性高、 环境污染小, 而且非常适合制造浸渍法膜制品。  The solventless polyurethane obtained by the present invention is not only safe, but also has low environmental pollution, and is very suitable for producing an impregnated film product.
在笫二个实施方案中, 本发明涉及上文所述的无溶剂型聚氨酯的 制造方法, 它包括在缩聚催化剂的存在下, 在不存在溶剂的情况下, 使上文所述的组分(a ) 、 (b )和(c )进行缩聚反应的步骤。  In two embodiments, the present invention relates to a process for producing a solventless polyurethane as described above, which comprises subjecting the above-mentioned components in the absence of a solvent in the presence of a polycondensation catalyst ( a), (b) and (c) are the steps of carrying out the polycondensation reaction.
本发明的无溶剂型聚氨酯的制造方法可以按照本领域在制备无溶 剂型聚氨酯时常规采用的方式进行。 作为反应条件比如可以举出, 反 应温度一般为 50°C -100°C, 反应时间一般为 3-8 小时, 搅拌速度为 100-170rpm。 The method for producing the solventless polyurethane of the present invention can be carried out in a manner conventionally employed in the art for preparing a solventless polyurethane. As a reaction condition, for example, The temperature is generally from 50 ° C to 100 ° C, the reaction time is usually from 3 to 8 hours, and the stirring speed is from 100 to 170 rpm.
为了进一步提高本发明无溶剂型聚氨酯的安全性及其在浸渍法膜 制品制造中的适合性, 在本发明的无溶剂型聚氨酯的制造方法中, 所 采用的催化剂选自毒性较小的有机锡类化合物。 作为该有机锡类化合 物, 可以举出二月桂酸二丁基锡、 辛酸亚锡、 二十二烷基硫二丁基锡 和二醋酸二丁基锡等, 特别优选毒性较小并且适合用于医疗产品的辛 酸亚锡。  In order to further improve the safety of the solventless polyurethane of the present invention and its suitability in the production of the impregnated film product, in the method for producing a solventless polyurethane of the present invention, the catalyst used is selected from organotin which is less toxic. Class of compounds. Examples of the organotin compound include dibutyltin dilaurate, stannous octoate, dibutyltin didodecyltin, and dibutyltin diacetate, and particularly preferably stannous octoate which is less toxic and suitable for use in medical products. .
虽然不做具体的限定, 但按照重量计, 所述催化剂的具体用量优 选为所述组分(a ) 、 (b ) 和 (c ) 总重量的 0·01%-0·06%, 进一步 优选 0.03%-0.05%。  Although not specifically limited, the specific amount of the catalyst is preferably from 0. 01% to 0.06% by weight based on the total weight of the components (a), (b) and (c), further preferably 0.03%-0.05%.
本发明的无溶剂型聚氨酯非常适合用于制造浸渍法膜制品。  The solventless polyurethane of the present invention is very suitable for use in the manufacture of impregnated film articles.
因此, 本发明在一个进一步的实施方案中涉及一种浸清法膜制 品。 该浸渍法膜制品是采用本发明的无溶剂型聚氨酯通过浸渍法制造 的。 在一个最优选的实施方案中, 所述浸渍法膜制品是手套。  Accordingly, the present invention, in a further embodiment, relates to a immersion film product. The impregnated film product is produced by the impregnation method using the solventless polyurethane of the present invention. In a most preferred embodiment, the impregnated film article is a glove.
为了赋予所制造的浸渍法膜制品以各种附加性能 (比如耐紫外线 性、 抗老化性和抗静电性等) , 或者使制造过程更为容易, 可以按照 本领域常规的添加量, 在该浸渍法膜制品制造之前或制造过程中, 向 本发明的无溶剂型聚氨酯中添加浸渍法膜制品制造过程中常用的添加 剂, 比如消泡剂、 抗氧化剂、 紫外线吸收剂等。 因此, 本发明的浸渍 法膜制品可以是直接由本发明的无溶剂型聚氨酯制造的, 也可以是在 该无溶剂型聚氨酯中添加了适当的添加剂之后制造的。  In order to impart various additional properties (such as ultraviolet resistance, aging resistance, antistatic property, etc.) to the impregnated film product to be produced, or to make the manufacturing process easier, the impregnation may be carried out according to a conventional addition amount in the art. Additives commonly used in the manufacture of impregnated film products, such as antifoaming agents, antioxidants, ultraviolet absorbers, etc., are added to the solventless polyurethane of the present invention before or during the manufacture of the film product. Therefore, the impregnated film product of the present invention may be produced directly from the solventless polyurethane of the present invention, or may be produced by adding an appropriate additive to the solventless polyurethane.
与现有技术的胶乳型浸渍法膜制品相比, 由本发明的无溶剂型聚 氨酯制造的浸渍法膜制品, 其制造工艺简单 (无需增加涂饰步骤或者 无粉或有粉处理步骤, 以提高其爽滑性) 、 无环境污染, 并且无资源 浪费, 最终制品在爽滑性、 强度、 舒适感和弹性等各项使用性能方面 均有明显的改善。 而且, 与直接采用现有技术的无溶剂型聚氨酯制造 的浸渍法膜制品相比, 也克服了其安全性差 (比如制造过程中存在大 量有毒的游离异氰酸酯, 并且所制造的制品中会残留重金属等, 以至 对人体有害) 的问题, 并且在爽滑性、 强度、 舒适感和弹性等各项使 用性能方面也均有明显的改善。  Compared with the latex type impregnated film product of the prior art, the impregnated film product made of the solventless polyurethane of the present invention has a simple manufacturing process (no need to increase the coating step or the powder-free or powder-processing step to improve its coolness). Slip), no environmental pollution, and no waste of resources, the final product has obvious improvement in various performances such as smoothness, strength, comfort and elasticity. Moreover, compared with the impregnated film product made directly from the prior art solventless polyurethane, the safety is also poorly overcome (for example, a large amount of toxic free isocyanate is present in the manufacturing process, and heavy metals remain in the manufactured product. The problem is even harmful to the human body, and there are also significant improvements in the performance of the smoothness, strength, comfort and elasticity.
本发明的浸渍法膜制品是采用本发明的无溶剂型聚氨酯通过浸渍 法制造的, 因此, 在一个实施方案中, 本发明还涉及上述浸渍法膜制 品的制造方法 (制造方法 1) , 其特征在于, 包含以下步骤: The impregnated film product of the present invention is impregnated by the solventless polyurethane of the present invention. The present invention also relates to a method for producing the above-mentioned impregnated film product (manufacturing method 1), characterized in that it comprises the following steps:
(1)将浸渍法膜制品制造用模具 (以下有时简称模具) 浸渍在 本发明无溶剂型聚氨酯中的浸渍步驟; 和  (1) an impregnation step of immersing a mold for producing an impregnated film product (hereinafter sometimes referred to simply as a mold) in the solventless polyurethane of the present invention;
(2)将步骤(1)获得的被覆了无溶剂型聚氨酯的该模具进行热 处理, 以使所述无溶剂型聚氨酯固化的热处理步骤。  (2) A heat treatment step of heat-treating the mold coated with the solventless polyurethane obtained in the step (1) to cure the solventless polyurethane.
在另一个实施方案中, 本发明的浸渍法膜制品的制造方法是一种 连续的制造方法(制造方法 2) , 即, 它包含以下步驟:  In another embodiment, the method of producing the impregnated film article of the present invention is a continuous manufacturing method (manufacturing method 2), that is, it comprises the following steps:
(1)在缩聚催化剂的存在下, 在不存在溶剂的情况下, 使前述 组分(a) 、 (b) 和 (c) 进行缩聚反应以制备无溶剂型聚氨酯的步 骤;  (1) a step of subjecting the above components (a), (b) and (c) to a polycondensation reaction in the absence of a solvent in the presence of a polycondensation catalyst to prepare a solventless polyurethane;
(2)在步驟(1)制备的无溶剂型聚氨酯中浸溃模具的浸渍步骤; 和  (2) an impregnation step of dipping the mold in the solventless polyurethane prepared in the step (1);
(3)将步骤(2)获得的被覆了无溶剂型聚氨酯的模具进行热处 理, 以使所述无溶剂型聚氨酯固化的热处理步骤。  (3) A heat treatment step of heat-treating the mold coated with the solventless polyurethane obtained in the step (2) to cure the solventless polyurethane.
也就是说, 在该连续的制造方法中, 使制造无溶剂型聚氨酯的步 骤(即制造方法 2 中的步驟(1) )和利用该无溶剂型聚氨酯来制造 浸渍法膜制品的步驟(即制造方法 2 中的步骤(2)和(3) )结合成 为一体, 连续进行。 该连续制造方法可省却无溶剂型聚氨酯的运输、 贮存和加热等步骤, 使得膜制品的制造方法更为简化, 节省了能源和 资源, 并降低了膜制品的制造成本。 而且, 通过适当调节无溶剂型聚 氨酯的制造步骤, 就可以在线直接获得符合预期要求的浸渍法膜制 品, 因此该方法的工艺灵活度较高, 适应性强。 再者, 该连续制造方 法通过将制造无溶剂型聚氨酯的步驟和利用该无溶剂型聚氨酯来制造 浸渍法膜制品的步骤整合在一起, 可以降低工业生产线的复杂度和尺 寸, 由此降低设备成本和维护成本等, 从而进一步降低浸渍法膜制品 的制造成本, 这对于工业应用而言是非常有利的。  That is, in the continuous manufacturing method, the step of producing the solventless polyurethane (that is, the step (1) in the production method 2) and the step of producing the impregnated film product using the solventless polyurethane (that is, the production) The steps (2) and (3) in the method 2 are combined and integrated. The continuous manufacturing method can eliminate the steps of transportation, storage and heating of the solventless polyurethane, thereby simplifying the manufacturing method of the film product, saving energy and resources, and reducing the manufacturing cost of the film product. Further, by appropriately adjusting the manufacturing steps of the solvent-free polyurethane, the impregnated film product which meets the expected requirements can be directly obtained online, and therefore the method has high process flexibility and high adaptability. Furthermore, the continuous manufacturing method can reduce the complexity and size of the industrial production line by integrating the steps of manufacturing the solventless polyurethane and the step of manufacturing the impregnated film product using the solventless polyurethane, thereby reducing the equipment cost. And maintenance costs and the like, thereby further reducing the manufacturing cost of the impregnated film product, which is very advantageous for industrial applications.
在该连续的制造方法中, 所述无溶剂型聚氨酯的制造步骤(即制 造方法 2 中的步骤(1) )适用本发明之前所述的无溶剂型聚氨酯制 造方法的全部内容。  In the continuous production method, the production step of the solventless polyurethane (i.e., the step (1) in the production method 2) is applied to the entire contents of the solventless polyurethane production method described in the present invention.
另外, 在本发明的制造方法 1和 2中, 任何未提到的事宜, 均适 用本文中在先对其所作的具体说明, 在此不再赘述。 如前所述, 无论是在制造方法 1还是制造方法 2中, 都可以根据 需要向所述无溶剂型聚氨酯中添加本领域常用的添加剂, 然后再进行 所述浸渍法膜制品的制造。 In addition, in the manufacturing methods 1 and 2 of the present invention, any matters not mentioned are applied to the specific descriptions previously made herein, and will not be described again. As described above, in the production method 1 or the production method 2, additives commonly used in the art may be added to the solventless polyurethane as needed, and then the production of the impregnated film product may be carried out.
为了使所制造的浸渍法膜制品更好地从所述模具上剥离下来, 所 述模具在进行所述浸渍步骤之前根据需要可以进行外脱模剂处理。 对 本发明所用的外脱模剂并没有特别的限制, 可以选用聚氨酯弹性体制 造领域常用的那些, 比如可以举出有机硅、 石蜡(包括液体石蜡) 、 聚乙烯蜡、 滑石粉、 高级脂肪酸金属盐或其一种或多种的混合物等, 或者包含一种或多种这些外脱模剂的水乳液等。  In order to facilitate the peeling of the produced impregnated film product from the mold, the mold may be subjected to an external release agent treatment as needed before performing the impregnation step. The external mold release agent used in the present invention is not particularly limited, and those which are commonly used in the field of polyurethane elastomer production can be used, and examples thereof include silicone, paraffin (including liquid paraffin), polyethylene wax, talc, and higher fatty acid metal salts. Or a mixture of one or more thereof, or an aqueous emulsion or the like comprising one or more of these external release agents.
虽然没有特别的限制, 但根据需要, 所述模具在进行所述浸渍步 骤之前优选被预热至 95-100°C。 在制造方法 1 中, 所述无溶剂型聚氨 酯在进行所述浸渍步骤之前也优选被预热至 95-100Ό ; 而在制造方法 2中, 通过将步骤(1 ) 所制造的无溶剂型聚氨酯的温度调节至 95-100 °C, 即可进行所述浸渍步驟。  Although not particularly limited, the mold is preferably preheated to 95 to 100 ° C before the impregnation step, as needed. In the production method 1, the solventless polyurethane is also preferably preheated to 95 to 100 Torr before the impregnation step; and in the production method 2, by the solventless polyurethane produced by the step (1) The impregnation step can be carried out by adjusting the temperature to 95-100 °C.
在进行所述浸渍步骤时, 对浸渍时间没有特别的限定, 但一般为 1-10秒。  In the impregnation step, the immersion time is not particularly limited, but is usually from 1 to 10 seconds.
在所述热处理步骤中, 热处理温度一般为 150Χ 180Ό, 优选 160 °C-170°C , 热处理时间一般为 5-15 分钟, 优选 7-12 分钟, 由此使得 所述无溶剂型聚氨酯固化, 从而获得本发明的浸渍法膜制品。  In the heat treatment step, the heat treatment temperature is generally 150 Χ 180 Ό, preferably 160 ° C to 170 ° C, and the heat treatment time is generally 5-15 minutes, preferably 7-12 minutes, thereby curing the solventless polyurethane, thereby The impregnated film product of the present invention is obtained.
另外, 待所述模具上的所述无溶剂型聚氨酯固化后, 就可以从所 述模具上剥离所获得的浸渍法膜制品了。  Further, after the solventless polyurethane on the mold is cured, the obtained impregnated film product can be peeled off from the mold.
本发明所获得的浸渍法膜制品, 从外观来看, 表面不存在亮点、 流痕和水纹等, 并且抗粘连性也好。 而且, 与现有技术的胶乳型浸渍 法膜制品相比, 在爽滑性、 强度、 舒适感和弹性等各项使用性能方面 均有明显的改善。  In the impregnated film product obtained by the present invention, there are no bright spots, flow marks, water marks, and the like on the surface, and the blocking resistance is also good. Moreover, compared with the prior art latex-type impregnated film products, there are significant improvements in various performance properties such as smoothness, strength, comfort and elasticity.
. 对本发明所制得的浸渍法膜制品的种类没有特别的限制, 但一般 为膜类制品, 优选本发明的浸渍法膜制品为手套。 因此, 此时所使用 的模具即为手模。  The type of the impregnated film product produced by the present invention is not particularly limited, but is generally a film type product, and the impregnated film product of the present invention is preferably a glove. Therefore, the mold used at this time is a hand mold.
关于针对特定的浸渍法膜制品, 如何来选择模具、 所选择的模具 的结构和形状特征等, 所制造的膜制品的结构和形状特征, 以及制造 这些膜制品时采用的各种本文中未提及的工艺参数和注意事项等, 可 以适用本领域公知的那些常识, 在此就省略其说明。 在一个具体优选的实施方案中, 本发明涉及一种手套的制造方 法, 其制备过程具体举例如下, 但本发明的手套制造方法并不限于此。 Regarding the specific impregnated film product, how to select the mold, the structure and shape characteristics of the selected mold, the structure and shape characteristics of the manufactured film product, and various kinds of articles used in the manufacture of these film products are not mentioned herein. The process parameters, precautions, and the like can be applied to those common knowledge well known in the art, and the description thereof will be omitted. In a particularly preferred embodiment, the present invention relates to a method of producing a glove, the preparation of which is specifically exemplified below, but the method of manufacturing the glove of the present invention is not limited thereto.
将经过表面清洁处理、 加热至 95 °C的手模浸入外脱模剂组分中, 然后轻甩, 至手模指尖不再悬挂有液滴。 然后, 将该经过处理的手模 浸入温度为 95-100Ό的本发明无溶剂型聚氨酯中 3-5秒, 提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将表面覆盖了一层无溶剂型聚氨酯的 手模送入烘箱中在 150°C均匀加热 10分钟后拿出。 接着, 将手模降温 至 100 °C, 将手套套口处卷成环形端口。 然后, 使手模降温至 90°C以 下, 将手套从手模上脱下, 即得手套制品。  The hand mold which has been surface-cleaned and heated to 95 °C is immersed in the outer mold release agent component, and then gently rubbed until the fingertips of the hand mold are no longer suspended. Then, the treated hand mold is immersed in the solvent-free polyurethane of the present invention at a temperature of 95-100 3-5 for 3-5 seconds, lifted, and gently smeared, and the surface is covered when the fingertip is no longer suspended by the fingertip. A handful of solvent-free polyurethane was placed in an oven and heated at 150 ° C for 10 minutes and then taken out. Next, cool the hand mold to 100 °C and roll the glove cover into a ring port. Then, the hand mold is cooled to below 90 ° C, and the glove is removed from the hand mold to obtain a glove product.
所述手模一般为陶瓷或者硅铝合金材质。 实施例  The hand mold is generally made of ceramic or silicon aluminum alloy. Example
以下例举实施例和比较例对本发明进行更为具体的说明, 但本发 明并不限于此。 实施例和比较例中使用的所有试剂均为化学纯试剂, 并且是普通的市售品, 除非另有特别说明。  The present invention will be more specifically described by the following examples and comparative examples, but the invention is not limited thereto. All reagents used in the examples and comparative examples are chemically pure reagents and are common commercial products unless otherwise specified.
以下实施例和比较例中的部分性能参数是按照以下方法测定的。 另外, 未具体说明的测试方法均采用本领域常规的那些方法。 测试方法:  Some of the performance parameters in the following examples and comparative examples were determined in the following manner. In addition, test methods not specifically described employ those methods conventional in the art. testing method:
1 ) 力学性能测试: 在所制造的膜制品样品上裁取哑铃型试样(试 样总长度 L为 115mm, 夹具间距离 L2为 80mm, 中间平行窄条部分 长度 1^为 33mm, 标距 LQ为 25mm, 端部宽度 W 为 25mm, 窄小部 分宽度 W。为 6mm ) , 按照 GB/T1040, 在拉力机(深圳新三思公司制 造, 型号 CMT4204 ) 上以 300mm/min 的速度进行拉伸, 测定拉伸强 度和断裂伸长率。 1) Mechanical property test: The dumbbell type specimen is cut on the manufactured film product sample (the total length L of the sample is 115 mm, the distance between the clamps is 80 mm, and the length of the middle parallel strip is 1 mm is 33 mm, the gauge length L Q is 25mm, the width W of the end is 25mm, and the width W of the narrow part is 6mm. According to GB/T1040, it is stretched at 300mm/min on the tensile machine (manufactured by Shenzhen New Sansi Co., model CMT4204). Tensile strength and elongation at break were measured.
2 ) 防粘连性测试: 将 10只膜制品样品叠放于 10kg铁板下, 置于 70°C条件下放置 24小时, 然后检查各膜制品的表面之间是否有粘连。 无粘连的膜制品评价为合格。 2) Anti-blocking test: Ten film samples were stacked under a 10 kg iron plate, placed at 70 ° C for 24 hours, and then examined for adhesion between the surfaces of the film products. Non-adhesive film products were evaluated as acceptable.
3 )爽滑性测试: 选五名资深手套销售者, 用手指捏搓膜制品样品, 按照感官评定, 对爽滑性能打分, 最高分 10分, 最低分 1分, 对五名 评审者的打分综合后求平均值, 以平均值的高低进行评价。  3) Slip test: Select five senior glove sellers, use your fingers to pinch the sample of the enamel film, and score the smoothness according to the sensory evaluation. The highest score is 10 points, the lowest score is 1 point, and the scores of the five reviewers are scored. After the combination, the average value was evaluated and the average value was evaluated.
4 )外观测试: 检测膜制品样品表面是否有亮点、 流痕和水紋。 无 亮点、 流痕和水纹的膜制品评价为合格。 4) Appearance test: Check the surface of the sample of the film product for bright spots, flow marks and water marks. No Film products with bright spots, flow marks and water marks were evaluated as qualified.
5 )舒适感测试: 选五名化学实验负在操作实验时穿戴手套, 每天 5) Comfort test: Choose five chemical experiments, wear gloves when operating the experiment, daily
4小时, 连续穿戴 30个工作日, 记录穿戴者出现过敏不适感的人次数。 记录的数值越小, 舒适感就越好。 首先给出本发明的无溶剂型聚氨酯的制造实例。 4 hours, 30 working days in a row, recording the number of people with allergies in the wearer. The smaller the recorded value, the better the comfort. First, a production example of the solventless polyurethane of the present invention is given.
在表征该无溶剂型聚氨酯时, 粘度是采用旋转粘度计方法在 95Ό 下测定的, 残余 NCO含量是采用滴定法测定的, 游离异氰酸酯含量是 采用分光光度法测定的, 并且残余催化剂含量和溶剂含量是通过计算 值确定的。 合成例 1  In characterizing the solventless polyurethane, the viscosity is measured by a rotational viscometer method at 95 Torr, the residual NCO content is determined by titration, the free isocyanate content is determined spectrophotometrically, and the residual catalyst content and solvent content are determined. It is determined by the calculated value. Synthesis example 1
按照表 1的配方, 将计量的多元醇组分(b ) (聚己二酸系二醇, 牌号 PBA-580, 烟台万华聚氨酯集团公司, 羟值为 205.00 mgKOH/g, 分子量为 580, 粘度(75°C )为 50-150 mPa.s, 熔点为 30-40°C )和多 元醇组分(c ) (聚己内酯三醇, 牌号 CAPA-3050, 英国 Solvay lnterox 公司, 羟值为 310.00 mgKOH/g, 分子量为 540, 粘度( 60°C )为 160 mPa.s, 熔点为 0-10°C )在 100°C:、 真空条件(真空度 -0.09MPa )下蒸 馏处理 1小时, 然后降温到 50°C温度条件下, 将作为组分(a )的 IPDI 和 L-MDI (液化改性 MDI, 牌号 MDI-50, 烟台万华聚氨酯集团公司, NCO 含量为 33.50%, 熔点为 15°C以下, 粘度( 50°C )为 3-5mPa.s ) 的二元二异氰酸酯混合物在搅拌条件下緩慢加入, 之后加入计量的催 化剂辛酸亚锡, 搅拌速度为 100r/min, 反应 3 小时, 即获得本发明的 无溶剂型聚氨酯, 其具体表征参见表 1。 合成例 2 According to the formulation of Table 1, the metered polyol component (b) (polyadipate diol, grade PBA- 580 0, Yantai Wanhua Polyurethane Group Co., Ltd., having a hydroxyl value of 205.00 mgKOH/g and a molecular weight of 580, Viscosity (75 ° C) is 50-150 mPa.s, melting point is 30-40 ° C) and polyol component (c) (polycaprolactone triol, grade CAPA-30 5 0, Solvay lnterox, UK, The hydroxyl value is 310.00 mgKOH/g, the molecular weight is 540, the viscosity (60 ° C) is 160 mPa·s, the melting point is 0-10 ° C), and the distillation is carried out under vacuum conditions (vacuum degree -0.09 MPa) at 100 ° C: After 1 hour, and then cooled to 50 ° C, IPDI and L-MDI (liquefaction modified MDI, grade MDI-50, Yantai Wanhua Polyurethane Group Co., Ltd., as component (a), NCO content of 33.50%, The binary diisocyanate mixture having a melting point of 15 ° C or less and a viscosity (50 ° C) of 3-5 mPa·s is slowly added under stirring, and then a metered catalyst of stannous octoate is added at a stirring speed of 100 r/min. The solventless polyurethane of the present invention was obtained in 3 hours, and its specific characterization is shown in Table 1. Synthesis Example 2
按照表 1 的配方, 将计量的多元醇组分(b ) (聚己二酸系二醇, 牌号 MX-355, 烟台万华聚氨酯集团公司, 羟值为 118.00 mgKOH/g, 分子量为 1000, 粘度(75°C ) 为 100-300 mPa.s, 熔点为 20-30°C )和 多元醇组分(c ) (聚己内酯三醇,牌号 CAPA3091 ,英国 Solvay Interox 公司, 羟值为 183.00 mgKOH/g, 分子量为 900, 粘度( 60Ό )为 165 mPa.s, 熔点为 0-10°C )在 110Ό、 真空条件(真空度 -0.09MPa )下蒸 馏处理 3小时, 然后降温到 60°C温度条件下, 将作为组分( a )的 IPDI 和 L-MDI (碳化二亚胺改性 MDI, 牌号 MDI-100HL, 烟台万华聚氨 酯集团公司, NCO含量为 23.00%, 熔点为 15Ό以下, 粘度(25Ό ) 为 60mPa.s ) 的二元二异氰酸酯混合物在搅拌条件下緩慢加入, 之后 加入计量的催化剂辛酸亚锡, 反应 4 小时, 搅拌速度为 130r/min, 即 获得本发明的无溶剂型聚氨酯, 其具体表征参见表 1。 合成例 3 According to the formulation of Table 1, the metered polyol component (b) (polyadipate diol, grade MX-355, Yantai Wanhua Polyurethane Group Co., Ltd., hydroxyl value 118.00 mgKOH/g, molecular weight 1000, viscosity (75 ° C) is 100-300 mPa.s, melting point is 20-30 ° C) and polyol component (c) (polycaprolactone triol, grade CAPA3091, Solvay Interox, UK, hydroxyl value 183.00 mgKOH /g, molecular weight 900, viscosity (60 Ό) 165 mPa.s, melting point 0-10 ° C) steamed under 110 Ό, vacuum conditions (vacuum degree -0.09 MPa) Distillation treatment for 3 hours, then cooling to 60 ° C, IPDI and L-MDI as component (a) (carbodiimide modified MDI, grade MDI-100HL, Yantai Wanhua Polyurethane Group, NCO The binary diisocyanate mixture having a content of 23.00%, a melting point of 15 Ό or less and a viscosity (25 Ό) of 60 mPa·s was slowly added under stirring, and then a metered catalyst of stannous octoate was added for 4 hours, and the stirring speed was 130 r/ Min, that is, the solventless polyurethane of the present invention is obtained, and its specific characterization is shown in Table 1. Synthesis Example 3
按照表 1的配方, 将计量的多元醇组分(b ) (聚己内酯系二醇, 牌号 CAPA2125A,英国 Solvay Interox公司,羟值为 90.00 mgKOH/g, 分子量为 1250, 粘度(60°C )为 175mPa.s, 熔点为 34-45 °C )和多元 醇组分(c ) (聚己内酯四醇, 牌号 CAPA4101 , 英国 Solvay Interox 公司, 羟值为 218.00 mgKOH/g, 分子量为 1000, 粘度(60°C )为 260 mPa.s, 熔点为 10-20Ό )在 120°C、 真空条件(真空度 -0.09MPa ) 下 蒸馏处理 6小时,然后降温到 70°C温度条件下,将作为组分 )的 EPDI 和 L-MDI (碳化二亚胺改性 MDI, 牌号 ISonatel43L, Dow Chemical, NCO 含量为 29,20%, 熔点为 25°C以下, 粘度(25°C )为 33mPa.s ) 的二元二异氰酸酯混合物在搅拌条件下緩慢加入, 之后加入计量的催 化剂辛酸亚锡, 反应 5 小时, 搅拌速度为 170r/min, 即获得本发明的 无溶剂型聚氨酯, 其具体表征参见表 1。  According to the formulation of Table 1, the metered polyol component (b) (polycaprolactone diol, grade CAPA2125A, Solvay Interox, UK, hydroxyl value 90.00 mgKOH / g, molecular weight 1250, viscosity (60 ° C ) is 175 mPa.s, melting point is 34-45 ° C) and polyol component (c) (polycaprolactone tetraol, grade CAPA4101, Solvay Interox, UK, hydroxyl value 218.00 mgKOH/g, molecular weight 1000, Viscosity (60 ° C) is 260 mPa.s, melting point is 10-20 Ό) Distilled at 120 ° C under vacuum conditions (vacuum degree -0.09 MPa) for 6 hours, then cooled to 70 ° C temperature conditions, will be used as Component) EPDI and L-MDI (carbodiimide modified MDI, grade ISonatel 43L, Dow Chemical, NCO content 29, 20%, melting point below 25 ° C, viscosity (25 ° C) 33 mPa.s) The binary diisocyanate mixture was slowly added under stirring, and then the metered catalyst stannous octoate was added, and the reaction was carried out for 5 hours at a stirring rate of 170 r/min to obtain the solventless polyurethane of the present invention. The specific characteristics are shown in Table 1.
以下以手套的制造方法为例, 具体说明本发明的浸渍法膜制品及 其制造方法, 但本发明并不限于手套, 其他浸渍法膜制品可参照以下 方法类似地制造。 实施例 1  Hereinafter, the method for producing a glove will be specifically described, and the impregnated film product of the present invention and the method for producing the same will be specifically described. However, the present invention is not limited to gloves, and other impregnated film products can be similarly produced by the following methods. Example 1
将本发明的无溶剂型聚氨酯预热至 95Ό (如果该无溶剂型聚氨酯 在合成后直接用于制造本发明的手套制品 (相应于本发明的制造方法 2 ) , 则在制造后将其温度调节为 95Ό并保持该温度待用即可) 。 将经 过表面清洁处理、 加热至 95 °C的手模 (高氧化铝含量陶瓷基手模, Thailand, Euroceramic Technologies Co., Ltd., 牌号为 ECT )浸入外 脱模剂 (液体石蜡, 北京燕兰化工厂有限公司) 中, 提起后轻甩, 至 手模指尖不再悬挂有液滴。 将该经过处理的手模浸入该无溶剂型聚氨 酯中 2 秒钟, 然后提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将手 模送入烘箱中均匀加热至 165°C, 持续 10分钟后拿出。 将手模降温至 100 , 然后将手套套口处卷成环形端口。 将手模降温至 90°C以下, 将 手套从手模上脱下, 即得手套制品。 Preheating the solventless polyurethane of the present invention to 95 Torr (if the solventless urethane is directly used in the production of the glove article of the present invention after synthesis (corresponding to the production method 2 of the present invention), the temperature is adjusted after the production. It is 95 Ό and keep the temperature ready for use). A hand mold (high alumina content ceramic hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yanlan) Chemical Factory Co., Ltd.) The fingertips are no longer suspended with droplets. The treated hand mold is immersed in the solventless polyurethane for 2 seconds, then lifted up, and gently rubbed. When the fingertip is no longer suspended by the fingertip, the hand mold is sent to the oven and uniformly heated to 165 °C. , take it out after 10 minutes. Cool the hand mold to 100 and then roll the glove cover into a ring port. The hand mold is cooled to below 90 ° C, and the glove is removed from the hand mold to obtain a glove product.
在该实施例 1 中, 分别采用了合成例 I-3 制得的无溶剂型聚氨酯 制造了手套制品。 In this Example 1, a glove product was produced using the solventless polyurethane obtained in Synthesis Example I- 3 , respectively.
对所制得的手套制品分别按照之前规定的方法测定其力学性能、 防粘连性、 爽滑性、 外观和舒适感, 测定结果汇总于表 2。 对照例 1 (丁腈胶乳浸渍法手套 +水性聚氨酯涂饰层)  The obtained glove products were measured for mechanical properties, anti-blocking properties, smoothness, appearance and comfort according to the previously specified methods, and the results of the measurements are summarized in Table 2. Comparative Example 1 (Nitrile latex impregnated gloves + waterborne polyurethane finish)
将市售的丁腈胶乳(兰州石化制)预热至 95Ό。 将经过表面清洁 处理、 加热至 95 °C的手模(高氧化铝含量陶瓷基的手模, Thailand, Euroceramic Technologies Co., Ltd., 牌号为 ECT )浸入外脱模剂 (液 体石蜡, 北京燕兰化工厂有限公司) 中, 提起后轻甩, 至手模指尖不 再悬挂有液滴。 将该经过处理的手模浸入该丁腈胶乳中 2 秒钟, 然后 提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将手模送入烘箱中均匀 加热至 180°C, 持续 15分钟后拿出。 将手模降温至 110°C, 再浸入水 性聚氨酯乳液(牌号 LS122 ) 中 3秒钟, 然后提起, 轻甩, 待手模指 尖不再悬挂有坠滴时, 将手模送入烘箱中均匀加热至 180°C, 持续 I5 分钟后拿出。 将手模降温至 100Ό, 然后将手套套口处卷成环形端口。 将手模降温至 90Ό以下, 从手模上脱下, 即得手套制品。 A commercially available nitrile latex (manufactured by Lanzhou Petrochemical Co., Ltd.) was preheated to 95 Torr. A hand mold (high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yan) In Lanhua Factory Co., Ltd., it is lightly swayed after lifting, and no droplets are suspended from the fingertips of the hand mold. The treated hand mold is immersed in the nitrile latex for 2 seconds, then lifted up, gently rubbed, and when the fingertip is no longer suspended with a drop, the hand mold is sent to the oven and uniformly heated to 180 ° C. Take it out after 15 minutes. The hand mold is cooled to 110 ° C, and then immersed in water-based polyurethane emulsion (brand LS122) for 3 seconds, then lifted, gently smashed, when the fingertips are no longer hanging with drops, the hand mold is sent into the oven evenly Heat to 180 ° C, take it for 5 minutes and take it out. Cool the hand mold to 100 Ό and then roll the glove cover into a ring port. The hand mold is cooled to below 90 , and removed from the hand mold to obtain a glove product.
对所制得的手套制品分别按照之前规定的方法测定其力学性能、 防粘连性、 爽滑性、 外观和舒适感, 测定结果汇总于表 2。 对照例 2 (天然胶乳浸渍法手套 +水性聚氨酯涂饰层)  The obtained glove products were measured for mechanical properties, anti-blocking properties, smoothness, appearance and comfort according to the previously specified methods, and the results of the measurements are summarized in Table 2. Comparative Example 2 (Natural Latex Dipping Gloves + Waterborne Polyurethane Finish)
将市售的天然胶乳(产地: 马来西亚)预热至 95°C。 将经过表面 清洁处理、加热至 95Ό的手模(高氧化铝含量陶瓷基的手模, Thailand, Euroceramic Technologies Co., Ltd., 牌号为 ECT )浸入外脱模剂 (液 体石蜡, 北京燕兰化工厂有限公司) 中, 提起后轻甩, 至手模指尖不 再悬桂有液滴。 将该经过处理的手模浸入该热的天然胶乳中 2 秒钟, 然后提起, 轻甩, 待手模指尖不再悬桂有坠滴时, 将手模送入烘箱中 均匀加热至 180°C , 持续 15分钟后拿出。 将手模降温至 110°C , 再浸 入水性聚氨酯乳液(牌号 LS120 ) 中 3 秒钟, 然后提起, 轻甩, 待手 模指尖不再悬挂有坠滴时, 将手模送入烘箱中均匀加热至 180°C, 持续 15 分钟后拿出。 将手模降温至 100Ό , 然后将手套套口处卷成环形端 口。 将手模降温至 90°C以下, 从手模上脱下, 即得手套制品。 Commercially available natural rubber latex (Origin: Malaysia) preheated to 9 5 ° C. A hand mold (high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 浸 is immersed in an external release agent (liquid paraffin, Beijing Yanlan Chemical) Factory Co., Ltd.), scorned after lifting, until the fingertips of the hand model are no longer suspended. Immerse the treated hand mold into the hot natural latex for 2 seconds, then lift it up and gently smear it. When the fingertips of the hand die are no longer suspended, the hand mold is sent to the oven. Heat evenly to 180 ° C for 15 minutes and take out. The hand mold is cooled to 110 ° C, and then immersed in water-based polyurethane emulsion (brand LS120) for 3 seconds, then lifted, gently smashed, when the fingertips are no longer hanging with drops, the hand mold is sent to the oven evenly Heat to 180 ° C, take it out after 15 minutes. Cool the hand mold to 100 Ό and then roll the glove cover into a ring port. The hand mold is cooled to below 90 ° C and taken off from the hand mold to obtain a glove product.
对所制得的手套制品分别按照之前规定的方法测定其力学性能、 防粘连性、 爽滑性、 外观和舒适感, 测定结果汇总于表 2。 对照例 3 (丁腈胶乳浸渍法手套 +淀粉处理)  The obtained glove products were measured for mechanical properties, anti-blocking properties, smoothness, appearance and comfort according to the previously specified methods, and the results of the measurements are summarized in Table 2. Comparative Example 3 (Nitrile latex impregnated gloves + starch treatment)
将市售的丁腈胶乳(兰州石化制)预热至 95 °C。 将经过表面清洁 处理、 加热至 95 °C的手模(高氧化铝含量陶瓷基的手模, Thailand, Euroceramic Technologies Co., Ltd. , 牌号为 ECT )浸入外脱模剂 (液 体石蜡, 北京燕兰化工厂有限公司) 中, 提起后轻甩, 至手模指尖不 再悬挂有液滴。 将该经过处理的手模浸入该丁腈胶乳中 2 秒钟, 然后 提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将手模送入烘箱中均匀 加热至 180。C, 持续 15分钟后拿出。 将手模降温至 110°C , 再浸入改 性淀粉水分散体(临沂市变性淀粉厂, 表面施胶淀粉) 中 3 秒钟, 然 后提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将手模送入烘箱中均 匀加热至 180°C , 持续 15分钟后拿出。 将手模降温至 100°C, 然后将 手套套口处卷成环形端口。 将手模降温至 90 °C以下, 将手套从手模上 脱下, 即得手套制品。  A commercially available nitrile latex (manufactured by Lanzhou Petrochemical Co., Ltd.) was preheated to 95 °C. A hand mold (high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yan) In Lanhua Factory Co., Ltd., it is lightly swayed after lifting, and no droplets are suspended from the fingertips of the hand mold. The treated hand mold was immersed in the nitrile latex for 2 seconds, then lifted, and gently rubbed. When the fingertips were no longer suspended by the fingertips, the hand mold was sent to the oven and uniformly heated to 180. C, take it out after 15 minutes. The hand mold is cooled to 110 ° C, and then immersed in a modified starch aqueous dispersion (Linyi City Modified Starch Factory, surface sizing starch) for 3 seconds, then lifted, scorned, and the fingertips are no longer suspended. When dropping, the hand mold is sent to an oven and uniformly heated to 180 ° C for 15 minutes and then taken out. The hand mold was cooled to 100 ° C, and then the glove sleeve was rolled into a ring port. The hand mold is cooled to below 90 °C, and the glove is removed from the hand mold to obtain a glove product.
对所制得的手套制品分别按照之前规定的方法测定其力学性能、 防粘连性、 爽滑性、 外观和舒适感, 测定结果汇总于表 2。 对照例 4 (丁腈胶乳浸渍法手套 +硅油处理)  The obtained glove products were measured for mechanical properties, anti-blocking properties, smoothness, appearance and comfort according to the previously specified methods, and the results of the measurements are summarized in Table 2. Comparative Example 4 (Nitrile latex impregnated gloves + silicone oil treatment)
将市售的丁腈胶乳(兰州石化制)预热至 95 °C。 将经过表面清洁 处理、 加热至 95 °C的手模(高氧化铝含量陶瓷基的手模, Thailand, Euroceramic Technologies Co., Ltd. , 牌号为 ECT )浸入外脱模剂 (液 体石蜡, 北京燕兰化工厂有限公司) 中, 提起后轻甩, 至手模指尖不 再悬桂有液滴。 将该经过处理的手模浸入该丁腈胶乳中 2 秒钟, 然后 提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将手模送入烘箱中均匀 加热至 180°C, 持续 15分钟后拿出。 将手模降温至 110。C, 再浸入水 性氨基硅油 (QL-402, 黄山市强力化工) 中 3秒钟, 然后提起, 轻甩, 待手模指尖不再悬挂有坠滴时, 将手模送入烘箱中均匀加热至 180°C, 持续 15分钟后拿出。 将手模降温至 100°C, 然后将手套套口处卷成环 形端口。 将手模降温至 90°C以下, 将手套从手模上脱下, 即得手套制 对所制得的手套制品分别按照之前规定的方法测定其力学性能、 防粘连性、 爽滑性、 外观和舒适感, 测定结果汇总于表 2。 A commercially available nitrile latex (manufactured by Lanzhou Petrochemical Co., Ltd.) was preheated to 95 °C. A hand mold (high alumina content ceramic based hand mold, Thailand, Euroceramic Technologies Co., Ltd., grade ECT) that has been surface cleaned and heated to 95 ° C is immersed in an external release agent (liquid paraffin, Beijing Yan) Lanhua Factory Co., Ltd.), scorned after lifting, until the fingertips of the hand model no longer hangs. The treated hand mold is immersed in the nitrile latex for 2 seconds, then lifted up, gently rubbed, and when the fingertip is no longer suspended with a drop, the hand mold is sent to the oven and uniformly heated to 180 ° C. Take it out after 15 minutes. Cool the hand mold to 110. C, then immersed in water Amino silicone oil (QL-402, Huangshan City Strong Chemicals) for 3 seconds, then lift, squat, when the fingertips are no longer hanging with drops, the hand mold is sent to the oven and heated evenly to 180 °C , take it out after 15 minutes. The hand mold was cooled to 100 ° C and the glove cuff was rolled into a ring port. The hand mold is cooled to below 90 ° C, and the glove is removed from the hand mold, so that the glove product obtained by the glove is respectively measured for mechanical properties, anti-blocking property, smoothness and appearance according to the previously specified method. And the comfort, the measurement results are summarized in Table 2.

Claims

权 利 要 求 Rights request
1. 一种无溶剂型聚氨酯, 其特征在于, 它是以下组分的缩聚反 应产物: A solventless polyurethane characterized in that it is a polycondensation reaction product of the following components:
(a) 由二苯基曱烷二异氰酸酯和异佛尔酮二异氰酸酯构成的二 元二异氰酸酯混合物,  (a) a diisocyanate mixture composed of diphenylnonane diisocyanate and isophorone diisocyanate,
(b)熔点为 30-35°C、 分子量为 300-1500并且官能度为 2 的聚 酯多元醇, 和  (b) a polyester polyol having a melting point of 30-35 ° C, a molecular weight of 300-1500 and a functionality of 2, and
(c)熔点为 30-35°C、 分子量为 300-1500并且官能度大于 2的聚 酯多元醇。  (c) a polyester polyol having a melting point of 30 to 35 ° C, a molecular weight of 300 to 1,500 and a functionality of more than 2.
2. 权利要求 1 的无溶剂型聚氨酯, 其特征在于, 所述二苯基曱 烷二异氰酸酯在 25 °C下为液态。  The solventless polyurethane according to claim 1, wherein the diphenylnonane diisocyanate is in a liquid state at 25 °C.
3. 权利要求 1 的无溶剂型聚氨酯, 其特征在于, 在所述二元二 异氰酸酯混合物中, 所述异佛尔酮二异氰酸酯与所述二苯基甲烷二异 氰酸酯的摩尔比为 1-10:1。  3. The solventless polyurethane of claim 1, wherein in the binary diisocyanate mixture, the molar ratio of the isophorone diisocyanate to the diphenylmethane diisocyanate is 1-10: 1.
4. 一种无溶剂型聚氨酯的制造方法, 包含在缩聚催化剂的存在 下, 在不存在溶剂的情况下, 使上述组分(a) 、 (b) 和 (c) 进行 缩聚反应的步驟。  A method for producing a solventless polyurethane comprising the step of subjecting the above components (a), (b) and (c) to a polycondensation reaction in the absence of a solvent in the presence of a polycondensation catalyst.
5. —种浸渍法膜制品, 其特征在于, 它是采用权利要求 1-3任一 项的无溶剂型聚氨酯通过浸渍法制造的。  An impregnated film product characterized in that it is produced by a dipping method using the solventless polyurethane of any one of claims 1-3.
6. 权利要求 5的浸渍法膜制品, 其特征在于, 它是手套。  6. The impregnated film article of claim 5, which is a glove.
7. 一种浸溃法膜制品的制造方法, 其特征在于, 包含以下步骤: A method of producing an impregnated film product, comprising the steps of:
( 1 )将浸渍法膜制品制造用模具浸渍在权利要求 1-3任一项所述 的无溶剂型聚氨酯中的浸渍步骤; 和 (1) an impregnation step of immersing a mold for producing an impregnated film product in the solventless polyurethane according to any one of claims 1 to 3;
(2)将步骤(1)获得的被覆了无溶剂型聚氨酯的模具进行热处 理, 以使所述无溶剂型聚氨酯固化的热处理步骤。  (2) A heat treatment step of heat-treating the mold coated with the solventless polyurethane obtained in the step (1) to cure the solventless polyurethane.
8. 一种浸渍法膜制品的制造方法, 其特征在于, 包含以下步骤: A method of producing an impregnated film product, comprising the steps of:
(1)在缩聚催化剂的存在下, 在不存在溶剂的情况下, 使上述 组分(a) 、 (b)和 (c) 进行缩聚反应以制备无溶剂型聚氨酯的步 骤; (1) a step of subjecting the above components (a), (b) and (c) to a polycondensation reaction in the absence of a solvent in the presence of a polycondensation catalyst to prepare a solventless polyurethane;
(2)将浸溃法膜制品制造用模具浸渍在步骤(1) 制备的无溶剂 型聚氨酯中的浸渍步骤; 和 ( 3 )将步驟(2 )获得的被覆了所述无溶剂型聚氨酯的所述模具 进行热处理, 以使所述无溶剂型聚氨酯固化的热处理步驟。 (2) an impregnation step of immersing the mold for manufacturing the impregnated film product in the solventless polyurethane prepared in the step (1); (3) The heat treatment step of heat-treating the mold coated with the solventless polyurethane obtained in the step (2) to cure the solventless polyurethane.
9. 权利要求 7 或 8 的浸溃法膜制品的制造方法, 其特征在于, 所述模具为手模。  The method of producing an impregnated film product according to claim 7 or 8, wherein the mold is a hand mold.
10. 一种浸渍法膜制品, 其特征在于, 它是采用方面 7-9 任一项 的浸渍法膜制品的制造方法制造的。  An impregnated film product, which is produced by the method for producing an impregnated film product according to any one of aspects 7-9.
PCT/CN2006/003548 2006-12-22 2006-12-22 Solvent-free polyurethane, its preparation and application WO2008077270A1 (en)

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