WO2019128520A1 - 无溶剂树脂及其制备方法、制备试剂盒和应用 - Google Patents

无溶剂树脂及其制备方法、制备试剂盒和应用 Download PDF

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Publication number
WO2019128520A1
WO2019128520A1 PCT/CN2018/115755 CN2018115755W WO2019128520A1 WO 2019128520 A1 WO2019128520 A1 WO 2019128520A1 CN 2018115755 W CN2018115755 W CN 2018115755W WO 2019128520 A1 WO2019128520 A1 WO 2019128520A1
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Prior art keywords
butanediol
glycol
parts
polyol
solvent
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PCT/CN2018/115755
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English (en)
French (fr)
Inventor
安荣万
杨骏
Original Assignee
三星聚合物有限公司
杨骏
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Publication of WO2019128520A1 publication Critical patent/WO2019128520A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

Definitions

  • the invention relates to a solventless resin, a preparation method thereof, a preparation kit and an application.
  • the main materials of the existing artificial leather are polyvinyl chloride (PVC), silicon (Silicone), polyurethane (Polyurethane), etc., and polyvinyl chloride (PVC) and polyurethane are widely used on the market.
  • PVC polyvinyl chloride
  • silicon Silicone
  • Polyurethane Polyurethane
  • PVC polyvinyl chloride
  • PVC polyurethane
  • Polyurethane for artificial leather can be classified into solventborne resins and Solvent-free resins.
  • the artificial leather is conventionally produced by applying a solvent-type skin resin on top of a release paper, and then applying a solvent-based adhesive layer resin, and then re-combining after a certain period of time.
  • the molecular weight of the resin is usually above 30,000, but the larger the molecular weight of the resin, the higher the viscosity, the higher the viscosity.
  • the resin is not directly usable, and therefore, a solvent is usually used to dissolve the resin to lower the viscosity.
  • DMF dimethylformamide
  • EA ethyl acetate
  • toluene solvents
  • the solvent mass percentage is 30-70% of the resin product.
  • the broad solvent-free type is divided into water base type, high-solid type, and MOCA, 4,4-methylene bis (2-chloroaniline) type.
  • DMF free type Although water-soluble type does not use organic solvents such as DMF, water is used as the dissolution medium, but in the application process of the product, it is similar to the existing solvent-based application process. Water-soluble products, in order to better dissolve the polyurethane resin, still use 3-10% of organic solvents such as DMF or NMP, but also claim to be water-soluble products.
  • the high solid content processing temperature is up to 150 degrees, resulting in processing It is not easy, and the viscosity of the resin itself is relatively high.
  • the present invention provides a solventless resin, a preparation method thereof, a preparation kit, and an application.
  • the solventless resin described in the present invention specifically refers to a resin which does not contain water, does not contain a plasticizer, and does not contain an organic solvent, and is simply a resin composed of 100% curable component.
  • the solvent-free resin does not contain a solvent component which is harmful to the human body and the environment, and the resin having the function of the surface layer and the adhesive layer can be directly coated and formed one or more times, so that the process is simple and harmless to the human body and the environment.
  • a isocyanate prepolymer is obtained by reacting isocyanate with polyol (Polyol), the NCO content is 10-24% in A material, and the viscosity is 200-10000 centipoise (cp) at 25 degrees Celsius;
  • the polyol has 2-3 functional groups and a molecular weight of 500-6000.
  • the polyol is selected from the group consisting of polyester polyols, polyether polyols, and polyester/polyether polyols.
  • the material B 100 parts by weight of the polyol, 0.1-15 parts of the crosslinking agent, 0.1-5 parts of the surfactant, 0.01-2 parts of the catalyst, and 30 minutes of stirring at 50-60 degrees Celsius.
  • the isocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, toluene diisocyanate (TDI, toluene diisocyanate), Methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI, hexamethylene diisocyanate), isophorone diisocyanate (IPDI, isophorone diisocyanate), hydrogenated phenylmethane diisocyanate (H12- One or more of MDI, dicyclohexylmethane diisocyanate), including MDI (pure-MDI), modified MDI (modified-MDI), and polymeric MDI (polymer-MDI).
  • TDI toluene diisocyanate
  • MDI Methylene diphenyl diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI is
  • the polyester polyol is obtained by a condensation polymerization reaction of a multi-diacid and a multi glycol, and has a molecular weight of 500-6000; Diacid, choose adipic acid, glutaric acid, succinic acid, phtalic acid, phthalic anhydride, isophthalic acid One or more of isophthalic acid, terephthalic acid; the polyglycol selected from ethylene glycol (EG, ethylene glycol), diethylene glycol (DEG, diethylene) Glycol), 1,4-butanediol (1,4-BD, 1,4-butanediol), 1,6-hexanediol (1,6-HD, 1,6-hexanediol), 1,2-butyl Glycol (1,2-BD, 1,2-butanediol), 1,3-butanediol (1,3-BD, 1,3-butanediol), 1,2-propanediol, 1,3-prop
  • the crosslinking agent is selected from the group consisting of ethylene glycol (EG, ethylene glycol), diethylene glycol (DEG, diethlene glycol), 1,4-butanediol (1,4-BD, 1,4-butanediol), 1,6-hexanediol (1,6-HD, 1,6-hexanediol), 1,2-butanediol (1,2-BD, 1,2-butanediol), 1,3-butanediol ( 1,3-BD, 1,3-butanediol), 1,2-propanediol, 1,3-propanediol, dipropylene glycol (DPG), tripropylene glycol (TPG, tripropylene glycol), one or more of methyl glycol (PG, propylene glycol), trimethylolpropane (TMP), glycerine.
  • EG ethylene glycol
  • DEG diethylene glycol
  • DEG diethylene glycol
  • the surfactant is a polyether modified polysiloxane.
  • the catalyst comprises a thermally sensitive catalyst of an amine and/or a metal; the metal catalyst comprises dibutyltin dilaurate, stannous octoate, zinc carboxylate, tannic acid.
  • Bismuth decanoate the amine catalyst includes triethyldiamine (TEDA), N-ethylmorpholine, 1,2-dimethylimidazole (1) , 2-dime imidazole), N-(N',N'-2-dimethylaminoethyl)morpholine.
  • the material B in the step 2) further comprises 10-200 parts of the color paste.
  • a kit for preparing the solventless resin comprising the A material and the B material; or comprising a raw material for preparing a material A and a material B; or comprising a material A and a raw material for preparing the material B .
  • the present invention does not use any organic solvent, and can be used to coat the solvent-free resin which functions as a surface layer and an adhesive layer at one time, and the solvent-type surface layer resin coating and solvent are separately performed by two or more coatings.
  • the adhesive layer resin coating method simplifies the production process and improves the new environmentally friendly method (one or more times of coating the solvent-free resin, while having the function of the surface layer and the adhesive layer), so that the artificial leather / Synthetic leather products take into account environmental protection and economy.
  • the A material isocyanate prepolymer is obtained by reacting an isocyanate with a polyol (Polyol).
  • the A material has an NCO content of 10-24% and a viscosity of 200-10000 centipoise (cp) at 25 degrees Celsius.
  • the isocyanate content is about 10%.
  • the viscosity of the isocyanate prepolymer is from 200 to 10,000 centipoise, and the material A is usually liquid at normal temperature, but may be in a solid state under certain conditions (for example, low temperature in advance), and thus may be required to be dissolved. For use, it is better to adjust the viscosity to 500-5000 cps.
  • the polyol is selected from the group consisting of polyester polyols, polyether polyols, polyester/ether copolyols, copolymers of polyester polyols and polyether polyols, It may be a physical mixture or a chemical combination), polytetramethylene ether glycol (PTMEG), polycarbonate diol, polylactone polyol One or more of them.
  • PTMEG polytetramethylene ether glycol
  • PTMEG polycarbonate diol
  • polylactone polyol polylactone polyol
  • the polyol has 2-3 functional groups and a molecular weight of 500-6000. If the average functional group of the polyester polyol is lower than the above range, the molecule does not grow sufficiently, it feels hard, and physical properties such as tensile strength and tear strength decrease, and the functional group decreases. If it is higher than the above range, problems such as a decrease in physical properties or an excessively high viscosity may occur, resulting in difficulty in application.
  • the material B 100 parts by weight of the polyol, 0.1-15 parts of the crosslinking agent, 0.1-5 parts of the surfactant, 0.01-2 parts of the catalyst, and 30 minutes of stirring at 50-60 degrees Celsius.
  • the isocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, toluene diisocyanate (TDI, toluene diisocyanate), Methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI, hexamethylene diisocyanate), isophorone diisocyanate (IPDI, isophorone diisocyanate), hydrogenated phenylmethane diisocyanate (H12- One or more of MDI, dicyclohexylmethane diisocyanate), including MDI (pure-MDI), modified MDI (modified-MDI), and polymeric MDI (polymer-MDI).
  • MDI pure-MDI
  • modified MDI modified-MDI
  • polymeric MDI polymer-MDI
  • the polyester polyol is obtained by a condensation polymerization reaction of a multi-diacid and a multi glycol, and has a molecular weight of 500 to 6000.
  • the average functional group of the polyester polyol is lower than the above range, the molecular growth is insufficient to cause a problem of harder hand feeling and lower physical properties such as tear strength. If the functional group is too high in the above range, the problem of deterioration in physical properties or excessive viscosity may occur, resulting in difficulty in use.
  • the molecular weight is 500 or less, the hand feel is hard, and it is difficult to achieve the softness of the artificial leather.
  • the molecular weight is 6,000 or more, the hand is excessively soft or sticky, and the viscosity may be too high, which may make it difficult to use.
  • the diacid is selected from the group consisting of adipic acid, glutaric acid, succinic acid, phtalic acid, and phthalic anhydride.
  • An anhydride one or more of isophthalic acid, terephthalic acid;
  • the polyglycol is selected from the group consisting of ethylene glycol (EG, ethylene glycol), diethylene glycol (DEG), 1,4-butanediol (1,4-BD, 1,4-butanediol). 1,6-hexanediol (1,6-HD, 1,6-hexanediol), 1,2-butanediol (1,2-BD, 1,2-butanediol), 1,3-butanediol (1,3-BD, 1,3-butanediol), 1,2-propanediol, 1,3-propanediol, dipropylene glycol (DPG), three One or more of propylene glycol (TPG, tripropylene glycol), propylene glycol (PG), trimethylolpropane (TMP), glycerine.
  • EG ethylene glycol
  • DEG diethylene glycol
  • 1,4-butanediol 1,4-butanedio
  • the crosslinking agent is selected from the group consisting of ethylene glycol (EG, ethylene glycol), diethylene glycol (DEG, diethlene glycol), 1,4-butanediol (1,4-BD, 1,4-butanediol), 1,6-hexanediol (1,6-HD, 1,6-hexanediol), 1,2-butanediol (1,2-BD, 1,2-butanediol), 1,3-butanediol ( 1,3-BD, 1,3-butanediol), 1,2-propanediol, 1,3-propanediol, dipropylene glycol (DPG), tripropylene glycol (TPG, tripropylene glycol), one or more of methyl glycol (PG, propylene glycol), trimethylolpropane (TMP), glycerine.
  • the crosslinking agent is selected for use according to the physical properties of the solventless resin, such as modulus
  • the surfactant is added for the purpose of improving the diffusibility, lubricity, abrasion resistance, hand feeling, and the like of the solventless resin, and the surfactant may be a polyether modified polysiloxane.
  • the catalyst employs a thermal sensitivity catalyst of an amine and/or a metal;
  • the metal catalyst comprises dibutyltin dilaurate, stannous octoate, a zinc carboxylate, a bismuth decanoate or the like, a tin (Zin), a zinc (Zinc), a bismuth (Bismuth) catalyst,
  • the amine catalyst including triethylene sulphate Amine (TEDA, triethylenediamine), N-ethylmorpholine, 1,2-dimethylimidazole, N-(N', N'-2-dimethylamino N-(N', N'-2-dimethylamino ethyl morpholine).
  • the catalyst can be diluted if necessary.
  • the polyester catalyst is classified into a blowing catalyst and a gelling catalyst, and can be classified into room temperature hardening and thermosetting catalysis.
  • the present invention contemplates a hardening (curing) temperature of 100 to 150 degrees and a hardening time of usually 1 minute to 10 minutes.
  • the foaming catalyst and the gel catalyst can be used singly or simultaneously, and at the same time, have microfoaming properties and thermosetting properties.
  • the material B in the step 2) further comprises 10-200 parts of the color paste.
  • the use of color paste can achieve a variety of color on the surface of the coating.
  • the addition of the color paste depends on whether or not the color and the kind of the color are required, which is a general knowledge of those skilled in the art.
  • additives are applied according to the use of the fabric, and are mainly applied to an antioxidant, a UV absorber, and the like.
  • the fabrics include artificial leather, synthetic leather, microfiber leather, and the like.
  • a kit for preparing the solventless resin comprising the A material and the B material; or comprising a raw material for preparing a material A and a material B; or comprising a material A and a raw material for preparing the material B .
  • the solventless resin can be prepared relatively easily.
  • the synthesis is carried out in accordance with the method of Example 1, except that the isocyanate may be used alone or in combination of two or more kinds, and the polyol may be produced by a combination of two or more types.
  • the reaction conditions can be changed as described in Example 1, in accordance with the type of isocyanate, the kind of the polyol, and the molecular weight.
  • AA Adipic acid, adipic acid
  • EG 1,4-BG
  • 1,4-BG 1,4-butanediol
  • the synthesis is carried out in accordance with the method of Example 6, except that the polyols are used alone or in combination of two or more kinds, and the crosslinking agent may be used alone or in combination of two or more types.
  • the conventional solvent-based artificial leather manufacturing method is to apply a surface layer resin containing 30-40% solid content on a release paper, and dry it in an oven at 90-120 degrees Celsius for 40-90 seconds, and then apply it.
  • the adhesive layer resin with a solid content of 60-70% is further dried in an oven at 90-120 degrees Celsius for 60-120 seconds. After semi-drying, it is combined with the cloth under a specific pressure and placed in an oven. After a long period of time: 1) directly peeling off the release paper to obtain an artificial leather product; or 2) after a certain temperature and time of aging, and then with the release paper glass, an artificial leather product is obtained.
  • the A material isocyanate prepolymer prepared in Examples 1-5 and the B material polyol mixture prepared in Examples 6-10 were metered according to the ratio (the results are shown in Table 3), using a stirrer 500-1000 rpm. Stir for 30-60 seconds, mix well, then coat on the release paper, place it in an oven at 125 ° C for drying, after 1 minute 30 seconds to 3 minutes 30 seconds, in semi-dry state, with cloth 5-6kg Recombination at a pressure of /cm 2 , after 12 to 48 hours, in a 60-90 ° C hot chamber, or in a semi-dry state, with a fabric under a pressure of 5-6 kg / cm 2 to obtain artificial synthesis leather.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种无溶剂树脂及其制备方法、制备试剂盒和应用。无溶剂树脂的制备方法，1)配制A料异氰酸酯预聚物，2)配制B料多元醇混合物，B料包括多元醇100份,交联剂0.1-15份,表面活性剂0.1-5份，催化剂0.01-2份，3)将A料和B料混合，按质量份，A料20-200份，B料100份，用于涂布。无溶剂树脂用于制备无溶剂型面料。无溶剂树脂的试剂盒包括所述的A料和B料；或者包括用于配制A料的原材料和B料；或者包括A料和用于配制B料的原材料。无溶剂树脂是不含有水分、不含有增塑剂、不含有有机溶剂的树脂，是一种由可固化成分组成的树脂。不使用任何有机溶剂，可以一次涂布完成面层和粘合层功能的无溶剂型树脂，简化了生产工艺，兼顾环保性和经济性。

Description

无溶剂树脂及其制备方法、制备试剂盒和应用 技术领域
本发明涉及一种无溶剂树脂及其制备方法、制备试剂盒和应用。
背景技术
人造皮革既有天然皮革的手感，又克服了天然皮革的缺点，所以在沙发、椅子、箱包、鞋子、汽车坐垫以及内装材料等各种生活消费品和工业产品上得到了广泛应用。
现有的人造皮革的主要材料为聚氯乙烯(PVC)、硅(Silicone)、聚氨酯(Polyurethane)等，市场上聚氯乙烯(PVC)和聚氨酯的使用较为广泛。但是,使用PVC时，为了触感柔软，必须使用增塑剂(plasticizer),部分增塑剂检出了对环境有害的成分，因此PVC的使用量越来越少，而聚氨酯的使用量越来越扩大。
人造皮革用聚氨酯可以分为溶剂型树脂(solventborne resins)和无溶剂型树脂(Solvent-free resins)。人造皮革的传统制造方式为在离型纸上面涂布溶剂型面层(skin)树脂之后干燥，然后再涂上溶剂型粘合层树脂，等一定时间后，再复合。
人造皮革需要拥有和天然皮革类似的触感，同时还要克服天然皮革的物性缺点，为了满足这些条件，要求树脂分子量通常在30000以上，但是树脂分子量越大，粘度往往也同时增大，高粘度会导致树脂不能直接使用，因此，通常使用溶剂来溶解树脂，降低粘度。以二甲基甲酰胺(DMF，dimethylformamide)为主的溶剂，通常用来溶解树脂；丁酮(MEK，methyl ethyl ketone),丙酮(acetone)，乙酸乙酯(EA，ethyl acetate),甲苯(toluene)等各种溶剂，通常配合DMF使用用来降低粘度或者溶解树脂。但是，人体吸入DMF或皮肤长时间接触DMF的话，会导致肝肾等内脏的损伤，因此，各国严格限制或者取缔对人体有害的溶剂的使用。
通常溶剂质量百分比占树脂产品的30-70％。目前，行业内，广义的无溶剂型分为水溶性型(water base type),高固含量型(high-solid type),莫卡型(MOCA，4,4-methylene bis(2-chloroaniline)type,无DMF型(DMF free type)。水溶性型虽然不使用DMF等有机 溶剂，使用水作为溶解介质，但是在产品的应用工艺方面，与现有溶剂型的应用工艺，较为类似。而且，部分水溶性种类的产品，为了更好的溶解聚氨酯树脂，仍然使用3-10％的DMF或者NMP等有机溶剂，但是也自称是水溶性产品。高固含量型的加工温度要到150度，导致加工不容易，而且树脂本身的粘度比较高，为了降低粘度，一般需要3-10％的有机溶剂，但是，同样也自称无溶剂产品。莫卡型的主要原料MOCA是被美国环境保护局(EPA)分类为最有害的化学物质，对人体有害的化学物质之一，故被限制使用。DMF free type的树脂产品，虽然不使用DMF溶剂，但是同样使用其他有机溶剂。
发明内容
为了克服现有技术中的问题，本发明提供了一种无溶剂树脂及其制备方法、制备试剂盒和应用。本发明中所述的无溶剂树脂，特指不含有水分、不含有增塑剂、不含有有机溶剂的树脂，简单而言，是一种由100％的可固化成分组成的树脂。无溶剂树脂完全不包含对人体以及环境有害的溶剂成分，而且同时拥有面层以及粘合层功能的树脂，可一次或多次直接涂布成型，因此工艺简单，对人体、环境无害。
一种无溶剂树脂的制备方法，
1)配制A料异氰酸酯预聚物，
通过异氰酸酯和多元醇(Polyol)反应得到A料异氰酸酯预聚物，A料中，NCO含量10-24％，25摄氏度下粘度为200-10000厘泊(cp)；
所述的多元醇的官能基为2-3个，分子量500-6000，所述的多元醇选自聚酯多元醇(polyester polyol),聚醚多元醇(polyether polyol),聚酯/聚醚多元醇(polyester/ether copolyol),聚四亚甲基醚二醇(PTMEG,polyetramethylene ether glycol),聚碳酸酯二醇(polycarbonatediol),聚内酯多元醇(polylactone polyol)中的一种或多种；
2)配制B料多元醇混合物，
B料中，按质量份，包括所述的多元醇(polyol)100份，交联剂0.1-15份，表面活性剂0.1-5份，催化剂0.01-2份；在50-60摄氏度搅拌30分钟后得到；
3)将A料和B料混合，按质量份，A料20-200份，B料100份，用于涂布。
进一步，4)涂布在离型纸上，放置在烘箱里进行干燥，在半干燥状态时，与布料在压力下复合。
所述的异氰酸酯，选自2,4-甲苯二异氰酸酯(2,4-toluene diisocyanate)，2,6-甲苯二 异氰酸酯(2,6-toluene diisocyanate)，甲苯二异氰酸酯(TDI,toluene diisocyanate),亚甲基二苯基二异氰酸酯(Methylene diphenyl diisocyanate，MDI)，六亚甲基二异氰酸酯(HDI，hexamethylene diisocyanate)，异佛尔酮二异氰酸酯(IPDI，isophorone diisocyanate)，氢化苯基甲烷二异氰酸酯(H12-MDI，dicyclohexylmethane diisocyanate)中的一种或者多种，所述的MDI包括纯MDI(pure-MDI)，变性MDI(modified-MDI)，聚合MDI(polymer-MDI)。
所述的聚酯多元醇(Polyester polyol)是通过多二元酸(multi diacid)和多乙二醇(multi glycol)的浓缩聚合(condensation polymerization)反应得到，分子量500-6000；所述的二元酸(diacid),选自己二酸(adipic acid)，戊二酸(glutaric acid),琥珀酸(succinic acid),邻苯二甲酸(phtalic acid),邻苯二甲酸酐(phthalic anhydride),间苯二甲酸(isophthalic acid),对苯二甲酸(terephthalic acid)中的一种或者多种；所述的多乙二醇，选自乙二醇(EG,ethylene glycol)，二甘醇(DEG,diethylene glycol),1,4-丁二醇(1,4-BD,1,4-butanediol),1,6-己二醇(1,6-HD,1,6-hexanediol),1,2-丁二醇(1,2-BD,1,2-butanediol),1,3-丁二醇(1,3-BD,1,3-butanediol),1,2-丙二醇(1,2-propanediol),1,3-丙二醇(1,3-propanediol),二丙二醇(DPG,dipropylene glycol),三丙二醇(TPG,tripropylene glycol),丙二醇(PG,propylene glycol),三羟甲基丙烷(TMP,trimethylolpropane)，甘油(glycerine)中的一种或者多种。
所述的交联剂，选自乙二醇(EG，ethylene glycol),二甘醇(DEG,diethlene glycol)，1,4-丁二醇(1,4-BD,1,4-butanediol)，1,6-己二醇(1,6-HD,1,6-hexanediol)，1,2-丁二醇(1,2-BD,1,2-butanediol),1,3-丁二醇(1,3-BD,1,3-butanediol),1,2-丙二醇(1,2-propanediol),1,3-丙二醇(1,3-propanediol),二丙二醇(DPG,dipropylene glycol),三丙二醇(TPG,tripropylene glycol),甲基乙二醇(PG,propylene glycol),三羟甲基丙烷(TMP,trimethylolpropane),甘油(glycerine)中的一种或者多种。
所述的表面活性剂为聚醚改性聚硅氧烷(polyether modified polysiloxane)。
所述的催化剂采用胺类和/或者金属的热灵敏度的催化剂；所述的金属催化剂包括二月桂酸二丁基锡(Dibutyltindilaurate),辛酸亚锡(stannous octoate)，羧酸锌(zinc carboxylate),癸酸铋(bismuth decanoate)，所述的胺类催化剂(amine catalyst)包括三乙稀二胺(TEDA，triethylenediamine),N-乙基吗啉(N-ethylmorpholine),1,2-二甲基咪唑 (1,2-dime imidazole),N-(N'，N'-2-二甲氨基乙基)吗啉(N-(N',N'-2-dimethylamino ethyl)morpholine)。
步骤2)所述的B料中进一步包括色浆10-200份。
一种根据所述的制备方法得到的无溶剂树脂。
一种所述的无溶剂树脂的应用，用于制备无溶剂型面料。
一种用于制备所述的无溶剂树脂的试剂盒，包括所述的A料和B料；或者包括用于配制A料的原材料和B料；或者包括A料和用于配制B料的原材料。
本发明的有益效果
本发明不使用任何有机溶剂，可以一次涂布完成面层和粘合层功能的无溶剂型树脂，从传统方式(经过两次或者以上的涂布，分别完成溶剂型面层树脂涂布和溶剂型粘合层树脂涂布的方式)，简化了生产工艺，改善为新型的环保方式(一次或者多次涂布无溶剂型树脂，同时拥有面层以及粘合层功能的方式)，使得人造革/合成革产品兼顾环保性和经济性。
具体实施方式
以下结合实施例对本发明做进一步的阐述。
一种无溶剂树脂的制备方法，
1)配制A料异氰酸酯预聚物，
通过异氰酸酯和多元醇(Polyol)反应得到A料异氰酸酯预聚物，A料中，NCO含量10-24％，25摄氏度下粘度为200-10000厘泊(cp)。
如果NCO的含量太低，会导致粘度大幅提高，很难使用面层。如果NCO的含量超过24％，粘度过低，就不能形成面层厚度，而且导致硬度高，也很难实现天然皮革的手感。如果只限用于胶粘剂，异氰酸酯的含量约为10％也没问题。
如果异氰酸酯预聚物的粘度过高，流动性降低，发生织物穿透性下降。反之，粘度过低，皮层难以增厚，原料过度参透到织物。因此，异氰酸酯预聚物的粘度为200到10000厘泊比较合适，该A料在常温下通常为液体，但是在特定条件下(比如预先受过低温)也可能为固体状态，因此有可能需要溶解后使用，粘度调节到500-5000厘泊使用比较好。
所述的多元醇选自聚酯多元醇(polyester polyol),聚醚多元醇(polyether polyol),聚酯/聚醚多元醇(polyester/ether copolyol，聚酯多元醇和聚醚多元醇的共聚物，可以是物 理上的混合，也可以使化学上的结合),聚四亚甲基醚二醇(PTMEG,polyetramethylene ether glycol),聚碳酸酯二醇(polycarbonatediol),聚内酯多元醇(polylactone polyol)中的一种或多种。
所述的多元醇的官能基为2-3个，分子量500-6000。聚酯多元醇的平均官能基若比上述的范围要低的话，分子没有充分成长，会感觉硬，而且抗拉强度(tensil stength),撕裂强度(tear strength)等物理性质会下降，官能基若比上述的范围高的话，会发生物理特性下降或者粘度过度高等问题，导致不容易应用。
2)配制B料多元醇混合物，
B料中，按质量份，包括所述的多元醇(polyol)100份，交联剂0.1-15份，表面活性剂0.1-5份，催化剂0.01-2份；在50-60摄氏度搅拌30分钟后得到；
3)将A料和B料混合，按质量份，A料20-200份，B料100份，用于涂布。
进一步，4)涂布在离型纸上，放置在烘箱里进行干燥，在半干燥状态时，与布料在压力下复合。
所述的异氰酸酯，选自2,4-甲苯二异氰酸酯(2,4-toluene diisocyanate)，2,6-甲苯二异氰酸酯(2,6-toluene diisocyanate)，甲苯二异氰酸酯(TDI,toluene diisocyanate),亚甲基二苯基二异氰酸酯(Methylene diphenyl diisocyanate，MDI)，六亚甲基二异氰酸酯(HDI，hexamethylene diisocyanate)，异佛尔酮二异氰酸酯(IPDI，isophorone diisocyanate),氢化苯基甲烷二异氰酸酯(H12-MDI，dicyclohexylmethane diisocyanate)中的一种或者多种，所述的MDI包括纯MDI(pure-MDI),变性MDI(modified-MDI),聚合MDI(polymer-MDI)。为了防止光线变黄，可以使用耐黄变性优秀的IPDI,HDI,H12-MDI等。
所述的聚酯多元醇(Polyester polyol)是通过多二元酸(multi diacid)和多乙二醇(multi glycol)的浓缩聚合(condensation polymerization)反应得到,分子量500-6000。聚酯多元醇的平均官能基比上述的范围低的话，分子成长不充分导致较硬的手感、降低撕裂强度等物理性质的问题。如果官能基比上述范围过高的话，也会发生物性降低或粘度过高的问题，导致不容易使用。分子量500以下的话，手感较硬，难以实现人造皮革的柔软，分子量6000以上的话，产生过度柔软或黏黏的手感，而且可能会因粘度过高，导致不容易使用。
所述的二元酸(diacid),选自己二酸(adipic acid)，戊二酸(glutaric acid),琥珀酸 (succinic acid),邻苯二甲酸(phtalic acid),邻苯二甲酸酐(phthalic anhydride),间苯二甲酸(isophthalic acid),对苯二甲酸(terephthalic acid)中的一种或者多种；
所述的多乙二醇，选自乙二醇(EG,ethylene glycol)，二甘醇(DEG,diethylene glycol),1,4-丁二醇(1,4-BD,1,4-butanediol),1,6-己二醇(1,6-HD,1,6-hexanediol),1,2-丁二醇(1,2-BD,1,2-butanediol),1,3-丁二醇(1,3-BD,1,3-butanediol),1,2-丙二醇(1,2-propanediol),1,3-丙二醇(1,3-propanediol),二丙二醇(DPG,dipropylene glycol),三丙二醇(TPG,tripropylene glycol),丙二醇(PG,propylene glycol),三羟甲基丙烷(TMP,trimethylolpropane)，甘油(glycerine)中的一种或者多种。
所述的交联剂，选自乙二醇(EG，ethylene glycol),二甘醇(DEG,diethlene glycol)，1,4-丁二醇(1,4-BD,1,4-butanediol)，1,6-己二醇(1,6-HD,1,6-hexanediol)，1,2-丁二醇(1,2-BD,1,2-butanediol),1,3-丁二醇(1,3-BD,1,3-butanediol),1,2-丙二醇(1,2-propanediol),1,3-丙二醇(1,3-propanediol),二丙二醇(DPG,dipropylene glycol),三丙二醇(TPG,tripropylene glycol),甲基乙二醇(PG,propylene glycol),三羟甲基丙烷(TMP,trimethylolpropane),甘油(glycerine)中的一种或者多种。交联剂按照无溶剂树脂的物性要求，如模量(modulus)、拉伸强度(tensile strength)撕裂强度(tear strength),伸长(elongation)等来选择使用。
添加表面活性剂是为了改善无溶剂树脂的扩散性、润滑性、耐磨性、手感等目的，所述的表面活性剂可采用聚醚改性聚硅氧烷(polyether modified polysiloxane)。
所述的催化剂采用胺类和/或者金属的热灵敏度(thermal sensitivity catalyst)的催化剂(thermal sensitivity catalyst)；所述的金属催化剂包括二月桂酸二丁基锡(Dibutyltindilaurate),辛酸亚锡(stannous octoate)，羧酸锌(zinc carboxylate),癸酸铋(bismuth decanoate)等锡类(Tin),锌类(Zinc),铋类(Bismuth)催化剂，所述的胺类催化剂(amine catalyst)包括三乙稀二胺(TEDA，triethylenediamine),N-乙基吗啉(N-ethylmorpholine),1,2-二甲基咪唑(1,2-dime imidazole),N-(N'，N'-2-二甲氨基乙基)吗啉(N-(N',N'-2-dimethylamino ethyl)morpholine)。催化剂必要时可稀释使用。聚酯催化剂区分为发泡催化剂(blowing catalyst)和凝胶催化剂(gelling catalyst)，还可区分为常温硬化和热硬化催化。本发明考虑到硬化(固化)温度100-150度、硬化时间一般在1分钟到10分钟以内。发泡催化剂和凝胶催化剂可以单独使用，也同时使用，同时使用则具有微发泡性能和热硬化性能。
步骤2)所述的B料中进一步包括色浆10-200份。色浆的使用，可以实现涂层表面颜色的多样性。色浆的添加，根据是否需要颜色以及颜色的种类而定，此为本领域技术人员的常规知识。
其它添加剂(additives)按照面料的用途来适用，主要适用抗氧化剂(antioxidant),耐黄变剂(UV absorber)等。
一种根据所述的制备方法得到的无溶剂树脂。
一种所述的无溶剂树脂的应用，用于制备无溶剂型面料。所述面料包括人造皮革、合成革、超纤革等等。
一种用于制备所述的无溶剂树脂的试剂盒，包括所述的A料和B料；或者包括用于配制A料的原材料和B料；或者包括A料和用于配制B料的原材料。对于本领域技术人员来说，如果得到了A料和B料这个组合，就可以比较容易的制备无溶剂树脂。
通过以下实施例的教导，本领域技术人员可以更直接的实施本发明，但这些实施例并不是用于限制本发明，对于本领域技术人员来说可以显而易见的做出多种改动和变型。
实施例1(A料1的配制)
充氮的烧瓶里加入纯MDI(4,4-二苯基甲烷二异氰酸酯，4,4-diphenylmethane diisocyanate)522.3克，在50-60摄氏度完全溶解。确认完全溶解以后，加入变性MDI(modified-MDI)104.5克，酯多元醇(ester polyol)373.2g，其中酯多元醇分子量为2000,组成成分为AA(Adipic acid，己二酸)、EG、DEG，按质量比为AA：EG：DEG＝60：20：20，按顺序加入，保持在72-78摄氏度三个小时合成。产物A料1的NCO％为19％，粘度为500到2000厘泊(25摄氏度)。
实施例2-5(A料2-5的配制)
参照实施例1的方法合成，但是异氰酸酯可以采用单独或两个种类以上组合，多元醇也可以采用单独或两个种类以上组合反应的方式来制造。反应条件可以参照实施例1，按照异氰酸酯的种类、多元醇的种类以及分子量进行相应变化。
实施例1-5的结果如表1所示。
表1
Figure PCTCN2018115755-appb-000001
实施例6(B料1的合成)
充氮的烧瓶里加入聚酯多元醇(polyester polyol)(分子量1，000，组成成分：AA(Adipic acid，己二酸)，EG，1，4-BG(1，4-丁二醇))445克，按质量比其中AA：EG：1，4-BG＝500：200：300，聚酯多元醇(polyester polyol)(分子量2，000，组成成分：AA，EG，1，4-BG)445克之后，在105摄氏度真空减压(vacuum)，这样的状态维持一个小时，这个过程中除掉残留的水分后，加入1，4-BG 80克，表面活性剂30克、催化剂0.8克后，在50-60摄氏度搅拌30分钟后得到。
实施例7-10(B料2-5的合成)
参照实施例6方法合成，但里面的多元醇(polyol)采用单独或两个种类以上组合，交联剂的话，可采用单独或两个种类以上组合。
实施例6-10的结果如表2所示。
表2
Figure PCTCN2018115755-appb-000002
应用实施例无溶剂型人造皮革的制造
传统的溶剂型人造皮革制造方法是在离型纸上面涂布包含30-40％固含量(solid content)的面层树脂,在90-120摄氏度的烘箱里放置40-90秒干燥后，涂布固含量为60-70％的粘合层树脂，在90-120摄氏度的烘箱里再过60-120秒，半干燥(semi-dry)后，与布料在特定的压力下复合，经过烘箱放置较长的一段时间之后：1)直接与离型纸剥离，得到人造革产品；或者2)经过特定温度和时间的熟化之后，再与离型纸玻璃，得到人造革产品。
本发明从实施例1-5制备得到的A料异氰酸酯预聚物和实施例6-10制备得到的B料多元醇混合物按照配比计量后(结果如表3所示)，用搅拌机500-1000rpm搅拌30-60秒进行充分混合，然后涂布在离型纸上面，放置在125摄氏度的烘箱里进行干燥，经过1分钟30秒到3分钟30秒，在半干燥状态，与布料用5-6kg/cm 2的压力下进行复合，经过12-48小时，在60-90摄氏度热室里熟成制造，或者在半干燥状态，与布料用5-6kg/cm 2的压力下进行复合，得到人造合成革。
表3
Figure PCTCN2018115755-appb-000003

Claims (11)

  1. 一种无溶剂树脂的制备方法，其特征在于，
    1)配制A料异氰酸酯预聚物，
    通过异氰酸酯和多元醇(Polyol)反应得到A料异氰酸酯预聚物，A料中，NCO含量10-24％，25摄氏度下粘度为200-10000厘泊(cp)；
    所述的多元醇的官能基为2-3个，分子量500-6000，所述的多元醇选自聚酯多元醇(polyester polyol)，聚醚多元醇(polyether polyol)，聚酯/聚醚多元醇(polyester/ether copolyol)，聚四亚甲基醚二醇(PTMEG,polyetramethylene ether glycol)，聚碳酸酯二醇(polycarbonatediol)，聚内酯多元醇(polylactone polyol)中的一种或多种；2)配制B料多元醇混合物，
    B料中，按质量份，包括所述的多元醇(polyol)100份，交联剂0.1-15份，表面活性剂0.1-5份，催化剂0.01-2份；在50-60摄氏度搅拌30分钟后得到；
    3)将A料和B料混合，按质量份，A料20-200份，B料100份，用于涂布。
  2. 根据权利要求1所述的制备方法，其特征在于，进一步，4)涂布在离型纸上，放置在烘箱里进行干燥，在半干燥状态时，与布料在压力下复合。
  3. 根据权利要求1所述的制备方法，其特征在于，所述的异氰酸酯，选自2,4-甲苯二异氰酸酯(2,4-toluene diisocyanate)，2,6-甲苯二异氰酸酯(2,6-toluene diisocyanate)，甲苯二异氰酸酯(TDI,toluene diisocyanate)，亚甲基二苯基二异氰酸酯(Methylene diphenyl diisocyanate，MDI)，六亚甲基二异氰酸酯(HDI，hexamethylene diisocyanate)，异佛尔酮二异氰酸酯(IPDI，isophorone diisocyanate)，氢化苯基甲烷二异氰酸酯(H12-MDI，dicyclohexylmethane diisocyanate)中的一种或者多种，所述的MDI包括纯MDI(pure-MDI)，变性MDI(modified-MDI)，聚合MDI(polymer-MDI)。
  4. 根据权利要求1所述的制备方法，其特征在于，所述的聚酯多元醇(Polyester polyol)是通过多二元酸(multi diacid)和多乙二醇(multi glycol)的浓缩聚合(condensation polymerization)反应得到，分子量500-6000；
    所述的二元酸(diacid)，选自己二酸(adipic acid)，戊二酸(glutaric acid)，琥珀酸 (succinic acid)，邻苯二甲酸(phtalic acid)，邻苯二甲酸酐(phthalic anhydride)，间苯二甲酸(isophthalic acid)，对苯二甲酸(terephthalic acid)中的一种或者多种；
    所述的多乙二醇，选自乙二醇(EG,ethylene glycol)，二甘醇(DEG,diethylene glycol)，1,4-丁二醇(1,4-BD,1,4-butanediol)，1,6-己二醇(1,6-HD,1,6-hexanediol)，1,2-丁二醇(1,2-BD,1,2-butanediol)，1,3-丁二醇(1,3-BD,1,3-butanediol)，1,2-丙二醇(1,2-propanediol)，1,3-丙二醇(1,3-propanediol)，二丙二醇(DPG,dipropylene glycol)，三丙二醇(TPG,tripropylene glycol)，丙二醇(PG,propylene glycol)，三羟甲基丙烷(TMP,trimethylolpropane)，甘油(glycerine)中的一种或者多种。
  5. 根据权利要求1所述的制备方法，其特征在于，
    所述的交联剂，选自乙二醇(EG，ethylene glycol)，二甘醇(DEG,diethlene glycol)，1,4-丁二醇(1,4-BD,1,4-butanediol)，1,6-己二醇(1,6-HD,1,6-hexanediol)，1,2-丁二醇(1,2-BD,1,2-butanediol)，1,3-丁二醇(1,3-BD,1,3-butanediol)，1,2-丙二醇(1,2-propanediol)，1,3-丙二醇(1,3-propanediol)，二丙二醇(DPG,dipropylene glycol)，三丙二醇(TPG,tripropylene glycol)，甲基乙二醇(PG,propylene glycol)，三羟甲基丙烷(TMP,trimethylolpropane)，甘油(glycerine)中的一种或者多种。
  6. 根据权利要求1所述的制备方法，其特征在于，所述的表面活性剂为聚醚改性聚硅氧烷(polyether modified polysiloxane)。
  7. 根据权利要求1所述的制备方法，其特征在于，所述的催化剂采用胺类和/或者金属的热灵敏度的催化剂；所述的金属催化剂包括二月桂酸二丁基锡(Dibutyltindilaurate)，辛酸亚锡(stannous octoate)，羧酸锌(zinc carboxylate)，癸酸铋(bismuth decanoate)，所述的胺类催化剂(amine catalyst)包括三乙稀二胺(TEDA，triethylenediamine)，N-乙基吗啉(N-ethylmorpholine)，1,2-二甲基咪唑(1,2-dime imidazole)，N-(N'，N'-2-二甲氨基乙基)吗啉(N-(N',N'-2-dimethylamino ethyl)morpholine)。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤2)所述的B料中进一步包括色浆10-200份。
  9. 一种根据权利要求1－8任一项所述的制备方法得到的无溶剂树脂。
  10. 一种根据权利要求9所述的无溶剂树脂的应用，其特征在于，用于制备无溶剂型面料。
  11. 一种用于制备根据权利要求9所述的无溶剂树脂的试剂盒，其特征在于，包括所述的 A料和B料；或者包括用于配制A料的原材料和B料；或者包括A料和用于配制B料的原材料。
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