CN108484873A - A kind of use for synthetic leather high solid content polyurethane surface layer resin and preparation method thereof - Google Patents

A kind of use for synthetic leather high solid content polyurethane surface layer resin and preparation method thereof Download PDF

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Publication number
CN108484873A
CN108484873A CN201810138119.3A CN201810138119A CN108484873A CN 108484873 A CN108484873 A CN 108484873A CN 201810138119 A CN201810138119 A CN 201810138119A CN 108484873 A CN108484873 A CN 108484873A
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preparation
resin
polyurethane
parts
curing agent
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CN108484873B (en
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李晓飞
王海峰
范仁祥
孔为青
姚克俭
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/48—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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes

Abstract

The invention discloses a kind of use for synthetic leather high solid content polyurethane surface layer resins and preparation method thereof, are made by following steps：The preparation of high solids content blocked polyurethane resin, the preparation of modified amine curing agent, take, enclosed type height consolidates resin, mill base and modified amine curing agent, stir evenly to get polyurethane cover resin.The present invention, which is reacted by isocyanates with hydroxy component, generates that molecular weight is smaller, the lower isocyanate terminated performed polymer of viscosity, using can the sealer of thermal dissociation terminal isocyanate is reacted to form blocked polyurethane storage-stable at room temperature, amine curing agent is added when use, it at room temperature can be with one week or more Storage period, and sealer dissociates under heating state, the isocyanates released forms the composite polymer material of the base containing Ureido-urethane of excellent in mechanical performance with amine hardener fast reaction.

Description

A kind of use for synthetic leather high solid content polyurethane surface layer resin and preparation method thereof
Technical field
The invention belongs to functional urethane synthetic leather fields, and in particular to a kind of use for synthetic leather high solid content polyurethane face Layer resin and preparation method thereof.
Background technology
Polyurethane high molecule material due to answering extensively with excellent flexility, wear-resisting property, anti-hydrolytic performance etc. For synthetic leather field, become the ideal material for substituting natural leather.Prepared by the processing of conventional urethane synthetic leather, either dry Method technique, wet processing, also or dry method is combined with wet processing, use in process be all withN,NDimethyl The polyurethane resin that organic solvents and the solid contents such as formamide (DMF), butanone (MEK), toluene (TOL) are 20-40% is former Material leads to the presence of organic solvent pollution in process.As country is to environmental pollution in enterprise production process The increasing of problem supervision and gradually increasing for people's environmental consciousness, Synthetic Leather is gradually from high pollution, maximum discharge Move towards no pollution, low emission clean manufacturing.
In recent years, related synthetic leather enterprise prepares foaming among synthetic leather using solvent-free bi-component mixing pouring technology Layer, substitutes traditional solvent type wet method aperture layer and obtains excellent feel, performance, gradually obtain the approval in market.It is solvent-free Bi-component technique greatly reduces the DMF contents that synthetic leather processing removes from office product in the process and finally, but bi-component is solvent-free at present Technique is limited only to apply in synthetic leather middle foaming layer.It is difficult to accurately since face layer is existed using solvent-free two-component technique The problem of controlling color, and aqueous polyurethane surface layer resin is used to be applied to synthetic leather product in physical property and processing performance side Still there is certain defect in face, and there has been no ideal settling modes for environment-friendly dry normal plane layer.
Therefore, a kind of use for synthetic leather high solid content polyurethane surface layer resin is developed, solvent-free two-component middle layer tree is coordinated Fat uses, and the synthetic leather processing production solution for providing loopful guarantor is particularly necessary.
Invention content
The purpose of the present invention is to provide a kind of preparation method of use for synthetic leather high solid content polyurethane surface layer resin and its Using providing solution for environment-friendly polyurethane synthetic leather product.
A kind of preparation method of use for synthetic leather high solid content polyurethane surface layer resin is made by following steps：
（1）The preparation of high solids content blocked polyurethane resin
Temperature of reaction kettle is controlled at 40-50 DEG C, after isocyanates, antioxidant stirring 10-30min is added, is sequentially added oligomeric Object polyalcohol, castor oil and chain extender, then at 60-80 DEG C reaction until NCO mass contents reach 1.5-5% to get to Isocyanate terminated performed polymer；
Sealer is added into isocyanate terminated performed polymer and carries out capping, the reaction at 60-80 DEG C is until NCO mass contents are 0%；Then solvent is added to adjust polyurethane resin solid content to 90%, after being eventually adding UV absorbers stirring 20-30min Cool down discharging packaging, and enclosed type height is made and consolidates resin；
（2）The preparation of modified amine curing agent
Temperature of reaction kettle is controlled at 40-50 DEG C, after amine terminated polyether, antioxidant stirring 10-20min is added, isocyanic acid is added Ester is in 40-50 DEG C of reaction to get modified amine curing agent until amine value reaches 35-156mgKOH/g；
（3）The preparation of polyurethane cover resin
Take step（1）The enclosed type height of preparation consolidates resin, mill base and step（2）The modified amine curing agent of preparation, stirs evenly, i.e., Obtain polyurethane cover resin.
Further scheme, step（1）The raw material quality number of middle high solids content blocked polyurethane resin is as follows：
100 parts of isocyanates
140-220 parts of oligomer polyol
50-100 parts of castor oil
4-10 parts of chain extender
10-40 parts of sealer
0.5-1 parts of antioxidant
0.5-1 parts of UV absorbers
38-43 parts of solvent.
Further scheme, step（2）The raw material quality number of middle modified amine curing agent is as follows：
100 parts of amine terminated polyether
3-15 parts of isocyanates
0.2-1 parts of antioxidant.
Further scheme, step（3）The mass ratio that middle enclosed type height consolidates resin, mill base and modified amine curing agent is 100：5- 10：40-66.
Further scheme, the isocyanates are 4,4 '-methyl diphenylene diisocyanates (MDI-100), 2,4 '-two The mixture (MDI-50) of methylenebis phenyl isocyanate and 4,4 '-methyl diphenylene diisocyanates, two isocyanide of isophorone One in acid esters (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-dicyclohexyl methyl hydride diisocyanates (HMDI) Kind is several.
Further scheme, step（1）Described in oligomer polyol be polyester polyethers copoly type oligomer polyol, with And one or more of polyester-type oligomer polyol, polycarbonate type oligomer polyol；The polyester polyethers copoly type Oligomer polyol is using polyester polyol as initiator, made from propylene oxide ring-opening polymerisation；
The hydroxyl average functionality of the castor oil is 2.7,156~160 mg KOH/g of hydroxyl value；
The chain extender is ethylene glycol, 1,3- propylene glycol, 1,4- butanediols, 1,5- pentanediols, neopentyl glycol, a contracting diethyl two Alcohol, 3- methyl-1s, one kind in 5- pentanediols；
The sealer is methyl ethyl ketoxime, 3,5- dimethyl pyrazoles, diethyl malonate, antifebrin, 1,2,4- triazoles Middle one kind；
The solvent is gamma-butyrolacton, 6-caprolactone, dimethyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl It is a kind of in acid esters, ethylene acetate.
Further scheme, step（2）Described in ending amino polyether be a kind of polypropylene oxide blocked by primary amino group Close object, molecular weight 400-2000.It is preferred that in the Yantai people's livelihood Chemical Company AMD-400, AMD-1000, AMD-2000 One kind.
Further scheme, the ultra-violet absorber are UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV- 234；The antioxidant is 245,1010,1035,1076,1098 or 3114.
Another goal of the invention of the present invention is to provide a kind of polyurethane cover prepared through preparation method described above Resin.
The present invention, which is reacted by isocyanates with hydroxy component, generates that molecular weight is smaller, viscosity is lower isocyanate terminated pre- Aggressiveness, using can the sealer of thermal dissociation terminal isocyanate is reacted to form the poly- ammonia of enclosed type storage-stable at room temperature Amine curing agent is added in ester, when use, at room temperature can be with one week or more Storage period, and sealer dissociates under heating state Out, the isocyanates released contains urea groups-carbamate groups with amine hardener fast reaction formation excellent in mechanical performance Composite polymer material.
Polyurethane cover resin prepared by the present invention is coated in release paper in 120-140 DEG C of baking oven 2-4min up to poly- Urethane face layer coating, then the solvent-free double-component polyurethane of coating Hefei Anli New Material Polyurethane Co., Ltd. production on it Then intermediate layer resin AL-1025A/AL-5040B is bonded base fabric and synthetic leather product is made.The VOC of synthetic leather product obtained Less than 10ppm, peel strength reaches 50N/3cm or more, 70 DEG C, 95%RH constant temperature and humidities after 7 weeks peel strength retention rate be more than 75%, wear-resisting property, folding quality are excellent, can be widely applied in the fields such as sofa furniture leather, luggage leather.
Specifically, compared with prior art, the present invention has following obvious advantage：
（1）The present invention can reach one at room temperature after modified amine curing agent is added in high solids content blocked polyurethane resin Storage period more than week, storge quality are stablized, and have traditional one-component resin is similar to operate processability；High temperature deblocking solidification Afterwards, the coating structure for forming similar dual-component polyurethane resin, maintains the advantage of bi-component resin product high-solid lower-viscosity.
（2）The present invention synthesizes enclosed type for mixed type soft segment with other types oligomer polyol using part castor oil and gathers Urethane, wherein the hydroxyl average functionality of castor oil are 2.7.This two kinds of polyalcohols are used in mixed way the polyurethane resin prepared Excellent mechanical strength and good mobile performance can be had both.
（3）The present invention is reacted by the amine terminated polyether of 400-2000 molecular weight with isocyanates, the amine-type cure of synthesis Agent boiling point is higher, not volatile, avoids using the volatile amine hardener for causing actual participation to be reacted of general amine curing agent And the larger problem of Theoretical Design value deviation ensure that the stability for the polyurethane coating mechanical property to be formed.
（4）Inventive closure type high solid content resin solid content is 90%, and it is preferably weak that a small amount of environmental-protecting performance is used only in product Dicyandiamide solution, without using the DMF organic solvents of difficult volatilization.Synthetic leather product environmental performance obtained is excellent, and VOC content highest is only It is the environment-friendly type synthetic leather product for being absolutely free of DMF for 10ppm.
Specific implementation mode
Below by several specific embodiments, the present invention is further illustrated, but it is to be noted that the present invention Specific material proportion, process conditions and result described in embodiment etc. are merely to illustrate the present invention, can not be limited with this Protection scope of the present invention processed, equivalent change or modification made by every Spirit Essence according to the present invention, should all cover In protection scope of the present invention.
Embodiment 1：
（1）The preparation of high solids content blocked polyurethane resin
By 100g 4,4 '-methyl diphenylene diisocyanates（MDI-100）In addition in three-necked flask, it is warming up to 40 DEG C of additions 1g antioxidant 1010s stir 10min, sequentially add 140g oligomer polyols（YNW-2000T）, 60g castor oil, 4g ethylene glycol （EG）It is warming up to 60 DEG C after stirring evenly to react 4 hours, detection NCO reaches 5%.
40g sealer methyl ethyl ketoximes are added, 60 DEG C are reacted 3 hours, and detection NCO content reaches 0%.38g solvents the third two are added Alcohol methyl ether acetate, 0.8g UV absorbers UV-P stir cooling discharging packaging after 20min.
（2）The preparation of amine curing agent
Temperature of reaction kettle is controlled at 40 DEG C, 100g amine terminated polyethers are added（AMD-400）, 1g antioxidant 1010s stir 10min, 15g hexamethylene diisocyanates are added dropwise into reaction kettle（HDI）.40 DEG C of reaction 4h reach 156mgKOH/g to amine value content. Cooling discharging is packed after stirring 30min.
（3）The preparation of polyurethane cover resin
Take step（1）The solvent-free mill bases of 5g and 40g steps is added in middle resin 100g（2）The amine curing agent of synthesis stirs evenly, Obtain polyurethane cover resin.
Polyurethane cover resin is coated in release paper in 130 DEG C of baking oven 3min up to polyurethane cover coating in poly- ammonia Re-coating Hefei Anli New Material Polyurethane Co., Ltd. produces solvent-free double-component polyurethane middle layer tree on the layer coating of ester face Then fat AL-1025A/AL-5040B is bonded base fabric and synthetic leather product is made.Its VOC is surveyed using HJ/H400-2007 standards（It waves Send out object total amount）Less than 10ppm.It is 73 N/3cm to survey its peel strength according to QB/T2888-2007 standards, in 70 DEG C, 95%RH It is 66 N/3cm to make peel strength after jungle is tested 7 weeks in climatic chamber, and Wei Shibo is not broken for wear-resisting 100,000 times, -10 DEG C 60,000 times It deflects and does not break, meet the requirement of sofa artificial leather basic physical properties.
The raw material used in the present embodiment：
MDI-100, HDI are the isocyanates of Yantai Wanhua company production；YNW-2000T is the one limited public affairs of Nowe new material of Shandong Take charge of the polyester polyethers copoly type oligomer polyol of production；AMD-400 is the end ammonia of Yantai people's livelihood Chemical Company production Base polyethers；Methyl ethyl ketoxime is the sealer of the Zhejiang chemical inc Sheng An production；1010, UV-P is respectively Taiwan double bond The antioxidant and ultra-violet absorber of Chemical Co., Ltd.；Castor oil, ethylene glycol, propylene glycol methyl ether acetate, solvent-free mill base For commercial product.
Embodiment 2：
（1）The preparation of high solids content blocked polyurethane resin
By the mixing isocyanates of 100g 2,4 '-methyl diphenylene diisocyanates and 4,4 '-methyl diphenylene diisocyanates （MDI-50）In addition in three-necked flask, it is warming up to 50 DEG C and 245 stirring 30min of 0.5g antioxidant is added, it is low to sequentially add 220g Polymers polyalcohol（PBA-2000）, 50g castor oil, 7.5g 1,4- butanediols（1,4-BG）80 DEG C are warming up to after stirring evenly instead It answers 4 hours, detection NCO reaches 3%.
27g sealers 3 are added, 5- dimethyl pyrazoles, 80 DEG C are reacted 2 hours, and detection NCO content reaches 0%.It is molten that 42g is added Agent gamma-butyrolacton, 1g UV absorbers UV-1 stir cooling discharging packaging after 30min.
（2）The preparation of amine curing agent
Temperature of reaction kettle is controlled at 50 DEG C, 100g amine terminated polyethers are added（AMD-1000）, 0.5g antioxidant 245 stir 8g hexamethylene diisocyanates are added dropwise into reaction kettle by 20min（HDI）.50 DEG C of reaction 3h reach to amine value content 54mgKOH/g.Cooling discharging is packed after stirring 60min.
（3）The preparation of polyurethane cover resin
Take step（1）Above-mentioned resin 100g is taken, the solvent-free mill bases of 8g and 66g steps is added（2）The amine curing agent of synthesis stirs Uniformly, polyurethane cover resin is obtained.
Polyurethane cover resin is coated in release paper in 130 DEG C of baking oven 3min up to polyurethane cover coating in poly- ammonia Re-coating Hefei Anli New Material Polyurethane Co., Ltd. produces solvent-free double-component polyurethane middle layer tree on the layer coating of ester face Then fat AL-1025A/AL-5040B is bonded base fabric and synthetic leather product is made.Its VOC is surveyed using HJ/H400-2007 standards（It waves Send out object total amount）Less than 10ppm.It is 78 N/3cm to survey its peel strength according to QB/T2888-2007 standards, in 70 DEG C, 95%RH It is 68 N/3cm to make peel strength after jungle is tested 7 weeks in climatic chamber, and Wei Shibo is not broken for wear-resisting 100,000 times, -10 DEG C 60,000 times It deflects and does not break, meet the requirement of sofa artificial leather basic physical properties.
The raw material used in the present embodiment：
MDI-50, HDI are the isocyanates of Yantai Wanhua company production；PBA-2000 is the poly- of Xu Chuan Chemical Co., Ltd.s production Ester type oligomer polyol；AMD-1000 is the amine terminated polyether of Yantai people's livelihood Chemical Company production；3,5- dimethyl Pyrazoles is the sealer of Hubei Ju Sheng Science and Technology Ltd.s；245, UV-1 is respectively the antioxidant of Taiwan double bond Chemical Co., Ltd. And ultra-violet absorber；Castor oil, 1,4- butanediols, gamma-butyrolacton, solvent-free mill base are commercial product.
Embodiment 3：
（1）The preparation of high solids content blocked polyurethane resin
By 100g 4,4 '-dicyclohexyl methyl hydride diisocyanates（HMDI）In addition in three-necked flask, it is warming up to 45 DEG C of additions 0.8g antioxidant 1076s stir 20min, sequentially add 170g oligomer polyols（PCDL-2000）, 100g castor oil, 10g mono- Diglycol ethylene is warming up to 70 DEG C and reacts 4 hours after stirring evenly, detection NCO reaches 1.5%.
1,2,4- triazole of 10g sealers is added, 70 DEG C are reacted 4 hours, and detection NCO content reaches 0%.43g solvents are added Dimethyl ether, 0.5g UV absorbers UV-1130 stir cooling discharging packaging after 25min.
（2）The preparation of amine curing agent
Temperature of reaction kettle is controlled at 45 DEG C, 100g amine terminated polyethers are added（AMD-2000）, 0.2g antioxidant 1076s stirring 3g hexamethylene diisocyanates are added dropwise into reaction kettle by 15min（HDI）.45 DEG C of reaction 3h reach to amine value content 35mgKOH/g.Cooling discharging is packed after stirring 45min.
（3）The preparation of polyurethane cover resin
Take step（1）Above-mentioned resin 100g is taken, the solvent-free mill bases of 10g and 57g steps is added（2）The amine curing agent of synthesis stirs Uniformly, polyurethane cover resin is obtained.
Polyurethane cover resin is coated in release paper in 130 DEG C of baking oven 3min up to polyurethane cover coating in poly- ammonia Re-coating Hefei Anli New Material Polyurethane Co., Ltd. produces solvent-free double-component polyurethane middle layer tree on the layer coating of ester face Then fat AL-1025A/AL-5040B is bonded base fabric and synthetic leather product is made.It is resistance to that its is surveyed using GB/T16422.3-1993 standards Xanthochromia grade is 4 grades, its VOC is surveyed using HJ/H400-2007 standards（Volatile matter total amount）Less than 10ppm.According to QB/T2888- It is 82 N/3cm that 2007 standards, which survey its peel strength, makees to remove after jungle is tested 7 weeks in 70 DEG C, the climatic chamber of 95%RH Intensity is 71 N/3cm, and Wei Shibo is not broken for wear-resisting 100,000 times, and -10 DEG C deflect for 60,000 times and not break, meet sofa artificial leather basic physical properties and want It asks.
The raw material used in the present embodiment：
HMDI, HDI are the isocyanates of Yantai Wanhua company production；PCDL-2000 is the poly- carbon of Japanese Asahi Kasei Corporation's production Acid esters type oligomer polyol；AMD-2000 is the amine terminated polyether of Yantai people's livelihood Chemical Company production；1,2,4- tri- Nitrogen azoles is the sealer of Weifang Huambo chemical inc；1076, UV-1130 is respectively Taiwan double bond Chemical Co., Ltd. Antioxidant and ultra-violet absorber；Castor oil, diglycol, dimethyl ether, solvent-free mill base are commercially available production Product.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims Variation is included within the present invention.

Claims (9)

1. a kind of preparation method of use for synthetic leather high solid content polyurethane surface layer resin, it is characterised in that：By following steps system ：
（1）The preparation of high solids content blocked polyurethane resin
Temperature of reaction kettle is controlled at 40-50 DEG C, after isocyanates, antioxidant stirring 10-30min is added, is sequentially added oligomeric Object polyalcohol, castor oil and chain extender, then at 60-80 DEG C reaction until NCO mass contents reach 1.5-5% to get to Isocyanate terminated performed polymer；
Sealer is added into isocyanate terminated performed polymer and carries out capping, the reaction at 60-80 DEG C is until NCO mass contents are 0%；Then solvent is added to adjust polyurethane resin solid content to 90%, after being eventually adding UV absorbers stirring 20-30min Cool down discharging packaging, and enclosed type height is made and consolidates resin；
（2）The preparation of modified amine curing agent
Temperature of reaction kettle is controlled at 40-50 DEG C, after amine terminated polyether, antioxidant stirring 10-20min is added, isocyanic acid is added Ester is in 40-50 DEG C of reaction to get modified amine curing agent until amine value reaches 35-156mgKOH/g；
（3）The preparation of polyurethane cover resin
Take step（1）The enclosed type height of preparation consolidates resin, mill base and step（2）The modified amine curing agent of preparation, stirs evenly, i.e., Obtain polyurethane cover resin.
2. preparation method according to claim 1, it is characterised in that：Step（1）Middle high solids content blocked polyurethane tree The raw material quality number of fat is as follows：
100 parts of isocyanates
140-220 parts of oligomer polyol
50-100 parts of castor oil
4-10 parts of chain extender
10-40 parts of sealer
0.5-1 parts of antioxidant
0.5-1 parts of UV absorbers
38-43 parts of solvent.
3. preparation method according to claim 1, it is characterised in that：Step（2）The raw material matter of middle modified amine curing agent It is as follows to measure number：
100 parts of amine terminated polyether
3-15 parts of isocyanates
0.2-1 parts of antioxidant.
4. preparation method according to claim 1, it is characterised in that：Step（3）Middle enclosed type height is consolidated resin, mill base and is changed Property amine hardener mass ratio be 100：5-10：40-66.
5. preparation method according to claim 1, it is characterised in that：The isocyanates is 4,4 '-diphenyl methanes two The mixing of isocyanates (MDI-100), 2,4 '-methyl diphenylene diisocyanates and 4,4 '-methyl diphenylene diisocyanates Object (MDI-50), isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-dicyclohexyls One or more of methane diisocyanate (HMDI).
6. preparation method according to claim 1, it is characterised in that：Step（1）Described in oligomer polyol be poly- One in ester polyether copoly type oligomer polyol and polyester-type oligomer polyol, polycarbonate type oligomer polyol Kind is several；The polyester polyethers copoly type oligomer polyol is opened by propylene oxide using polyester polyol as initiator Made from cyclopolymerization；
The hydroxyl average functionality of the castor oil is 2.7,156~160 mg KOH/g of hydroxyl value；
The chain extender is ethylene glycol, 1,3- propylene glycol, 1,4- butanediols, 1,5- pentanediols, neopentyl glycol, a contracting diethyl two Alcohol, 3- methyl-1s, one kind in 5- pentanediols；
The sealer is methyl ethyl ketoxime, 3,5- dimethyl pyrazoles, diethyl malonate, antifebrin, 1,2,4- triazoles Middle one kind；
The solvent is gamma-butyrolacton, 6-caprolactone, dimethyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl It is a kind of in acid esters, ethylene acetate.
7. preparation method according to claim 1, it is characterised in that：Step（2）Described in ending amino polyether be a kind of The polypropylene oxide compound blocked by primary amino group, molecular weight 400-2000.
8. preparation method according to claim 1, it is characterised in that：The ultra-violet absorber be UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234；The antioxidant is 245,1010,1035,1076,1098 or 3114.
9. the polyurethane cover resin as prepared by claim 1-8 any one of them preparation methods.
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CN114085356A (en) * 2021-11-19 2022-02-25 合肥安利聚氨酯新材料有限公司 Chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and preparation method thereof
CN116041659A (en) * 2023-03-27 2023-05-02 旭川化学（苏州）有限公司 Solvent-free bio-based polyurethane resin and preparation method and application thereof
CN116041659B (en) * 2023-03-27 2023-06-09 旭川化学（苏州）有限公司 Solvent-free bio-based polyurethane resin and preparation method and application thereof

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